Surface-treated filler for biaxially oriented polyester film

Abstract

The present invention relates to a single- or multi-layer biaxially oriented polyester film, to a process for the production of the single- or multi-layer biaxially oriented polyester film, to the use of a surface-treated filler material product as voiding agent in the single- or multi-layer biaxially oriented polyester film, to an article comprising the single- or multi-layer biaxially oriented polyester film, and to the use of the single- or multi-layer biaxially oriented polyester film in the following fields: packaging products, paper and glass coverings, insulation or thermal insulation materials, solar, marine and aeronautical applications, scientific, electronic and acoustic applications, electric wires, cables, radio frequency identification, flexible circuits, graphic arts, filtration products, cosmetics, household products, imaging and recording media or industrial products.

Description

Technical Field

[0001] This invention relates to single-layer or multi-layer biaxially oriented polyester films, methods for preparing such single-layer or multi-layer biaxially oriented polyester films, the use of surface-treated filler materials as voiding agents in such single-layer or multi-layer biaxially oriented polyester films, articles containing such single-layer or multi-layer biaxially oriented polyester films, and the use of such single-layer or multi-layer biaxially oriented polyester films in the following areas: packaging products, paper and glass coverings, insulating or heat-insulating materials, solar, marine and aerospace applications, scientific, electronic and acoustic applications, wires, cables, radio frequency identification, flexible circuits, graphic arts, filtration products, cosmetics, household products, imaging and recording media, or industrial products. Background Technology

[0002] Biaxially oriented polyester films, such as biaxially oriented polyethylene terephthalate (BOPET) films (also known as oriented polyester films), are used in a wide variety of technical applications, including: packaging products, paper and glass coverings, insulation or thermal insulation materials, solar, marine and aerospace applications, scientific, electronic and acoustic applications, wires and cables, radio frequency identification, flexible circuits, graphic arts, filtration products, cosmetics, household imaging and recording media, and industrial products.

[0003] It is well known that low-density articles can be produced by adding foaming agents (chemical or gaseous) or cavitation agents. For example, microporosity can be achieved throughout the molded article by blending cavitation agents (i.e., a small number of particles or incompatible polymers that form voids upon stretching). This process is called “voiding” and can also be referred to as “cavitation” or “microporosity”. Voids are obtained by introducing about 5-50% by weight of small organic or inorganic particles or “inclusions” (referred to in the art as “voiding” or “cavitation” agents) into a matrix polymer and oriented the polymer by stretching in at least one direction. During stretching, small cavities or microvoids are formed around the cavitation agent. When voids are introduced into the polymer film, the resulting cavitated film not only has a lower density than a non-cavitated film but also becomes opaque and develops a papery surface. Such surfaces also offer the advantage of increased printability; that is, compared to non-porosity films, the surface can accept a significantly greater capacity of ink. In either case, the formation of small voids / pores in the article results in reduced density, increased opacity and insulating or thermal insulation properties, and the elimination of the need for separate UV absorbers due to the inherent UV blocking of light scattering through the voids. Microporous articles offer additional benefits: lower overall film cost and greater separability / reusability, especially when these articles are used in packaging applications such as labels (see, for example, US 7297755 B2).

[0004] In principle, void formation is based on the generation of microcracks at the interface between the polymer and the voiding agent during longitudinal stretching. During subsequent transverse stretching, these fine longitudinal cracks are torn open to form air-filled, closed hollow spaces. Therefore, it seems reasonable that void formation during simultaneous orientation is much more difficult than during sequential orientation. In practice, it is evident that during simultaneous orientation, commonly incompatible particles in polypropylene, such as CaCO3 or PBT, do not generate voids at all, or only generate voids with selective particle shape or size (see, for example, WO03 / 033574). Therefore, alternative techniques for void formation using foaming agents have been developed for this approach.

[0005] Similar problems are known regarding the production of porous films made of polyethylene terephthalate. When using these films, the generation of voids in sequential orientation is technically much more difficult than with polypropylene films. Therefore, the LISIM process (linear motor synchronous stretching technology, available from Brückner Maschinenbau GmbH & Co. KG, Germany) is explicitly not recommended for the production of porous PET films (see, for example, EP 1 068 949).

[0006] It is understood that a porous polyester membrane typically comprises a blend of polyester polymer and a porousing agent (organic material or inorganic filler such as calcium carbonate), and is produced by forming a membrane from the blend by casting or blowing, followed by stretching or drawing the membrane in two orthogonal directions at two different temperatures.

[0007] In this field, various attempts have been made to improve the mechanical and optical properties of polyester films by adding inorganic filler materials, and particularly calcium carbonate-containing filler materials. For example, EP 0 554 654 A1 relates to a polyester resin film that is biaxially oriented and again longitudinally oriented, and has a coating formed on at least one surface of the film, wherein the coating comprises at least 50% by weight of a water-soluble or water-dispersible polyester resin with a glass transition temperature of at least 20°C. To prevent the coating from adhering to the heated roller during restretching, the coating may contain inorganic or organic particles. These particles are described as serving to improve anti-adhesion or anti-slip properties.

[0008] Similarly, DE 43 13 510 A1 relates to an oriented monolayer or multilayer film with a total thickness ≤ 4 μm and a roughness Ra < 30 nm on at least one film surface, wherein the surface airflow resistance on at least one film surface is t ≤ ad. b[s], where a = 0-10000 [s / μm], b = 3.0-0, and d (total film thickness) ≤ 4 μm. The film may contain first (I) and second (II) particles. The first particles are monodisperse and have an aspect ratio of 1.0-1.2.

[0009] EP 1 052 269 A1 relates to a biaxially oriented film with a thickness of 1-500 μm, having a crystallizable thermoplastic material as the main component, and also containing a UV stabilizer and a white pigment.

[0010] EP 1 612 237 A1 relates to a thermoplastic biaxially oriented film containing at least 500 ppm of pigment, with at least 20% by weight of the same type of recycled material added. The film may be single-layered or multi-layered, and is preferably 10-300 μm thick.

[0011] K. Nevalainen et al.'s paper, "Voiding behaviour and microstructure of a filled polyester film" (Materials Chemistry and Physics 92(2005)540-547), discusses the voiding behavior of a polyester film filled with polyethylene terephthalate. The filler used was barium sulfate, with an average particle size of 1-2 μm.

[0012] K. Nevalainen et al.'s "The microstructure of polyethylene terephthalate matrix near to a void under uniaxial draw" (Materials Chemistry and Physics 101 (2007) 103-111) describes the characterization of the matrix adjacent to the void. In particular, it relates to uniaxially drawn PET films and the voids formed around spherical 5 μm glass beads as fillers.

[0013] A. Sudár et al.'s "The mechanism and kinetics of void formation and growth in particulate filled PE composites" (Polymer Letters, Vol. 1, No. 11 (2007), 763-772) describes that the formation of voids in PE depends particularly on the properties of the matrix. Specifically, in a soft matrix, the number of voids is smaller and their size is larger than that of polymers with a larger solid modulus at the same deformation and filler content.

[0014] However, the disadvantage of the membrane is that it is almost impossible to produce a suitable pore size with low density and high opacity microporous membrane during the stretching of the biaxially oriented polyester membrane without membrane rupture during the stretching process.

[0015] Therefore, providing biaxially oriented polyester films with a microporous structure of low density and high opacity remains of interest to those skilled in the art. Furthermore, it is desirable to maintain high levels of mechanical and optical properties and to provide environmentally friendly films, which are derived from regenerated raw materials and can be disposed of in an environmentally friendly manner. Summary of the Invention

[0016] Therefore, the object of the present invention is to provide a biaxially oriented polyester film having a microporous structure. It is also desirable to provide a biaxially oriented polyester film or corresponding layer having a microporous structure at low densities, particularly densities lower than those typically achieved by biaxially oriented films or corresponding layers using barium sulfate or titanium dioxide as porosifectants. Thus, it is desirable to provide a film with a density lower than 1.4 g / cm³. 3 Biaxially oriented polyester films or layers (especially for PET) are desired. It is also desirable to provide biaxially oriented polyester films or layers with an opaque appearance. It is also desirable to provide biaxially oriented polyester films or layers that can be prepared without film / layer breakage. It is also desirable to provide biaxially oriented polyester films or layers with good mechanical and optical properties. It is also desirable to provide environmentally friendly biaxially oriented polyester films or layers that are produced from grown-back raw materials and can be disposed of in an environmentally friendly manner.

[0017] Another object of the present invention is to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers. It is also desirable to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers that exhibits good dispersibility and compounding properties in polyester film / layer applications. It is also desirable to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers that imparts a low density to the film or layer. It is also desirable to provide an inorganic pore-forming agent that does not cause film / layer rupture during the preparation of biaxially oriented polyester films or layers. It is also desirable to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers that imparts good mechanical properties such as tensile strength, elongation at break, or modulus of elasticity. It is also desirable to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers that imparts an opaque appearance to the film or layer. It is also desirable to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers that allows for processing into masterbatches or blends using continuous methods. Another object of the present invention is to provide an inorganic pore-forming agent for biaxially oriented polyester films or layers that allows for processing into masterbatches with low filtration pressure values.

[0018] The foregoing and other objectives are addressed by the subject matter defined herein in the independent claims.

[0019] According to one aspect of the invention, a single-layer or multi-layer biaxially oriented polyester film is provided. The single-layer or multi-layer biaxially oriented polyester film comprises at least one layer containing at least one polyester in an amount of 70-99.9% by weight based on the total weight of the layer and 0.1-30% by weight of a surface-treated filler material product, wherein the surface-treated filler material product contains…

[0020] A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and

[0021] B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising

[0022] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0023] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0024] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0025] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents. 30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0026] v. at least one polydialkylsiloxane, and / or

[0027] vi. To mix the materials from i. to v.

[0028] The surface-treated filler material product comprises a treated layer comprising 0.1-2.3% by weight of the total dry weight of the at least one milled calcium carbonate filler material.

[0029] According to another aspect, a method for producing a single-layer or multi-layer biaxially oriented polyester film as defined herein is provided, comprising the following steps:

[0030] a) Provides a composition comprising at least one polyester and a surface-treated filler material product, and

[0031] b) A film is formed from the composition of step a), and

[0032] c) Stretching the membrane obtained in step b) in the longitudinal (MD) and transverse (TD) directions in any order, wherein the stretching in the longitudinal (MD) and transverse (TD) directions is performed sequentially or simultaneously.

[0033] The surface-treated filler material product includes

[0034] A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and

[0035] B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising

[0036] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0037] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0038] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0039] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents. 30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0040] v. at least one polydialkylsiloxane, and / or

[0041] vi. To mix the materials from i. to v.

[0042] The surface-treated filler material product comprises a treated layer comprising 0.1-2.3% by weight of the total dry weight of the at least one milled calcium carbonate filler material.

[0043] According to another aspect of the invention, the use of a surface-treated filler material product as a porosifier in a single-layer or multi-layer biaxially oriented polyester film as defined herein is provided, wherein the surface-treated filler material product comprises

[0044] A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and

[0045] B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising

[0046] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0047] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0048] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0049] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents. 30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0050] v. at least one polydialkylsiloxane, and / or

[0051] vi. To mix the materials from i. to v.

[0052] The surface-treated filler material product comprises a treated layer comprising 0.1-2.3% by weight of the total dry weight of the at least one milled calcium carbonate filler material.

[0053] According to another aspect of the invention, articles comprising single-layer or multi-layer biaxially oriented polyester films as defined herein are provided, wherein the articles are selected from packaging products, preferably flexible packaging products, food contact applications, paper and glass coverings, insulating or heat-insulating materials, solar energy, preferably photovoltaic front and back sheets, marine and aerospace applications, scientific, electronic and acoustic applications, preferably displays, wires, cables, radio frequency identification, flexible circuits, graphic art, preferably labels, paper replacements and holograms, filtration products, cosmetics, household products, imaging and recording media, preferably photographic paper, X-ray films and thermal transfer imaging and industrial products, preferably capacitors, release sheets, fiberglass boards, laminates, thermally stamped foils and insulating or heat-insulating finishes.

[0054] According to another aspect of the invention, single-layer or multi-layer biaxially oriented polyester films as defined herein are provided for use in: packaging products, preferably flexible packaging products, food contact applications, paper and glass coverings, insulating or heat-insulating materials, solar energy, preferably photovoltaic front and back sheets, marine and aerospace applications, scientific, electronic and acoustic applications, preferably displays, wires, cables, radio frequency identification, flexible circuits, graphic art, preferably labels, paper alternatives and holograms, filtration products, cosmetics, household products, imaging and recording media, preferably photographic paper, X-ray film and thermal transfer imaging or industrial products, preferably capacitors, release sheets, fiberglass boards, laminates, thermally stamped foils and insulating or heat-insulating finishes.

[0055] Advantageous embodiments of the invention are defined herein and also in the corresponding dependent claims.

[0056] According to one embodiment of the invention, the layer of the film comprising at least one polyester and a surface-treated filler material product comprises an amount of the surface-treated filler material product of 1-28% by weight, preferably 2-26% by weight, more preferably 3-25% by weight, even more preferably 4.5-23% by weight, and most preferably 4-20% by weight, based on the total weight of the layer.

[0057] According to another embodiment, the at least one polyester is selected from polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), bio-based polyesters, PET recycled materials, and mixtures thereof.

[0058] According to another embodiment, the layer of the membrane comprising at least one polyester and a surface-treated filler material product comprises at least one polyester in an amount of 80-99.9% by weight, more preferably 80-96% by weight, based on the total weight of the layer.

[0059] According to one embodiment, the at least one milled calcium carbonate-containing filler material is a wet-milled or dry-milled calcium carbonate-containing filler material. Wet-milled calcium carbonate-containing filler materials relating to the foregoing aspects of the invention are particularly considered or preferred.

[0060] According to another embodiment, the at least one milled calcium carbonate-containing filler material is naturally milled calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface-treated calcium carbonate, or a mixture thereof, preferably naturally milled calcium carbonate.

[0061] According to another embodiment, the at least one milled calcium carbonate-containing filler material has a) a) a median weight particle size d 50 The particle size is 0.5μm-2μm, preferably 0.5μm-1.8μm, and most preferably 0.6μm-1.8μm, and / or b) the top-cut particle size d 98 ≤15μm, preferably ≤10μm, more preferably ≤7.5μm, even more preferably ≤7μm and most preferably ≤6.5μm, and / or c) such that at least 15% by weight, preferably at least 20% by weight, even more preferably at least 25% by weight and most preferably 30-40% by weight of all particles have a particle size of <0.5μm, and / or d) a specific surface area (BET) of 0.5-150m². 2 / g, preferably 0.5-50m 2 / g, more preferably 0.5-35m2 / g and the optimal value is 0.5-15m. 2 / g, as measured using the nitrogen and BET method according to ISO 9277.

[0062] According to one embodiment, the treated layer on the surface of the at least one milled calcium carbonate-containing filler material comprises at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product. Preferably, the at least one saturated aliphatic linear or branched carboxylic acid is selected from the group consisting of carboxylic acids: 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, icosanoic acid, benzanoic acid, tridecanoic acid, tetradecanoic acid, and mixtures thereof; and / or at least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is formed by using a mixture of substances selected from those having a total carbon atom count of at least C2 to C6 in the substituents. 30 It consists of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups.

[0063] According to another embodiment, the surface-treated filler material product comprises the treated layer in an amount of 0.2-2.0% by weight, preferably 0.4-1.9% by weight, and most preferably 0.5-1.8% by weight, based on the total dry weight of the at least one milled calcium carbonate filler material.

[0064] According to another embodiment, the layer of the membrane comprising at least one polyester and a surface-treated filler material comprises a thermoplastic polymer preferably crosslinked with a crosslinking agent, selected from polyolefins, preferably polypropylene, polyethylene, polybutene and mixtures thereof, cyclic olefin copolymers (COC), polyketones, polysulfones, fluoropolymers, polyacetals, ionomers, acrylic resins, polystyrene resins, polyurethanes, polyamides, polycarbonates, polyacrylonitrile, and copolymer resins and mixtures thereof.

[0065] According to one embodiment, the layer of the film comprising at least one polyester and a surface-treated filler material product comprises 0.1-29.9% by weight, preferably 1-28% by weight, more preferably 2-26% by weight, even more preferably 3-25% by weight, even more preferably 4.5-23% by weight, and most preferably 4-20% by weight, based on the total weight of the layer.

[0066] According to another embodiment, the membrane, preferably comprising at least one layer of the surface-treated filler material product, has a content of a) 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³.3 And the optimal value is 0.85-1.28 g / cm³. 3 The density, and / or b) ≥50%, preferably ≥55%, and most preferably ≥60% opacity.

[0067] According to another embodiment, the layer of the membrane comprising at least one polyester and a surface-treated filler material product further comprises an inorganic filler material different from the surface-treated filler material product, and preferably selected from alumina, silica, titanium dioxide, alkali metal salts such as barium carbonate, calcium sulfate, barium sulfate and mixtures thereof, preferably in an amount of 1-10% by weight based on the total weight of the layer.

[0068] According to one embodiment, the film, preferably comprising at least one polyester and a surface-treated filler material product, includes additives selected from light stabilizers, preferably 2-hydroxybenzophenone, 2-hydroxybenzotriazole, organonickel compounds, salicylates, cinnamic acid ester derivatives, resorcinol monobenzoate, oxaloyl aniline, hydroxybenzoate, sterically hindered amines and triazines, more preferably 2-hydroxybenzotriazole and triazines, most preferably hydroxyphenyl-triazine, optical brighteners, blue dyes, preferably blue dyes soluble in polyesters, antiblocking agents, white pigments, and mixtures thereof.

[0069] According to one embodiment, the composition provided in step a) of the method of the present invention is a masterbatch obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture and continuously granulating the obtained mixture.

[0070] According to another embodiment of the method, the masterbatch has a filtration pressure of 0.01-0.5 bar / g, preferably 0.01-0.15 bar / g, and most preferably 0.01-0.1 bar / g.

[0071] According to another embodiment of the method, the masterbatch comprises an amount of the surface-treated filler material product of >30 to 85% by weight, preferably 35-80% by weight and more preferably 40-70% by weight, based on the total weight of the masterbatch.

[0072] According to one embodiment of the method, if the composition provided in step a) is a masterbatch, then steps a) and b) are performed simultaneously, preferably by directly adding the at least one polyester and the surface-treated filler material product into an extruder to perform step b).

[0073] According to another embodiment of the method, the composition comprising at least one polyester and a surface-treated filler material product in step a) is obtained, if it is a masterbatch, by adding the surface-treated filler material product, preferably before or after, the polycondensation process of the at least one polyester.

[0074] According to yet another embodiment of the method, the composition provided in step a) of the method of the present invention is a compound obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture and continuously granulating the obtained mixture.

[0075] According to one embodiment of the method, the mixture has a filtration pressure of 0.01-0.5 bar / g, preferably 0.01-0.15 bar / g, and most preferably 0.01-0.1 bar / g.

[0076] According to another embodiment of the method, if the composition provided in step a) is a compound, then steps a) and b) are performed simultaneously, preferably by directly adding the at least one polyester and the surface-treated filler material product into the extruder to perform step b).

[0077] According to another embodiment of the method, the composition comprising at least one polyester and a surface-treated filler material product in step a), if it is a compound, is obtained by adding the surface-treated filler material product, preferably before or after, the polycondensation process of the at least one polyester.

[0078] The at least one polyester and the surface-treated filler material product, along with other optional additives if present, can be mixed using a suitable mixer such as a Henschel mixer, super mixer, drum mixer, or similar mixer. According to another embodiment, steps a) and b) are performed simultaneously, preferably with the at least one polyester and the surface-treated filler material product added directly to the extruder for step b). According to yet another embodiment, the composition comprising at least one polyester and the surface-treated filler material product in step a) is obtained by adding the surface-treated filler material product, preferably before or after, the polycondensation process of the at least one polyester.

[0079] It should be understood that, for the purposes of this invention, the following terms have the following meanings:

[0080] The term "biaxially oriented" polyester film indicates that the film is biaxially oriented, meaning that the film has undergone a stretching process in both the longitudinal (MD) and transverse (TD) directions to obtain a biaxially oriented polymer.

[0081] In the context of this invention, "film" refers to a sheet or layer of material having a median thickness less than its length and width. For example, the term "film" may refer to a sheet or layer of material having a median thickness of 0.5-500 μm, preferably 4-400 μm, more preferably 5-300 μm, and most preferably 6-250 μm, such as 8-150 μm. The film may be in the form of a single layer or multiple layers.

[0082] A "single-layer" membrane refers to a membrane consisting of only one layer. A "multilayer" membrane refers to a membrane consisting of two or more adjacent layers, such as two to ten layers, preferably three layers. If the multilayer membrane is a three-layer membrane, it may have a membrane structure of ABA or ABC. In such a multilayer membrane, the core layer is preferably porous.

[0083] The term "milled calcium carbonate-containing filler" as used in the spirit of this invention refers to a calcium carbonate-containing filler that has been manufactured by a method including at least one milling step. "Milled calcium carbonate-containing filler" includes fillers that can be "wet-milled" or "dry-milled," wherein "wet-milled calcium carbonate-containing filler" as used in the context of this invention refers to a milled calcium carbonate-containing filler that has been manufactured by a method including at least one milling step in an aqueous suspension with a solid content of 20-80% by weight, and "dry-milled calcium carbonate-containing filler" refers to a milled calcium carbonate-containing filler that has been manufactured by a method including at least one milling step in an aqueous suspension with a solid content of greater than 80% by weight to at most 100% by weight.

[0084] In the context of this invention, the term "microporous membrane" or "microporous layer" refers to a polyester membrane or corresponding layer that allows gas and moisture to pass through due to the presence of micropores. The presence of "micropores" in a biaxially oriented polyester membrane or layer can be measured by its water vapor transmission rate (WVTR), expressed in g / (m²). 2 • (day) indicates. For example, if the polymer film or layer has a content below 100 g / (m²), it indicates that the polymer film or layer has a content below 100 g / (m²). 2 A WVTR of · days can be considered "microporous". WVTR can be determined using a Lyssy L80-5000 measuring device according to ASTM E398.

[0085] In the context of this invention, the term "low density" refers to a density of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 A single-layer or multi-layer biaxially oriented polyester film or corresponding layer of a certain density.

[0086] For the purposes of this invention, the term "calcium carbonate-containing filler material" refers to a material containing at least 80% by weight of calcium carbonate based on the total dry weight of the calcium carbonate-containing filler material.

[0087] In the context of this invention, "naturally ground calcium carbonate" (GCC) refers to calcium carbonate obtained from natural sources (e.g., limestone, marble, dolomite, or chalk) and processed by wet treatments such as grinding, screening, and / or grading (e.g., by means of a cyclone or classifier).

[0088] In the context of this invention, "modified calcium carbonate" (MCC) can be characterized as naturally ground or precipitated calcium carbonate with internal structural modification or surface reaction products (i.e., "surface-reacted calcium carbonate").

[0089] “Surface-reacted calcium carbonate” refers to a material comprising calcium carbonate and an insoluble (preferably at least partially crystalline) calcium salt of an acid anion on its surface. Preferably, the 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 largely derived from the starting calcium carbonate material. MCC is described in, for example, the following documents: US 2012 / 0031576 A1, WO 2009 / 074492 A1, EP 2 264109 A1, EP 2 070 991 A1, or EP 2 264 108 A1.

[0090] In the context of this invention, the term "surface-treated filler material product" refers to a calcium carbonate-containing filler material that has been contacted with a surface-treated agent to obtain a coating layer on at least a portion of the surface of the calcium carbonate-containing filler material.

[0091] The term "dry" for calcium carbonate packing materials is understood to refer to packing materials containing less than 0.3% water by weight relative to the weight of the packing material. The water % (equal to "residual total moisture content") is determined according to the Coulomb Karl Fessel method, wherein the packing material is heated to 220°C and released as steam, and the water content is determined in a Coulomb Karl Fessel unit using a nitrogen flow (100 ml / min).

[0092] The term "polymer composition" refers to a composite material containing at least one additive (e.g., at least one filler) and at least one polyester material, which can be used in the production of polymer products.

[0093] The term "polymer masterbatch" (or "masterbatch") refers to a composition having a relatively high filler content (meaning at least or equal to 30% by weight (based on the total weight of the composition)). "Polymer masterbatch" can be added to unfilled or low-filled polyester during processing to achieve a higher filler content. Nevertheless, "polymer compositions" (or "compositions") as previously defined (and often referred to as "polymer blends" (or "blendings")) having a relatively low filler content (meaning less than 30% by weight (based on the total weight of the composition)) can also be used directly in the production of polymer products. Therefore, the term "polymer composition" (or "composition") as used herein includes both "polymer masterbatch" and "polymer blend."

[0094] The term "specific surface area" (in m²) for mineral fillers, as used in this invention, refers to the specific surface area of ​​the filler material. 2 The total surface area of ​​the mineral packing (in m²) was determined using the BET method (using nitrogen as the adsorbate gas), a method well-known to those skilled in the art (ISO 9277:2010). 2 The specific surface area is obtained by multiplying the mass of the mineral filler before processing (in grams) by the specific surface area.

[0095] Throughout this document, the "particle size" of calcium carbonate-containing fillers is described by the distribution of their particle size. 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 of d. This means d 20 The value refers to a particle size where 20% of the weight of all particles is less than this particle size, and d 98 The value refers to a particle size in which 98% of the weight of all particles is smaller than that particle size. d 98 The value is also called "top tangent". d 50 The value is therefore the weight-median particle size, i.e., the particle size for which 50% of the total 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 To determine the median particle size d... 50 Value or top-cut particle size d 98 The values ​​can be determined using a Sedigraph 5100 or 5120 apparatus from Micromeritics, USA. 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. Measurements are performed in an aqueous solution of 0.1% by weight Na₄P₂O₇. The sample is dispersed using a high-speed stirrer and ultrasonication.

[0096] For the purposes of this invention, the “solid content” of a liquid composition is a measure of the amount of material remaining after all solvents or water have been evaporated.

[0097] The term "suspension" or "slurry" as used in this invention includes insoluble solids and water, as well as optional additional additives, and typically contains a large amount of solids and is therefore more viscous and may have a higher density than the liquid in which it is formed.

[0098] In the context of this invention, "treatment layer" refers to a layer of surface treatment agent on the surface of the at least one milled calcium carbonate filler material, preferably a single layer. This "treatment layer" comprises, as the surface treatment agent, i. a mixture of one or more monophosphate esters and their salt reaction products and / or one or more phosphate diesters and their salt reaction products, and / or ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or iii. at least one aliphatic aldehyde and / or its salt reaction product, and / or iv. at least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is formed using a layer of surface treatment agent selected from those with a total carbon atom count of at least C2 to C3 in the substituents. 30 The composition of linear, branched, aliphatic and cyclic groups of monosubstituted succinic anhydrides, and / or v. at least one polydialkylsiloxane, and / or vi. a mixture of materials according to i. to v.

[0099] When the term "comprising" is used in this specification and claims, it does not exclude other elements not specifically mentioned that are of primary or secondary functional importance. For the purposes of this invention, the term "consisting of" is considered a preferred embodiment of the term "comprising of". If a group is defined below as including at least a certain number of embodiments, this is also understood to disclose a group that is preferably constituted only by these embodiments.

[0100] Wherever the terms “including” or “having” are used, they are considered equivalent to “comprising” as defined above.

[0101] 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 in some cases.

[0102] 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 through a sequence of steps following the term “obtainable,” although the terms “obtainable” or “defined” always include such limiting understanding as a preferred embodiment.

[0103] The single-layer or multi-layer biaxially oriented polyester film of the present invention comprises at least one layer comprising at least one polyester in an amount of 70-99.9% by weight based on the total weight of the film and 0.1-30% by weight of a surface-treated filler material product. The surface-treated filler material product comprises (A) at least one milled calcium carbonate-containing filler material having a median particle size d by weight. 50 The thickness is 0.5 μm to 2.5 μm, and (B) a treatment layer on the surface of the at least one milled calcium carbonate-containing filler material, comprising i. a phosphate blend of one or more monophosphate esters and their salt reaction products and / or one or more phosphate diesters and their salt reaction products, and / or ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or iii. at least one aliphatic aldehyde and / or its salt reaction product, and / or iv. at least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is formed by utilizing a carbon atom selected from the group having a total carbon atom count of at least C2 to C4. 30 The product comprises monosubstituted succinic anhydrides of linear, branched, aliphatic, and cyclic groups, and / or v. at least one polydialkylsiloxane, and / or vi. a mixture of materials according to i. to v. The surface-treated filler material product contains the treated layer in an amount of 0.1-2.3% by weight based on the total dry weight of the at least one milled calcium carbonate-containing filler material.

[0104] The details and preferred embodiments of the product of the present invention will be set forth in more detail below. It should be understood that these technical details and embodiments also apply to the method of the present invention for producing the single-layer or multi-layer biaxially oriented polyester film, and to the use of the single-layer or multi-layer biaxially oriented polyester film and the surface-treated filler material product of the present invention.

[0105] Polyester

[0106] The single-layer or multi-layer biaxially oriented polyester film of the present invention comprises at least one layer comprising at least one polyester. It should be understood that the at least one polyester is not limited to a specific material, as long as the polymer is suitable for preparing the single-layer or multi-layer biaxially oriented polyester film. Those skilled in the art will select the polyester according to the desired application of the single-layer or multi-layer biaxially oriented polyester film.

[0107] One requirement of this invention is that the at least one polyester and the surface-treated filler material product exist in the same layer. Therefore, the surface-treated filler material product is dispersed within the at least one polyester.

[0108] Therefore, a multilayer biaxially oriented polyester film comprises at least one layer comprising the at least one polyester and the surface-treated filler material product. If the multilayer biaxially oriented polyester film comprises two or more layers comprising polyester and the surface-treated filler material product, it should be understood that the two or more layers may be the same or different, for example, they may differ in the amount of the at least one polyester and the surface-treated filler material product.

[0109] It should be understood that the statement "at least one" polyester means that the polyester comprises one or more types of polyester, preferably consisting of one or more types of polyester.

[0110] Therefore, it should be noted that the at least one polyester can be a single type of polyester. Alternatively, the at least one polyester can be a mixture of two or more types of polyester. For example, the at least one polyester can be a mixture of two or three types of polyester (such as two types of polyester).

[0111] In one embodiment of the invention, the at least one polyester comprises a type of polyester, preferably composed of a type of polyester.

[0112] Generally, the term "polyester" refers to a polymer obtained by at least partial condensation polymerization of a diol and a dicarboxylic acid. As the dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, or sebacic acid can be used. As the diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, or cyclohexanediol can be used.

[0113] Additionally or alternatively, the at least one polyester may be a partially or fully bio-based polyester, i.e., wherein the monomers are derived from a renewable biomass source. Examples of monomers include those that can be produced using bio-derived compounds. For example, said monomers include, but are not limited to, ethylene glycol (EG), furanyl dicarboxylic acid (FDCA), polyethylene furanyl dicarboxylate (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 / 100265 A1, which is therefore incorporated herein by reference.

[0114] Additionally or alternatively, the at least one polyester is a PET recycled material, such as PET bottle waste from a PET recycling stream.

[0115] Therefore, the polyesters of the present invention are preferably polyglycolic acid, polylactic acid, polycaprolactone, polyhydroxybutyrate (PHB), polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, poly(1,4-cyclohexanedimethyl terephthalate), polyethylene naphthalate-2,6-dicarboxylate, polyethylene naphthalate-1,5-dicarboxylate, polyethylene naphthalate / dibenzoate, or other combinations derived from the above monomers, or mixtures of these polyesters. For example, the polyesters that can be used are selected from polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanate (PEF), bio-based polyesters, recycled PET materials, and mixtures thereof.

[0116] Preferred materials include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene furanate (PEF), and mixtures thereof. Most preferably, the at least one polyester is polyethylene terephthalate (PET).

[0117] These polyesters can be homopolymers or copolymers. As components to be copolymerized, glycol components such as diethylene glycol, neopentyl glycol, or polyalkylene glycols and dicarboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, or 2,6-naphthalenedicarboxylic acid can be used.

[0118] In a preferred embodiment, the polyester further comprises at least 0.5% by weight, preferably at least 1% by weight and more preferably at least 2% by weight of isophthalic acid, a monomer derived by condensation with a diol, based on the total weight of the polyester.

[0119] The polyester of the present invention preferably has an intrinsic viscosity of 0.5-1.4 dl / g, more preferably 0.65-1.0 dl / g, and most preferably 0.65-0.85 dl / g, as measured according to ISO 1628-1 (in naphthalene at 135°C). For example, the polyester of the present invention has an intrinsic viscosity of 0.78-0.82 dl / g, as measured according to ISO 1628-1 (in naphthalene at 135°C).

[0120] In one embodiment, the polyester has a crystallization temperature (Tc) measured by differential scanning calorimetry (DSC). cThe temperature should be at least 120°C, preferably at least 140°C, for example, 140-180°C.

[0121] Additionally or alternatively, the polyethylene terephthalate (PET) preferably contains ≤3% by weight, more preferably ≤1.5% by weight and most preferably ≤1.2% by weight of diethylene glycol based on the total weight of the polyethylene terephthalate (PET).

[0122] It should be understood that the at least one polyester is preferably an amorphous or crystalline polyester, such as crystalline polyethylene terephthalate (PET).

[0123] The single-layer or multi-layer biaxially oriented polyester film comprises at least one polyester and a surface-treated filler material. The layer of the product contains at least one polyester in an amount of 70-99.9% by weight, based on the total weight of the layer.

[0124] According to one embodiment, the single-layer or multi-layer biaxially oriented polyester film comprises at least one polyester and a surface-treated filler material product, wherein the layer comprises at least one polyester in an amount of 80-99.9% by weight, more preferably 80-96% by weight, based on the total weight of the layer.

[0125] In cases where at least one layer of the single-layer or multi-layer biaxially oriented polyester film further comprises a thermoplastic polymer, the layer of the film comprising at least one polyester and a surface-treated filler material product comprises at least one polyester in an amount of 70-99.8% by weight, preferably 80-99.8% by weight, more preferably 80-96% by weight, based on the total weight of the layer.

[0126] Surface-treated filler materials

[0127] The at least one layer of the single-layer or multi-layer biaxially oriented polyester film of the present invention further comprises a surface-treated filler material product, wherein the surface-treated filler material product comprises at least one milled calcium carbonate-containing filler material. The surface-treated filler material product has several essential characteristics, defined in claim 1 and described in more detail below.

[0128] The at least one milled calcium carbonate-containing filler material is a wet-milled or dry-milled calcium carbonate-containing filler material. Preferably, the at least one milled calcium carbonate-containing filler material is a wet-milled calcium carbonate-containing filler material.

[0129] Typically, this grinding step can be carried out, for example, with any conventional grinding apparatus under conditions where the refinement is mainly produced 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 crusher, hammer mill, pulverizer, shredder, deblocker, knife cutter, or other such equipment known to those skilled in the art.

[0130] When the at least one milled calcium carbonate-containing filler material is a wet-milled calcium carbonate-containing filler material, the wet milling step can be carried out under conditions that allow self-milling to occur and / or by horizontal ball milling and / or other such methods known to those skilled in the art. The resulting processed milled calcium carbonate-containing filler material can be washed and dehydrated by well-known methods, such as by flocculation, filtration, or forced evaporation (before drying). The subsequent drying step can be carried out in a single step (such as spray drying) or in at least two steps, for example, by subjecting the wet-milled calcium carbonate-containing filler material to a first heating step to reduce the relevant moisture content to a level not exceeding about 0.5% by weight based on the total dry weight of the at least one wet-milled calcium carbonate-containing filler material. The residual total moisture content of the packing material can be measured by Karl Fischer coulometric titration, in which moisture is desorbed in an oven at 195°C and dried N2 is continuously passed through a KF coulometric meter (Mettler Toledo coulometric KF Titrator C30, combined with a Mettler oven DO 0337) at 100 ml / min for 10 min. The residual total moisture content can be determined using a calibration curve, taking into account the 10-min blind zone without sample flow. The residual total moisture content can be further reduced by applying a second heating step to the at least one wet-milled calcium carbonate-containing packing material. When the drying is carried out by more than one drying step, the first step can be carried out by heating in a hot air stream, while the second and additional drying steps are preferably carried out by indirect heating, wherein the atmosphere in the corresponding container contains a surface treatment agent. It is also common for the at least one wet-milled calcium carbonate-containing packing material to undergo a mineral processing step (such as flotation, bleaching, or magnetic separation) to remove impurities.

[0131] In another preferred embodiment, the at least one milled calcium carbonate-containing filler material is a material that has been milled in a horizontal ball mill and subsequently dried using a known spray drying method.

[0132] In the context of this invention, the at least one milled calcium carbonate-containing filler material refers to a filler material selected from the following: naturally milled calcium carbonate (GCC), precipitated calcium carbonate (PCC), modified calcium carbonate (MCC), surface-treated calcium carbonate, or mixtures thereof.

[0133] According to a preferred embodiment, the at least one milled calcium carbonate-containing filler material is naturally milled calcium carbonate (GCC), more preferably, the milled calcium carbonate-containing filler is wet-milled natural calcium carbonate.

[0134] GCC is understood to refer to naturally occurring calcium carbonate, mined from sedimentary rocks such as limestone or chalk, or metamorphic marble, and processed by wet treatments such as grinding, screening, and / or grading (e.g., by means of a cyclone or classifier). In one embodiment of the invention, the GCC is selected from marble, chalk, dolomite, limestone, and mixtures thereof.

[0135] In the context of this invention, "precipitated calcium carbonate" (PCC) refers to a synthetic material, typically obtained by precipitation in an aqueous environment following the reaction of carbon dioxide with lime, or by precipitation of calcium and carbonate ion sources in water, or by precipitation of 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 with 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, chisel-shaped 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.

[0136] Modified calcium carbonate can be characterized as GCC or PCC with internal structural modifications or surface-reacted GCC or PCC. Surface-reacted calcium carbonate can be prepared by providing GCC or PCC in the form of an aqueous suspension and adding an acid to the suspension. Suitable acids are, for example, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, or mixtures thereof. In a next step, the calcium carbonate is treated with gaseous carbon dioxide. If a strong acid such as sulfuric acid or hydrochloric acid is used in the acid treatment step, carbon dioxide will be automatically formed in situ. Alternatively or additionally, the carbon dioxide can be supplied from an external source. Surface-reacted calcium carbonate is described, for example, in the following documents: US 2012 / 0031576 A1, WO 2009 / 074492 A1, EP 2 264 109 A1, EP 2070 991 A1, or EP 2 264 108 A1.

[0137] In a preferred embodiment, the at least one milled calcium carbonate filler material is marble, more preferably wet-milled marble.

[0138] It should be understood that the amount of ground calcium carbonate in the at least one calcium carbonate-containing filler material is at least 80% by weight, for example at least 95% by weight, preferably 97-100% by weight, and more preferably 98.5-99.95% by weight, based on the total dry weight of the at least one ground calcium carbonate-containing filler material.

[0139] The at least one milled calcium carbonate-containing filler material is preferably in the form of a granular material and may have a particle size distribution conventionally used for materials involved in the type of product to be produced. Typically, a particular requirement of the present invention is that the at least one milled calcium carbonate-containing filler material has a median weight particle size d. 50 The value is 0.5-2.5 μm. For example, the median weight particle size d of this at least one milled calcium carbonate-containing filler material is... 50 The value is 0.5μm-2μm, preferably 0.5μm-1.8μm, and most preferably 0.6μm-1.8μm, for example about 0.8μm or about 1.7μm.

[0140] Preferably, the at least one milled calcium carbonate-containing filler material has a top shear value (d) ≤15μm. 98 For example, the at least one milled calcium carbonate-containing filler material has a top shear value (d) of ≤10 μm, preferably ≤7.5 μm, more preferably ≤7 μm, and most preferably ≤6.5 μm. 98 ).

[0141] It should be understood that the median particle size d of the at least one milled calcium carbonate-containing filler material is... 50 Value and top tangent value (d) 98 ( ) Meets a specific ratio. For example, the at least one milled calcium carbonate-containing filler material has a median particle size d of 0.1 to 0.4, preferably 0.1 to 0.3, and most preferably 0.2 to 0.3 by weight. 50 Value and top tangent value (d) 98 The proportion of ) [d 50 / d 98 ].

[0142] Additionally or alternatively, the at least one milled calcium carbonate filler material has a fineness such that at least 15% by weight, preferably at least 20% by weight, even more preferably at least 25% by weight, and most preferably 30-40% by weight of all particles have a particle size of <0.5 μm.

[0143] In one embodiment, the at least one milled calcium carbonate-containing filler material has

[0144] i) A median weight particle size d of 0.5-2.5 μm, preferably 0.5-2 μm, more preferably 0.5-1.8 μm, and most preferably 0.6-1.8 μm. 50 ;as well as

[0145] ii) Top-cut particle size ≤15μm, preferably ≤10μm, more preferably ≤7.5μm, even more preferably ≤7μm and most preferably ≤6.5μm (d 98 ),as well as

[0146] iii) such that at least 15% by weight, preferably at least 20% by weight, even more preferably at least 25% by weight, and most preferably 30-40% by weight of all particles have a particle size of <0.5 μm.

[0147] For example, the at least one milled calcium carbonate-containing filler material has

[0148] i) Median particle size d (0.6-1.8 μm) 50 ;as well as

[0149] ii) Top shear value ≤ 6.5 μm (d 98 ),as well as

[0150] iii) to make 30-40% of the weight of all particles have a particle size of <0.5μm.

[0151] It should also be understood that the at least one milled calcium carbonate-containing filler material has a particle size of 0.5 to 150 μm as measured using the nitrogen and BET method according to ISO 9277. 2 BET specific surface area per g. For example, the at least one milled calcium carbonate-containing filler material has a specific surface area of ​​0.5 to 50 m² / g as measured by the nitrogen and BET method according to ISO 9277. 2 / g, more preferably 0.5 to 35m 2 / g and the optimal value is 0.5 to 15m 2 / g specific surface area (BET).

[0152] In one embodiment of the invention, the at least one milled calcium carbonate-containing filler material preferably has a median particle size d of 0.5-2.5 μm, more preferably 0.5-2 μm, more preferably 0.5-1.8 μm, and most preferably 0.6-1.8 μm, for example about 0.8 μm or about 1.7 μm. 50 Marble. In this case, the at least one milled calcium carbonate filler material exhibits a particle size of 0.5 to 150 μm as measured using the nitrogen and BET method according to ISO 9277. 2 / g, preferably 0.5 to 50m 2 / g, more preferably 0.5 to 35m 2 / g and the optimal value is 0.5 to 15m 2 / g BET specific surface area.

[0153] According to the present invention, the at least one milled calcium carbonate-containing filler material has a residual moisture content of ≤1% by weight based on the total dry weight of the at least one milled calcium carbonate-containing filler material. Depending on the at least one milled calcium carbonate-containing filler material, the at least one milled calcium carbonate-containing filler material has a residual total moisture content of 0.01-1% by weight, preferably 0.01-0.2% by weight, more preferably 0.02-0.15% by weight, and most preferably 0.04-0.15% by weight based on the total dry weight of the at least one milled calcium carbonate-containing filler material.

[0154] For example, when using ground and spray-dried marble as the at least one ground calcium carbonate-containing filler material, the residual total moisture content of the at least one ground calcium carbonate-containing filler material, based on the total dry weight of the at least one ground calcium carbonate-containing filler material, is preferably 0.01-0.1% by weight, more preferably 0.02-0.08% by weight, and most preferably 0.04-0.07% by weight. If PCC is used as the at least one ground calcium carbonate-containing filler material, the residual total moisture content of the at least one ground calcium carbonate-containing filler material, based on the total dry weight of the at least one ground calcium carbonate-containing filler material, is preferably 0.01-0.2% by weight, more preferably 0.05-0.17% by weight, and most preferably 0.05-0.10% by weight.

[0155] According to the present invention, the surface-treated filler material product further comprises a treatment layer on the surface of the at least one milled calcium carbonate-containing filler material.

[0156] This processing layer contains

[0157] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0158] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0159] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0160] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents. 30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0161] v. at least one polydialkylsiloxane, and / or

[0162] vi. A mixture of materials according to i. to v.

[0163] According to one embodiment of the invention, the surface-treated filler material product comprises a treatment layer on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material, wherein the treatment layer comprises a phosphate blend of one or more monophosphate esters and their salt reaction products and / or one or more diesters and their salt reaction products.

[0164] In the context of this invention, the term "phosphate monoester" refers to a phosphoric acid molecule monoesterified with an alcohol molecule selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0165] In the context of this invention, the term "phosphodiester" refers to a phosphoric acid molecule diesterized by two alcohol molecules selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0166] In the context of this invention, the term "salty reaction product of a phosphate blend of one or more monophosphates and / or one or more diesters" refers to a product obtained by contacting a calcium carbonate-containing filler material with one or more monophosphates and one or more diesters and optionally phosphoric acid. The salty reaction product is formed between the applied one or more monophosphates and one or more diesters and optionally phosphoric acid and reactive molecules located on the surface of the filler material, preferably at least one milled calcium carbonate-containing filler material.

[0167] Alkyl esters of phosphoric acid are well known in industry, particularly as surfactants, lubricants, and antistatic agents (Die Tenside; Kosswig und Stache, Carl Hanser Verlag München, 1993).

[0168] Synthesizing alkyl esters of phosphoric acid by various methods and using alkyl esters of phosphoric acid for surface treatment of minerals are well known to those skilled in the art, for example, from the following literature: Pesticide Formulations and Application Systems: 15th Volume; Collins HM, Hall FR, Hopkinson M, STP1268; published in 1996, US 3,897,519 A, US 4,921,990 A, US 4,350,645 A, US 6,710,199 B2, US 4,126,650 A, US 5,554,781 A, EP 1092000 B1 and WO 2008 / 023076 A1.

[0169] It should be understood that the expression "one or more" phosphate monoesters means that one or more types of phosphate monoesters may be present in the phosphate blend.

[0170] Therefore, it should be noted that the one or more monophosphate esters may be of one type. Alternatively, the one or more monophosphate esters may be a mixture of two or more types of monophosphate esters. For example, the one or more monophosphate esters may be a mixture of two or three types of monophosphate esters, such as a mixture of two types of monophosphate esters.

[0171] In one embodiment of the invention, the one or more phosphate monoesters are composed of an orthophosphate molecule esterified with an alcohol selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C6 to C30 in the alcohol substituents. For example, the one or more phosphate monoesters are composed of an orthophosphate molecule esterified with an alcohol selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0172] In one embodiment of the invention, the one or more phosphate monoesters are composed of an orthophosphate molecule esterified with an alcohol selected from saturated and branched or linear aliphatic alcohols having a total carbon atom count of C6 to C30 in the alcohol substituents. For example, the one or more phosphate monoesters are composed of an orthophosphate molecule esterified with an alcohol selected from saturated and branched or linear aliphatic alcohols having a total carbon atom count of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0173] In one embodiment of the invention, the one or more phosphate monoesters are composed of an orthophosphate molecule esterified with an alcohol, wherein the alcohol is selected from saturated and linear aliphatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents. Alternatively, the one or more phosphate monoesters are composed of an orthophosphate molecule esterified with an alcohol, wherein the alcohol is selected from saturated and branched aliphatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0174] In one embodiment of the present invention, the one or more monophosphate esters are selected from alkyl phosphate monoester, heptyl phosphate monoester, octyl phosphate monoester, 2-ethylhexyl phosphate monoester, nonyl phosphate monoester, decyl phosphate monoester, undecyl phosphate monoester, dodecyl phosphate monoester, tetradecyl phosphate monoester, hexadecyl phosphate monoester, heptylnonyl phosphate monoester, octadecyl phosphate monoester, 2-octyl-1-decyl phosphate monoester, 2-octyl-1-dodecyl phosphate monoester, and mixtures thereof.

[0175] For example, the one or more phosphate monoesters are selected from 2-ethylhexyl phosphate monoester, hexadecyl phosphate monoester, heptylnonyl phosphate monoester, octadecyl phosphate monoester, 2-octyl-1-decyl phosphate monoester, 2-octyl-1-dodecyl phosphate monoester, and mixtures thereof. In one embodiment of the invention, the one or more phosphate monoesters are 2-octyl-1-dodecyl phosphate monoester.

[0176] It should be understood that the expression "one or more" phosphate diesters means that one or more types of phosphate diesters may be present in the phosphate ester blend and / or the treatment layer of the surface-treated material product.

[0177] Therefore, it should be noted that the one or more phosphate diesters may be of one type. Alternatively, the one or more phosphate diesters may be a mixture of two or more types of phosphate diesters. For example, the one or more phosphate diesters may be a mixture of two or three types of phosphate diesters, such as a mixture of two types of phosphate diesters.

[0178] In one embodiment of the invention, the one or more phosphate diesters are composed of orthophosphate molecules esterified with two alcohols, wherein the alcohols are selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C6 to C30 in the alcohol substituents. For example, the one or more phosphate diesters are composed of orthophosphate molecules esterified with two alcohols, wherein the alcohols are selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0179] It should be understood that the two alcohols used for esterifying phosphoric acid can be independently selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms of C6 to C30 in the alcohol substituents. In other words, the one or more phosphate diesters may contain two substituents derived from the same alcohol or the phosphate diester molecule may contain two substituents derived from different alcohols.

[0180] In one embodiment of the invention, the one or more phosphate diesters are composed of orthophosphate molecules esterified with two alcohols, wherein the alcohols are selected from the same or different saturated and linear or branched aliphatic alcohols having a total carbon atom count of C6 to C30 in the alcohol substituents. For example, the one or more phosphate diesters are composed of orthophosphate molecules esterified with two alcohols, wherein the alcohols are selected from the same or different saturated and linear or branched aliphatic alcohols having a total carbon atom count of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0181] In one embodiment of the invention, the one or more phosphate diesters are composed of orthophosphate molecules esterified with two alcohols, wherein the alcohols are selected from the same or different saturated and linear aliphatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents. Alternatively, the one or more phosphate diesters are composed of orthophosphate molecules esterified with two alcohols, wherein the alcohols are selected from the same or different saturated and branched aliphatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0182] In one embodiment of the invention, the one or more phosphate diesters are selected from autoyl phosphate diesters, heptyl phosphate diesters, octyl phosphate diesters, 2-ethylhexyl phosphate diesters, nonyl phosphate diesters, decyl phosphate diesters, undecyl phosphate diesters, dodecyl phosphate diesters, tetradecyl phosphate diesters, hexadecyl phosphate diesters, heptylnonyl phosphate diesters, octadecyl phosphate diesters, 2-octyl-1-decyl phosphate diesters, 2-octyl-1-dodecyl phosphate diesters, and mixtures thereof.

[0183] For example, the one or more phosphate diesters are selected from 2-ethylhexyl phosphate diester, hexadecyl phosphate diester, heptylnonyl phosphate diester, octadecyl phosphate diester, 2-octyl-1-decyl phosphate diester, 2-octyl-1-dodecyl phosphate diester, and mixtures thereof. In one embodiment of the invention, the one or more phosphate diesters are 2-octyl-1-dodecyl phosphate diesters.

[0184] In one embodiment of the present invention, the one or more phosphate monoesters are selected from 2-ethylhexyl phosphate monoester, hexadecyl phosphate monoester, heptylnonyl phosphate monoester, octadecyl phosphate monoester, 2-octyl-1-decyl phosphate monoester, 2-octyl-1-dodecyl phosphate monoester, and mixtures thereof, and the one or more phosphate diesters are selected from 2-ethylhexyl phosphate diester, hexadecyl phosphate diester, heptylnonyl phosphate diester, octadecyl phosphate diester, 2-octyl-1-decyl phosphate diester, 2-octyl-1-dodecyl phosphate diester, and mixtures thereof.

[0185] For example, at least a portion of the surface of the calcium carbonate-containing filler material comprises a phosphate blend of a monophosphate ester and its salt reaction product, and a diester phosphate ester and its salt reaction product. In this case, the monophosphate ester is selected from 2-ethylhexyl phosphate monoester, hexadecyl phosphate monoester, heptylnonyl phosphate monoester, octadecyl phosphate monoester, 2-octyl-1-decyl phosphate monoester, and 2-octyl-1-dodecyl phosphate monoester, and the diester phosphate ester is selected from 2-ethylhexyl phosphate diester, hexadecyl phosphate diester, heptylnonyl phosphate diester, octadecyl phosphate diester, 2-octyl-1-decyl phosphate diester, and 2-octyl-1-dodecyl phosphate diester.

[0186] If at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of a monophosphate and its salt reaction product and a phosphate diester and its salt reaction product, it should be understood that the alcohol substituents of the monophosphate and the phosphate diester are preferably the same. For example, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of 2-ethylhexyl phosphate and its salt reaction product and 2-ethylhexyl phosphate diester and its salt reaction product. Alternatively, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of 2-octyl-1-decyl phosphate and its salt reaction product and 2-octyl-1-decyl phosphate diester and its salt reaction product. Alternatively, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of hexadecyl phosphate and its salt reaction product and hexadecyl phosphate diester and its salt reaction product. Alternatively, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of octadecyl phosphate monoester and its salt reaction product and octadecyl phosphate diester and its salt reaction product. Alternatively, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of 2-octyl-1-dodecyl phosphate monoester and its salt reaction product and 2-octyl-1-dodecyl phosphate diester and its salt reaction product.

[0187] In one embodiment of the invention, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of two or more types of monophosphate esters and their salt reaction products, and two or more types of diesters and their salt reaction products. In this case, the two or more monophosphate esters are selected from 2-ethylhexyl phosphate monoester, hexadecyl phosphate monoester, heptylnonyl phosphate monoester, octadecyl phosphate monoester, 2-octyl-1-decyl phosphate monoester, and 2-octyl-1-dodecyl phosphate monoester, and the two or more diesters are selected from 2-ethylhexyl phosphate diester, hexadecyl phosphate diester, heptylnonyl phosphate diester, octadecyl phosphate diester, 2-octyl-1-decyl phosphate diester, and 2-octyl-1-dodecyl phosphate diester.

[0188] In one embodiment of the invention, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of two monophosphates and their salt reaction products, and two phosphate diesters and their salt reaction products. For example, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of hexadecyl phosphate monoester, octadecyl phosphate monoester, hexadecyl phosphate diester, octadecyl phosphate diester, and their salt reaction products.

[0189] According to one embodiment of the invention, the phosphate blend on at least a portion of the surface of the at least one milled calcium carbonate filler material comprises a specific molar ratio of one or more monophosphates and their salt reaction products to one or more diesters and their salt reaction products. Specifically, the molar ratio of one or more monophosphates and their salt reaction products to one or more diesters and their salt reaction products in the treated layer and / or the phosphate blend can be from 1:1 to 1:100.

[0190] The expression "the molar ratio of one or more monophosphate molecules and their salt reaction products to one or more diphosphate molecules and their salt reaction products" in the context of this invention refers to the ratio of the total molecular weight of monophosphate molecules and the total molecular weight of monophosphate molecules in their salt reaction products to the total molecular weight of diphosphate molecules and the total molecular weight of diphosphate molecules in their salt reaction products.

[0191] According to one embodiment, the molar ratio of one or more monophosphates and their salt reaction products to one or more diesters and their salt reaction products in the phosphate blend is 1:1 to 1:100, preferably 1:1.1 to 1:80, more preferably 1:1.1 to 1:60, even more preferably 1:1.1 to 1:40, even more preferably 1:1.1 to 1:20, and most preferably 1:1.1 to 1:10.

[0192] Additionally or alternatively, the phosphate blend of the treated layer comprises one or more monophosphates and their salt reaction products, in an amount of 1 to 50 mol% based on the total molar amount of one or more monophosphates and their salt reaction products and one or more phosphate diesters and their salt reaction products. For example, the phosphate blend of the treated layer comprises one or more monophosphates and their salt reaction products, in an amount of 10 to 45 mol% based on the total molar amount of one or more monophosphates and their salt reaction products and one or more phosphate diesters and their salt reaction products.

[0193] According to one embodiment of the present invention,

[0194] I) The one or more phosphate monoesters are composed of an orthophosphate molecule monoesterified with an alcohol molecule, wherein the alcohol molecule is selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents, and / or

[0195] II) The one or more phosphate diesters are composed of orthophosphate molecules diesterized by two alcohol molecules, wherein the alcohol molecules are selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic fatty alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20 and most preferably C8 to C18 in the alcohol substituents.

[0196] In one embodiment of the invention, the phosphate blend of the treatment layer further comprises one or more triphosphates and / or phosphoric acid and their salt reaction products.

[0197] In the context of this invention, the term "triphosphate" refers to a phosphoric acid molecule composed of three alcohol molecules triesterified together, wherein the alcohol molecules are selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic fatty alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0198] It should be understood that the expression "one or more" triphosphates means that one or more types of triphosphates may be present on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material.

[0199] Therefore, it should be noted that the one or more triphosphates may be of one type of triphosphate. Alternatively, the one or more triphosphates may be a mixture of two or more types of triphosphates. For example, the one or more triphosphates may be a mixture of two or three types of triphosphates, such as a mixture of two types of triphosphates.

[0200] In one embodiment of the invention, the one or more triphosphate esters are composed of orthophosphate molecules esterified with three alcohols, wherein the alcohols are selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C6 to C30 in the alcohol substituents. For example, the one or more triphosphate esters are composed of orthophosphate molecules esterified with three alcohols, wherein the alcohols are selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon atom count of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0201] It should be understood that the three alcohols used for esterifying phosphoric acid can be independently selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms (C6 to C30) in the alcohol substituents. In other words, the one or more phosphate triester molecules may contain three substituents derived from the same alcohol or the phosphate triester molecule may contain three substituents derived from different alcohols.

[0202] In one embodiment of the invention, the one or more triphosphate esters are composed of orthophosphate molecules esterified with three alcohols, wherein the alcohols are selected from the same or different saturated and linear or branched aliphatic alcohols having a total carbon atom count of C6 to C30 in the alcohol substituents. For example, the one or more triphosphate esters are composed of orthophosphate molecules esterified with three alcohols, wherein the alcohols are selected from the same or different saturated and linear or branched aliphatic alcohols having a total carbon atom count of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0203] In one embodiment of the invention, the one or more triphosphate esters are composed of orthophosphate molecules esterified with three alcohols, wherein the alcohols are selected from saturated and linear aliphatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents. Alternatively, the one or more triphosphate esters are composed of orthophosphate molecules esterified with three alcohols, wherein the alcohols are selected from saturated and branched aliphatic alcohols having a total carbon atom count of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituents.

[0204] In one embodiment of the invention, the one or more triphosphates are selected from autoyl phosphate triester, heptyl phosphate triester, octyl phosphate triester, 2-ethylhexyl phosphate triester, nonyl phosphate triester, decyl phosphate triester, undecyl phosphate triester, dodecyl phosphate triester, tetradecyl phosphate triester, hexadecyl phosphate triester, heptylnonyl phosphate triester, octadecyl phosphate triester, 2-octyl-1-decyl phosphate triester, 2-octyl-1-dodecyl phosphate triester, and mixtures thereof.

[0205] For example, the one or more phosphate triesters are selected from 2-ethylhexyl phosphate triester, hexadecyl phosphate triester, heptylnonyl phosphate triester, octadecyl phosphate triester, 2-octyl-1-decyl phosphate triester, 2-octyl-1-dodecyl phosphate triester and mixtures thereof.

[0206] In one embodiment of the invention, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of one or more monophosphates and their salt reaction products, one or more phosphate diesters and their salt reaction products, and one or more triphosphates and optionally phosphoric acid and its salt reaction products. For example, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of one or more monophosphates and their salt reaction products, one or more phosphate diesters and their salt reaction products, and one or more triphosphates and phosphoric acid and its salt reaction products.

[0207] Alternatively, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of one or more monophosphates and their salt reaction products, one or more phosphate diesters and their salt reaction products, and optionally, phosphoric acid and its salt reaction products. For example, at least a portion of the surface of the at least one milled calcium carbonate-containing filler material comprises a phosphate blend of one or more monophosphates and their salt reaction products, one or more phosphate diesters and their salt reaction products, and optionally, phosphoric acid and its salt reaction products.

[0208] If at least a portion of the surface of the at least one milled calcium carbonate-containing filler material contains a phosphate blend comprising one or more triphosphates, then preferably, the phosphate blend comprises one or more triphosphates in an amount ≤10 mol% based on the total molar amount of one or more monophosphates and their salt reaction products, one or more diphosphates and their salt reaction products, and one or more triphosphates and phosphoric acid and their salt reaction products. For example, the phosphate blend comprises one or more triphosphates in an amount ≤8 mol%, preferably ≤6 mol%, and more preferably ≤4 mol%, such as 0.1 to 4 mol%, based on the total molar amount of one or more monophosphates and their salt reaction products, one or more diphosphates and their salt reaction products, and one or more triphosphates and phosphoric acid and their salt reaction products.

[0209] Additionally or alternatively, if at least a portion of the surface of the at least one milled calcium carbonate-containing filler material contains a phosphate ester blend comprising phosphoric acid and its salt reaction products, preferably, the phosphate ester blend comprises phosphoric acid and its salt reaction products in an amount ≤10 mol% based on the total molar amount of one or more monophosphate esters and their salt reaction products, one or more diesters and their salt reaction products, and one or more triphosphate esters and their salt reaction products. For example, the phosphate ester blend comprises phosphoric acid and its salt reaction products in an amount ≤8 mol%, preferably ≤6 mol%, and more preferably ≤4 mol%, such as 0.1 to 4 mol%, based on the total molar amount of one or more monophosphate esters and their salt reaction products, one or more diesters and their salt reaction products, and one or more triphosphate esters and their salt reaction products.

[0210] If the phosphate blend further comprises phosphoric acid and its salt reaction products and one or more triphosphates, then preferably, the molar ratio of phosphoric acid and its salt reaction products to one or more monophosphates and their salt reaction products, one or more diphosphates and their salt reaction products, and one or more triphosphates and phosphoric acid and their salt reaction products in the phosphate blend is ≤10 mol% : ≤40 mol% : ≥40 mol% : ≤10 mol%, based on the total molar amount of one or more monophosphates and their salt reaction products, one or more diphosphates and their salt reaction products, and one or more triphosphates.

[0211] The expression "molar ratio of phosphoric acid and its salt reaction products to one or more monophosphates and their salt reaction products to one or more diphosphates and their salt reaction products to one or more triphosphates" in this invention refers to the ratio of the total molecular weight of phosphoric acid and the total molecular weight of phosphoric acid molecules in its salt reaction products to the total molecular weight of monophosphate molecules in its salt reaction products to the total molecular weight of monophosphate molecules in its salt reaction products to the total molecular weight of diphosphate molecules in its salt reaction products to the total molecular weight of triphosphate molecules.

[0212] It should be understood that the phosphate blend may comprise a salt reaction product obtained by contacting the at least one filler material, preferably the at least one milled calcium carbonate-containing filler material, with one or more monophosphates and one or more diesters and optionally phosphoric acid. In this case, the phosphate blend preferably comprises one or more calcium, magnesium, and / or aluminum salts of the salt reaction product such as monophosphate, one or more calcium, magnesium, and / or aluminum salts of diester, and optionally one or more calcium, magnesium, and / or aluminum salts of phosphoric acid. Preferably, the phosphate blend comprises one or more calcium and / or magnesium salts of the salt reaction product such as monophosphate, one or more calcium and / or magnesium salts of diester, and optionally one or more calcium and / or magnesium salts of phosphoric acid.

[0213] In one embodiment of the invention, the one or more phosphate monoesters and / or one or more phosphate diesters, and optionally phosphoric acid, may be at least partially neutralized by one or more hydroxides of monovalent and / or divalent and / or trivalent cations and / or one or more weak acid salts of monovalent and / or divalent and / or trivalent cations prior to the preparation of the at least one filler material, preferably the at least one milled calcium carbonate-containing filler material. The one or more hydroxides of divalent and / or trivalent cations may be selected from Ca(OH)₂, Mg(OH)₂, Al(OH)₃, and mixtures thereof.

[0214] Additionally or alternatively, if the one or more monophosphates and / or one or more diesters and optionally phosphoric acid are at least partially neutralized by one or more hydroxides and / or one or more weak acid salts of a monovalent cation, the amount of the monovalent cation is preferably ≤10 mol% based on the total molar number of acidic groups in the one or more monophosphates and one or more diesters and optionally phosphoric acid. The one or more hydroxides and / or one or more weak acid salts of the monovalent cation used for neutralization may be selected from LiOH, NaOH, KOH, Na2CO3, Li2CO3, K2CO3 and mixtures thereof.

[0215] In one embodiment of the invention, the divalent cation used for partially neutralizing one or more monophosphates and / or one or more diesters and optionally phosphoric acid is a weak acid salt derived from such cation, preferably derived from carbonates and / or borates, such as calcium carbonate.

[0216] The term "weak acid" as used in this application refers to Brønsted-Lorais acid ( -Lowryacid), also known as H3O + Ion provider, characterized by pK a >2, preferably 4 to 7.

[0217] Therefore, the phosphate blend of the treated layer may further comprise salt reaction products, such as calcium and / or magnesium salts of one or more monophosphates and calcium and / or magnesium salts of one or more diesters and optionally calcium and / or magnesium salts of one or more phosphates. Additionally or optionally, the phosphate blend of the treated layer may further comprise salt reaction products, such as aluminum salts of one or more monophosphates and aluminum salts of one or more diesters and optionally one or more aluminum phosphates. Additionally or optionally, the phosphate blend of the treated layer may further comprise salt reaction products, such as lithium salts of one or more monophosphates and lithium salts of one or more diesters and optionally one or more lithium phosphates. Additionally or optionally, the phosphate blend of the treated layer may further comprise salt reaction products, such as sodium salts of one or more monophosphates and sodium salts of one or more diesters and optionally one or more sodium phosphates. Additionally or alternatively, the phosphate blend of the treated layer may further comprise a salt reaction product, such as a potassium salt of one or more monophosphates and a potassium salt of one or more diesters and optionally one or more potassium phosphates.

[0218] If one or more monophosphates and / or one or more diesters and optionally phosphoric acid are at least partially neutralized by one or more hydroxides and / or one or more weak acid salts of a monovalent cation, the treated layer and / or phosphate blend preferably contains a monovalent cation in an amount ≤10 mol% based on the total molar amount of acidic groups in one or more monophosphates and one or more diesters and optionally phosphoric acid.

[0219] In one embodiment of the invention, the phosphate blend of the treated layer may further comprise additional surface treatment agents that do not correspond to the one or more monophosphates, one or more diesters, and optionally one or more triphosphates and / or phosphoric acid of the invention.

[0220] In one embodiment, the molar ratio of the one or more monophosphates and / or the one or more diesters to their salt reaction products is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.

[0221] The expression "the molar ratio of the one or more monophosphate molecules and / or the one or more diphosphate molecules to its salt reaction product" in the context of this invention refers to the total molecular weight of monophosphate molecules and / or the total molecular weight of diphosphate molecules to the total molecular weight of monophosphate molecules in its salt reaction product and / or the total molecular weight of diphosphate molecules in its salt reaction product.

[0222] Methods for preparing surface-treated filler material products treated with at least one phosphate ester blend, and suitable compounds for coating, are described, for example, in EP 2 770 017A1, which is therefore incorporated herein by reference.

[0223] According to another embodiment of the invention, the surface-treated filler material product comprises a treatment layer on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material, wherein the treatment layer comprises at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product.

[0224] For example, the treatment layer contains saturated aliphatic linear or branched carboxylic acids having a total carbon atom count of C4 to C24 and / or their salt reaction products.

[0225] In the context of this invention, the term "salt reaction product" of saturated aliphatic linear or branched carboxylic acids refers to a product obtained by contacting at least one milled calcium carbonate-containing filler material with the at least one saturated aliphatic linear or branched carboxylic acid. The reaction product is formed between at least a portion of the applied at least one saturated aliphatic linear or branched carboxylic acid and reactive molecules located on the surface of the at least one milled calcium carbonate-containing filler material.

[0226] In the context of this invention, aliphatic carboxylic acids may be selected from one or more linear, branched, saturated, unsaturated, and / or alicyclic carboxylic acids. Preferably, the aliphatic carboxylic acid is a monocarboxylic acid, meaning that it is characterized by the presence of a single carboxyl group. The carboxyl group is located at the end of the carbon skeleton.

[0227] In one embodiment of the present invention, the aliphatic linear or branched carboxylic acid is selected from saturated unbranched chain carboxylic acids, that is, the aliphatic carboxylic acid is preferably selected from the group of carboxylic acids consisting of the following substances: 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, icosanoic acid, benzanoic acid, tridecanoic acid, tetradecanoic acid, and mixtures thereof.

[0228] In another embodiment of the invention, the aliphatic linear or branched carboxylic acid is selected from octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and mixtures thereof. Preferably, the aliphatic linear or branched carboxylic acid is selected from octanoic acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof.

[0229] For example, the aliphatic linear or branched carboxylic acid is octanoic acid or stearic acid. Preferably, the aliphatic linear or branched carboxylic acid is stearic acid.

[0230] In one embodiment, the molar ratio of the at least one saturated aliphatic linear or branched carboxylic acid to its salt reaction product is 99.9:0.1 to 0.1:99.9, preferably 70:30 to 90:10.

[0231] The expression "the molar ratio of the at least one saturated aliphatic linear or branched carboxylic acid to its salt reaction product" in the context of this invention refers to the total molecular weight of the saturated aliphatic linear or branched carboxylic acid relative to the total molecular weight of the saturated aliphatic linear or branched carboxylic acid in the salt reaction product.

[0232] According to another embodiment of the invention, the surface-treated filler material comprises a treatment layer on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material, wherein the treatment layer comprises at least one aliphatic aldehyde and / or its salt reaction product.

[0233] In this regard, the at least one aliphatic aldehyde refers to a surface treatment agent and can be selected from any linear, branched, or alicyclic, substituted or unsubstituted, saturated or unsaturated aliphatic aldehyde. The aldehyde is preferably selected such that the number of carbon atoms is greater than or equal to 6, and more preferably greater than or equal to 8. Furthermore, the aldehyde typically has a number of carbon atoms less than or equal to 14, preferably less than or equal to 12, and more preferably less than or equal to 10. In a preferred embodiment, the aliphatic aldehyde has a carbon number of 6-14, preferably 6-12, and more preferably 6-10.

[0234] In another preferred embodiment, the at least one aliphatic aldehyde is preferably selected such that the number of carbon atoms is 6-12, more preferably between 6-9, and most preferably 8 or 9.

[0235] The aliphatic aldehyde can be selected from the following aliphatic aldehydes: hexanal, (E)-2-hexenal, (Z)-2-hexenal, (E)-3-hexenal, (Z)-3-hexenal, (E)-4-hexenal, (Z)-4-hexenal, 5-hexenal, heptanal, (E)-2-hexenal, (Z)-2-hexenal, (E)-3-hexenal, (Z)-3-hexenal Aldehydes, (E)-4-heptenal, (Z)-4-heptenal, (E)-5-heptenal, (Z)-5-heptenal, 6-heptenal, octanal, (E)-2-octenal, (Z)-2-octenal, (E)-3-octenal, (Z)-3-octenal, (E)-4-octenal, (Z)-4-octenal, (E)-5-octenal, (Z) -5-Octenal, (E)-6-Octenal, (Z)-6-Octenal, 7-Octenal, Nonanal, (E)-2-Nonenal, (Z)-2-Nonenal, (E)-3-Nonenal, (Z)-3-Nonenal, (E)-4-Nonenal, (Z)-4-Nonenal, (E)-5-Nonenal, (Z)-5-Nonenal, (E)-6-Nonenal Aldehydes, (Z)-6-nonenal, (E)-6-nonenal, (Z)-6-nonenal, (E)-7-nonenal, (Z)-7-nonenal, 8-nonenal, decanal, (E)-2-decenal, (Z)-2-decenal, (E)-3-decenal, (Z)-3-decenal, (E)-4-decenal, (Z)-4-decenal, (E)- 5-Decenoal, (Z)-5-Decenoal, (E)-6-Decenoal, (Z)-6-Decenoal, (E)-7-Decenoal, (Z)-7-Decenoal, (E)-8-Decenoal, (Z)-8-Decenoal, 9-Decenoal, Undecenoal, (E)-2-Undecenoal, (Z)-2-Undecenoal, (E)-3-Undecenoal, (Z)-3-Undecenoal, (E)-4-Undecenoal, (Z)-4-Undecenoal, (E)-5-Undecenoal, (Z)-5-Undecenoal, (E)-6-Undecenoal, (Z)-6-Undecenoal, (E)-7-Undecenoal, (Z)-7-Undecenoal, (E)-8-Undecenoal, (Z)-8-Undecenoal, (E)-9-Undecenoal Enal, (Z)-9-undecenal, 10-undecenal, dodecenal, (E)-2-dodecenal, (Z)-2-dodecenal, (E)-3-dodecenal, (Z)-3-dodecenal, (E)-4-dodecenal, (Z)-4-dodecenal, (E)-5-dodecenal, (Z)-5-dodecenal, (E)-6-dodecenal, (Z)-6-dodecenal, (E)-7-dodecenal, (Z)-7-dodecenal, (E)-8-dodecenal, (Z)-8-dodecenal, (E)-9-dodecenal, (Z)-9-dodecenal, (E)-10-dodecenal, (Z)-10-dodecenal, 11-dodecenal, tridecanal, (E)-2-tridecanal(Z)-2-Trigenal, (E)-3-Trigenal, (Z)-3-Trigenal, (E)-4-Trigenal, (Z)-4-Trigenal, (E)-5-Trigenal, (Z)-5-Trigenal, (E)-6-Trigenal, (Z)-6-Trigenal, (E)-7-Trigenal, (Z)-7-Trigenal, (E)-8-Trigenal, (Z)-8-Trigenal, (E)-9-Trigenal, (Z)-9-Trigenal, (E)-10-Trigenal, (Z)-10-Trigenal, (E)-11-Trigenal, (Z)-11-Trigenal, 12-Trigenal, Tetradecanoal, (E)-2-Tetradecanoal, (Z)-2-Tetradecanoal Enal, (E)-3-tetradecenal, (Z)-3-tetradecenal, (E)-4-tetradecenal, (Z)-4-tetradecenal, (E)-5-tetradecenal, (Z)-5-tetradecenal, (E)-6-tetradecenal, (Z)-6-tetradecenal, (E)-7-tetradecenal, (Z)-7-tetradecenal, (E)-8-tetradecenal, (Z)-8-tetradecenal, (E)-9-tetradecenal, (Z)-9-tetradecenal, (E)-10-tetradecenal, (Z)-10-tetradecenal, (E)-11-tetradecenal, (Z)-11-tetradecenal, (E)-12-tetradecenal, (Z)-12-tetradecenal, 13-tetradecenal, and mixtures thereof. In a preferred embodiment, the aliphatic aldehyde is selected from hexanal, (E)-2-hexenal, (Z)-2-hexenal, (E)-3-hexenal, (Z)-3-hexenal, (E)-4-hexenal, (Z)-4-hexenal, 5-hexenal, heptanal, (E)-2-hexenal, (Z)-2-hexenal, (E)-3-hexenal, (Z)-3-hexenal, (E)-4-hexenal, (Z)-4-hexenal, (E)-5-hexenal, (Z)-5-hexenal, 6-hexenal, octanal, (E)-2-octenal, (Z)-2-octenal, (E)-3-octenal, (E)-2-octenal, (Z)-3-octenal, ( (Z)-3-Octenal, (E)-4-Octenal, (Z)-4-Octenal, (E)-5-Octenal, (Z)-5-Octenal, (E)-6-Octenal, (Z)-6-Octenal, 7-Octenal, Nonanal, (E)-2-Nonenal, (Z)-2-Nonenal, (E)-3-Nonenal, (Z)-3-Nonenal, (E)-4-Nonenal, (Z)-4-Nonenal, (E)-5-Nonenal, (Z)-5-Nonenal, (E)-6-Nonenal, (Z)-6-Nonenal, (E)-7-Nonenal, (Z)-7-Nonenal, 8-Nonenal, and mixtures thereof.

[0236] In another preferred embodiment, the at least one aliphatic aldehyde is a saturated aliphatic aldehyde. In this case, the aliphatic aldehyde is selected from acetal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal, and mixtures thereof. Preferably, the at least one aliphatic aldehyde in the form of a saturated aliphatic aldehyde is selected from acetal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, and mixtures thereof. For example, the at least one aliphatic aldehyde in the form of a saturated aliphatic aldehyde is selected from octanal, nonanal, and mixtures thereof.

[0237] If, according to the invention, a mixture of two aliphatic aldehydes, such as two saturated aliphatic aldehydes, such as octanal and nonanal, is used, the weight ratio of octanal to nonanal is 70:30 to 30:70, and more preferably 60:40 to 40:60. In a particularly preferred embodiment of the invention, the weight ratio of octanal to nonanal is about 1:1.

[0238] In the context of this invention, the term "salt reaction product" of the at least one aliphatic aldehyde refers to a product obtained by contacting the at least one milled calcium carbonate-containing filler material with the at least one aliphatic aldehyde. The reaction product is formed between at least a portion of the applied at least one aliphatic aldehyde and reactive molecules located on the surface of the at least one filler material, preferably the at least one milled calcium carbonate-containing filler material.

[0239] In one embodiment, the molar ratio of the at least one aliphatic aldehyde to its salt reaction product is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.

[0240] The expression "the molar ratio of the at least one aliphatic aldehyde to its salt reaction product" in the context of this invention refers to the total molecular weight of the aliphatic aldehyde relative to the total molecular weight of the aliphatic aldehyde in the salt reaction product.

[0241] Methods for preparing surface-treated filler material products treated with at least one aliphatic aldehyde, and suitable compounds for coating, are described, for example, in EP 2 390 285 A1, which is therefore incorporated herein by reference.

[0242] According to another embodiment of the invention, the surface-treated filler material comprises a treated layer on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material, wherein the treated layer comprises at least one monosubstituted succinic anhydride and / or its salt reaction product, the monosubstituted succinic anhydride being formed using a mixture of substituents with a total carbon atom count of at least C2 to C4. 30 It consists of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups.

[0243] The term "succinic anhydride" is also known as dihydro-2,5-furandione, the anhydride of succinic acid, or succinyl oxygen, and has the molecular formula C4H4O3 and is the anhydride of succinic acid.

[0244] In the context of this invention, the term "monosubstituted" succinic anhydride refers to succinic anhydride in which a hydrogen atom is replaced by another substituent.

[0245] In the context of this invention, the term "monosubstituted" succinic acid refers to succinic acid in which a hydrogen atom is replaced by another substituent.

[0246] The term "salt reaction product" for the at least one monosubstituted succinic anhydride refers to a product obtained by contacting the at least one milled calcium carbonate-containing filler material with one or more monosubstituted succinic anhydrides. The salt reaction product is formed between a monosubstituted succinic acid formed by the applied monosubstituted succinic anhydride and reactive molecules located on the surface of the at least one milled calcium carbonate-containing filler material. Alternatively, the salt reaction product may be formed between a monosubstituted succinic acid, optionally present with the at least one monosubstituted succinic anhydride, and reactive molecules located on the surface of the at least one milled calcium carbonate-containing filler material.

[0247] For example, the treated layer on the surface of the at least one milled calcium carbonate filler material comprises at least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by utilizing a mixture of substituents with a total carbon atom count of at least C2 to C4. 30 The material is composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups. More preferably, the treated layer on the surface of the at least one milled calcium carbonate-containing filler material comprises at least one monosubstituted succinic anhydride and / or its salt reaction product, the monosubstituted succinic anhydride being formed using a group selected from those with a total carbon atom count of at least C2 to C4 in the substituents. 30 C3 to C are preferred. 20 And the optimal choice is C4 to C 18 It consists of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups.

[0248] For the preparation of at least one monosubstituted succinic anhydride (made from a material selected from the substituents having a total carbon atom count of at least C2 to C3). 30 Methods for treating surface-treated filler material products (comprising monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups) and suitable compounds for coating are described, for example, in WO2016 / 023937 A1, which is therefore incorporated herein by reference.

[0249] According to another embodiment of the invention, the surface-treated filler material product comprises a treatment layer on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material, wherein the treatment layer comprises at least one polydialkylsiloxane.

[0250] Preferred polydialkylsiloxanes are described, for example, in US 2004 / 0097616 A1. Most preferred are polydialkylsiloxanes selected from polydimethylsiloxane, preferably dimethicone, polydiethylsiloxane, and polymethylphenylsiloxane and / or mixtures thereof.

[0251] For example, the at least one polydialkylsiloxane is preferably polydimethylsiloxane (PDMS).

[0252] The at least one polydialkylsiloxane is preferably present in an amount such that the total amount of the polydialkylsiloxane on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material is less than 1000 ppm, more preferably less than 800 ppm, and most preferably less than 600 ppm. For example, the total amount of the polydialkylsiloxane on at least a portion of the surface of the at least one milled calcium carbonate-containing filler material is 100-1000 ppm, more preferably 200-800 ppm, and most preferably 300-600 ppm, such as 400-600 ppm.

[0253] The treated layer on the surface of the at least one milled calcium carbonate filler material preferably comprises at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or at least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by utilizing a mixture of substituents with a total carbon atom count of at least C2 to C4. 30 The material is composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups. More preferably, the treated layer on the surface of the at least one milled calcium carbonate-containing filler material comprises at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product.

[0254] In one embodiment, the treatment layer on at least a portion of the surface of the at least one milled calcium carbonate filler material comprises a mixture of the above materials, preferably a mixture of two materials.

[0255] Therefore, a post-processing layer can exist on top of this processing layer.

[0256] In the context of this invention, "after treatment layer" refers to a layer that may be different from the surface treatment agent of the treatment layer, preferably a single layer, and the "after treatment layer" is located on the "treatment layer".

[0257] In a preferred embodiment, the surface treatment of the at least one milled calcium carbonate-containing filler material is performed in two steps. The first step includes the use of a phosphate blend of one or more monophosphates and / or one or more diesters, or at least one saturated aliphatic linear or branched carboxylic acid, or at least one aliphatic aldehyde, or at least one monosubstituted succinic anhydride (made by using a mixture of carbon atoms selected from those with a total carbon atom count of at least C2 to C4 in the substituents). 30 The treatment of a monosubstituted succinic anhydride (comprising linear, branched, aliphatic, and cyclic groups) is used to form a treatment layer, and the second step includes treatment with at least one polydialkylsiloxane to form a post-treatment layer.

[0258] In another embodiment, the surface treatment is performed by simultaneously utilizing a phosphate blend of one or more monophosphate esters and / or one or more diester phosphate esters, or at least one saturated aliphatic linear or branched carboxylic acid, or at least one aliphatic aldehyde, or at least one monosubstituted succinic anhydride (made by utilizing a mixture of carbon atoms selected from those in the substituents with a total carbon atom count of at least C2 to C4). 30 The at least one milled calcium carbonate-containing filler material is treated with linear, branched, aliphatic, and cyclic groups (comprising monosubstituted succinic anhydrides) and at least one polydialkylsiloxane to form a treated layer.

[0259] Furthermore, this surface treatment can be performed by first using a polydialkylsiloxane and then using a phosphate blend of one or more monophosphate esters and / or one or more diester phosphate esters, or at least one saturated aliphatic linear or branched carboxylic acid, or at least one aliphatic aldehyde, or at least one monosubstituted succinic anhydride (made by using a mixture of carbon atoms selected from those in the substituents with a total carbon atom count of at least C2 to C4). 30 The at least one milled calcium carbonate-containing filler material is treated with linear, branched, aliphatic, and cyclic groups of monosubstituted succinic anhydride.

[0260] Preferably, the post-treatment layer comprises at least one polydialkylsiloxane.

[0261] Therefore, the treatment layer on at least a portion of the surface of the at least one milled calcium carbonate filler material preferably comprises a phosphate blend of one or more monophosphate esters and their salt reaction products and / or one or more diesters and their salt reaction products, and the post-treatment layer comprises at least one polydialkylsiloxane.

[0262] Alternatively, the treatment layer on at least a portion of the surface of the at least one milled calcium carbonate filler material comprises at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and the post-treatment layer comprises at least one polydialkylsiloxane.

[0263] Alternatively, the treatment layer on at least a portion of the surface of the at least one milled calcium carbonate filler material comprises at least one aliphatic aldehyde and / or its salt reaction product, and the post-treatment layer comprises at least one polydialkylsiloxane.

[0264] Alternatively, the treated layer on the surface of the at least one milled calcium carbonate filler material comprises at least one monosubstituted succinic anhydride (made by utilizing carbon atoms selected from those in the substituents, with a total carbon atom count of at least C2 to C4). 30 The post-treatment layer comprises monosubstituted succinic anhydrides of linear, branched, aliphatic, and cyclic groups and / or their salt reaction products, and the post-treatment layer contains at least one polydialkylsiloxane.

[0265] More preferably, the treated layer on at least a portion of the surface of the at least one milled calcium carbonate filler material comprises, most preferably, the following substances: at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product or at least one monosubstituted succinic anhydride (made by utilizing a total carbon atom content of at least C2 to C4 in the substituents). 30 The post-treatment layer comprises, most preferably, at least one polydialkylsiloxane. For example, the post-treatment layer on at least a portion of the surface of the at least one milled calcium carbonate filler material comprises, most preferably, at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and the post-treatment layer comprises, most preferably, at least one polydialkylsiloxane.

[0266] According to one embodiment, the salt reaction product of a phosphate ester, a blend of one or more monophosphate esters, one or more diesters of phosphate, or at least one saturated aliphatic linear or branched carboxylic acid, at least one aliphatic aldehyde, or at least one monosubstituted succinic anhydride is one or more of its calcium and / or magnesium salts.

[0267] Therefore, it should be understood that the at least one milled calcium carbonate-containing filler material product comprises, and preferably consists of, at least one milled calcium carbonate-containing filler material and a treatment layer, the treatment layer comprising:

[0268] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0269] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0270] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0271] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents. 30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0272] v. at least one polydialkylsiloxane, and / or

[0273] vi. A mixture of materials according to i. to v.

[0274] The treatment layer is formed on the surface of at least one milled calcium carbonate filler material.

[0275] One requirement of the present invention is that the surface-treated filler material product comprises the treated layer in an amount of 0.1-2.3% by weight of the total dry weight of the at least one milled calcium carbonate filler material.

[0276] According to one embodiment, the surface-treated filler material product comprises the treated layer in an amount of 0.2-2.0% by weight, preferably 0.4-1.9% by weight, and most preferably 0.5-1.8% by weight, based on the total dry weight of the at least one milled calcium carbonate filler material.

[0277] The preferred feature of this treatment layer is that, on the surface of the surface-treated filler material product, there are phosphate blends of one or more monophosphate monoesters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or at least one aliphatic aldehyde and / or its salt reaction product, and / or at least one monosubstituted succinic anhydride and / or its salt reaction product (the monosubstituted succinic anhydride is formed by using carbon atoms selected from those in the substituents with a total carbon atom count of at least C2 to C4). 30 The total weight of the mixture of linear, branched, aliphatic, and cyclic groups of monosubstituted succinic anhydrides, and / or at least one polydialkylsiloxane, and / or the mixture of said materials is 0.05-1% by weight / m³. 2 More preferably 0.1-0.5% by weight / m 2 The optimal value is 0.15-0.25% by weight / m. 2 The at least one milled calcium carbonate-containing filler material.

[0278] In one embodiment of the invention, the treatment layer is characterized by having on the surface of the surface-treated filler material product a mixture of one or more monophosphate monoesters and their salt reaction products and / or one or more phosphate diesters and their salt reaction products, and / or at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or at least one aliphatic aldehyde and / or its salt reaction product, and / or at least one monosubstituted succinic anhydride and / or its salt reaction product (the monosubstituted succinic anhydride is formed by using carbon atoms selected from those with a total carbon atom count of at least C2 to C6 in the substituents). 30 The total weight of the mixture of linear, branched, aliphatic, and cyclic groups of monosubstituted succinic anhydrides, and / or at least one polydialkylsiloxane, and / or a mixture of said materials is 0.1-5 mg / m³. 2 More preferably, 0.25-4.5 mg / m³ 2 The optimal value is 1.0-4.0 mg / m². 2 The at least one milled calcium carbonate-containing filler material.

[0279] It should be understood that the surface-treated filler material product is preferably characterized by a volatilization initiation temperature ≥250°C. For example, the surface-treated filler material product is characterized by a volatilization initiation temperature ≥260°C or ≥270°C. In one embodiment, the surface-treated filler material product is characterized by a volatilization initiation temperature of 250°C to 400°C, preferably 260°C to 400°C, and most preferably 270°C to 400°C.

[0280] Additionally or alternatively, the surface-treated filler material product is characterized by total volatile matter content of less than 0.25% by mass at 25-350°C, and preferably less than 0.23% by mass, for example 0.04-0.21% by mass, preferably 0.08-0.15% by mass, and more preferably 0.1-0.12% by mass.

[0281] Furthermore, the surface-treated filler material product is characterized by low water absorption sensitivity. Preferably, the surface-treated filler material product has a water absorption sensitivity such that its total surface moisture level is less than 1 mg / g of dry calcium carbonate-containing filler material at a temperature of approximately +23°C (±2°C). For example, the surface-treated filler material product has a water absorption sensitivity of 0.1-1 mg / g, more preferably 0.2-0.9 mg / g, and most preferably 0.2-0.8 mg / g of dry calcium carbonate-containing filler material after being exposed to +23°C (±2°C).

[0282] Additionally or alternatively, the surface-treated filler material product has a hydrophilicity of less than 8:2 water:ethanol volume ratio, measured by sedimentation at +23°C (±2°C). For example, the surface-treated filler material product has a hydrophilicity of less than 7:3 water:ethanol volume ratio, measured by sedimentation at +23°C (±2°C).

[0283] In order to achieve favorable formation of voids, at least one layer of the single-layer or multi-layer biaxially oriented polyester film contains 0.1-30% by weight of the surface-treated filler material product based on the total weight of the layer.

[0284] According to one embodiment, at least one layer of the single-layer or multi-layer biaxially oriented polyester film comprises an amount of the surface-treated filler material product of 1-28% by weight, preferably 2-26% by weight, more preferably 3-25% by weight, even more preferably 4.5-23% by weight, and most preferably 4-20% by weight, based on the total weight of the layer.

[0285] According to one aspect of the invention, the surface-treated filler material product described above is used as a porosimeter in single-layer or multi-layer biaxially oriented polyester films.

[0286] Single-layer or multi-layer biaxially oriented polyester film

[0287] According to the present invention, a single-layer or multi-layer biaxially oriented polyester film is provided, wherein at least one layer of the film comprises at least one polyester in an amount of 70-99.9% by weight based on the total weight of the layer and 0.1-30% by weight of a surface-treated filler material product, wherein the surface-treated filler material product comprises

[0288] A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and

[0289] B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising

[0290] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0291] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0292] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0293] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents.30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0294] v. at least one polydialkylsiloxane, and / or

[0295] vi. To mix the materials from i. to v.

[0296] The surface-treated filler material product comprises a treated layer comprising 0.1-2.3% by weight of the total dry weight of the at least one milled calcium carbonate filler material.

[0297] It should be understood that the single-layer or multi-layer biaxially oriented polyester film is particularly characterized by low density. Therefore, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, preferably has a density of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 The density.

[0298] According to one embodiment, the median thickness of the single-layer or multi-layer biaxially oriented polyester film, particularly the layer comprising at least one polyester and a surface-treated filler material, is 0.5-500 μm, preferably 4-400 μm, more preferably 5-300 μm and most preferably 6-250 μm, for example 8-150 μm.

[0299] According to one embodiment, the single-layer or multi-layer biaxially oriented polyester film, particularly the layer comprising at least one polyester and a surface-treated filler material, has a median thickness of 0.5-500 μm, preferably 4-400 μm, more preferably 5-300 μm, and most preferably 6-250 μm, such as 8-150 μm, and a g / cm³ thickness of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 The density.

[0300] It should be understood that the biaxially oriented polyester film is a single-layer or multi-layer film.

[0301] In the case of a multilayer biaxially oriented polyester film, the film consists of two or more layers, such as two to ten layers, preferably three layers, adjacent to each other. If the multilayer film is a three-layer film, it preferably has a membrane structure of ABA or ABC. In this multilayer film, the core layer is preferably porous, that is, a layer containing the at least one polyester and the surface-treated filler material product. In one embodiment, the multilayer film includes a barrier layer located between two adjacent layers. As used herein, a "barrier layer" refers to a diffusion barrier, such as an oxygen and / or water vapor barrier, used to protect packaged articles from various external influences.

[0302] The barrier layer can be any material known in the art suitable for this purpose. For example, the barrier layer can be an aluminum layer, an Al2O3 layer, or a SiO2 layer. x Layers, including ethylene-vinyl alcohol layers, poly(vinyl alcohol) layers, or polyvinylidene chloride layers, polypropylene layers, preferably oriented polypropylene layers, polyethylene layers, preferably oriented polyethylene layers, and polyester barrier layers, for example... Those trademarks sold, and their mixtures.

[0303] It should be understood that the median thickness of the single-layer or multi-layer biaxially oriented polyester film, especially the layer containing surface-treated filler material, can vary within a wide range, depending on the product to be produced.

[0304] For example, the layer comprising at least one polyester and a surface-treated filler material is preferably thicker than other individual layers (i.e., layers that do not contain the at least one polyester and / or the surface-treated filler material). Alternatively, the layer comprising at least one polyester and a surface-treated filler material has substantially the same thickness as other individual layers (i.e., layers that do not contain the at least one polyester and / or the surface-treated filler material, preferably the at least one polyester and the surface-treated filler material).

[0305] Preferably, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a median thickness of 0.5-500 μm, preferably 4-400 μm, more preferably 5-300 μm, and most preferably 6-250 μm, for example 8-150 μm.

[0306] The single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, is advantageous because it is a well-balanced microporous membrane / layer. That is, it provides a microporous membrane or layer, achieved by controlling the formation of pores, with a low density and opaque appearance.

[0307] Therefore, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, preferably has

[0308] a) 0.8-1.4 g / cm³ 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 density, and / or

[0309] b) Opacity ≥50%, preferably ≥55%, and most preferably ≥60%.

[0310] For example, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, preferably has

[0311] a) 0.8-1.4 g / cm³ 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 density, or

[0312] b) Opacity ≥50%, preferably ≥55%, and most preferably ≥60%.

[0313] Unless otherwise specified, the mechanical and optical properties described herein refer to layers or films comprising polyester and surface-treated filler materials prepared according to the examples described below (i.e., by using a biaxial laboratory stretching frame (Model Maxi Grip750S Bi-axial Laboratory Stretching Frame, Dr. Collin GmbH, Germany) under the described conditions. Therefore, it should be understood that the results of layers or films comprising polyester and surface-treated filler materials prepared under different conditions may deviate from the mechanical and optical properties defined herein.

[0314] Furthermore, the single-layer or multi-layer biaxially oriented polyester film, especially the layer containing at least one polyester and a surface-treated filler material, is advantageous because the mechanical properties of the film (especially the layer) are maintained at a high level.

[0315] For example, in the range of 0.8-1.4 g / cm³ 3 The preferred concentration is 0.8-1.38 g / cm³.3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 At a given density, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a longitudinal tensile strength measured according to ISO 527-3 in the range of 80-200 MPa, more preferably in the range of 90-190 MPa, and most preferably in the range of 100-180 MPa.

[0316] Additionally or alternatively, at 0.8-1.4 g / cm³ 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 At a given density, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a transverse tensile strength measured according to ISO 527-3 in the range of 80-200 MPa, more preferably in the range of 90-180 MPa, and most preferably in the range of 100-160 MPa.

[0317] In one implementation scheme, the concentration is 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 At a given density, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a longitudinal modulus of elasticity measured according to ISO 527-3 in the range of 2,000-5,000 MPa, more preferably in the range of 2,200-4,500 MPa, and most preferably in the range of 2,400-4,000 MPa.

[0318] Additionally or alternatively, at 0.8-1.4 g / cm³ 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3And the optimal value is 0.85-1.28 g / cm³. 3 At a given density, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a transverse modulus of elasticity measured according to ISO 527-3 in the range of 2,000-5,000 MPa, more preferably in the range of 2,200-4,500 MPa, and most preferably in the range of 2,400-4,000 MPa.

[0319] In one implementation scheme, the concentration is 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 At a given density, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a maximum elongation at break in the longitudinal direction, measured according to ISO 527-3, in the range of 40-90%, more preferably in the range of 45-80%, and most preferably in the range of 50-70%.

[0320] Additionally or alternatively, at 0.8-1.4 g / cm³ 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 At a given density, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, has a maximum elongation at break in the transverse direction in the range of 40-90%, more preferably 45-80%, and most preferably 50-75%, as determined according to ISO 527-3.

[0321] Furthermore, it should be understood that the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, is microporous and has good optical properties.

[0322] The microporosity of the single-layer or multi-layer biaxially oriented polyester film, particularly the layer comprising at least one polyester and a surface-treated filler material, can be determined by its water vapor transmission rate. According to one embodiment, the single-layer or multi-layer biaxially oriented polyester film, particularly the layer comprising at least one polyester and a surface-treated filler material, has a microporosity of less than 100 g / (m³) as measured according to ASTM E398 using a Lyssy L80-5000 measuring device. 2 • (day), preferably 20-100g / (m 2 Water vapor transmission rate (WVTR) per day.

[0323] According to one embodiment, the single-layer or multi-layer biaxially oriented polyester film, particularly a layer comprising at least one polyester and a surface-treated filler material, preferably has a density of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 It has a whiteness Ry of 50-100%, preferably 60-98%, and most preferably 70-96% according to DIN 53163 at a density of .

[0324] Additionally or alternatively, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, preferably has a density of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 L* according to DIN 6174 has a density of 60-100, preferably 70-100 and most preferably 80-98.

[0325] Additionally or alternatively, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, preferably has a density of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3It has an opacity of ≥50%, preferably ≥55%, and most preferably ≥60% according to DIN 53146 at a given density.

[0326] Additionally or alternatively, the single-layer or multi-layer biaxially oriented polyester film, especially the layer comprising at least one polyester and a surface-treated filler material, preferably has a density of 0.8-1.4 g / cm³. 3 The preferred concentration is 0.8-1.38 g / cm³. 3 More preferably 0.85-1.35 g / cm³ 3 Even more preferred is 0.85-1.32 g / cm³. 3 And the optimal value is 0.85-1.28 g / cm³. 3 It has a transmittance of 2-60%, preferably 3-40%, and most preferably 4-25% according to ASTM D1003 at a density of .

[0327] According to one embodiment, the single-layer or multi-layer biaxially oriented polyester film, comprising at least one polyester and a surface-treated filler material product, further comprises a thermoplastic polymer preferably crosslinked with a crosslinking agent, selected from polyolefins, cyclic olefin copolymers (COC), polyketones, polysulfones, fluoropolymers, polyacetals, ionomers, acrylic resins, polystyrene resins, polyurethanes, polyamides, polycarbonates, polyacrylonitrile, and copolymer resins and mixtures thereof.

[0328] Therefore, if the single-layer or multi-layer biaxially oriented polyester film contains a thermoplastic polymer, the thermoplastic polymer exists in the same layer as the at least one polyester and the surface-treated filler material product.

[0329] It should be understood that the presence of the thermoplastic polymer in the layer of the monolayer or multilayer biaxially oriented polyester film comprising at least one polyester and a surface-treated filler material is advantageous because it acts as an organic porosimeter during the preparation of the film or layer and thus improves the formation of pores. However, the thermoplastic polymer typically does not contribute to increasing the opacity of the film or layer.

[0330] It should be noted that the thermoplastic polymer is insoluble in the at least one polyester. Therefore, the at least one polyester forms a continuous phase, i.e., a matrix, and the thermoplastic polymer is dispersed therein, i.e., a dispersed phase is formed.

[0331] The polyolefins that can be used are preferably selected from polypropylene, polyethylene, polybutene, and mixtures thereof.

[0332] The polyolefin can be a copolymer or a homopolymer, with the latter being particularly preferred.

[0333] When the polyolefin is a copolymer, the polyolefin is preferably selected from ethylene-vinyl acetate, ethylene-vinyl alcohol copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic acid copolymer, and mixtures thereof.

[0334] In one embodiment, the thermoplastic polymer is polypropylene, preferably a propylene homopolymer.

[0335] The thermoplastic polymer, as a polyolefin, preferably has a melt flow rate MFR2 (230°C; 2.16 kg) of 1-20 g / 10 min as measured according to ISO 1133, more preferably 1-15 g / 10 min, more preferably 1-10 g / 10 min, and most preferably 1-5 g / 10 min.

[0336] Additionally or alternatively, the thermoplastic polymer, as a polyolefin, preferably has a content of <920 g / cm³. 3 More preferably <910g / cm 3 Even better is 800-920g / cm³ 3 Even better, 850-910 g / cm³ 3 And the optimal value is 880-910 g / cm³. 3 The density.

[0337] If polyolefins such as polypropylene are used as pore-forming agents, it should be noted that polyolefins are generally not well dispersed and compatibilizers such as carboxylated polyethylene may be required to obtain a uniform pore distribution. When used with at least one polyester to produce a pore-forming film, polyolefins also tend to reduce the surface tension of the polyester film, thereby reducing its printability. Polyolefins are softer than at least one polyester at room temperature, which can sometimes reduce the overall modulus of the film to unacceptable levels. Finally, polyolefins are relatively inefficient pore-forming agents and require large amounts to achieve the necessary density reduction, resulting in poor surface roughness and printability problems, thus making it difficult to use polyolefins in monolayer films.

[0338] In the context of this invention, a cyclic olefin copolymer (COC) refers to a copolymer of ethylene with at least one cyclic olefin selected from bicyclic and tricyclic olefins.

[0339] Typical examples of cyclic olefin copolymers (COCs) include bicyclo[2.2.1]hept-2-ene, 6-methylbicyclo[2.2.1]hept-2-ene, 5,6-dimethylbicyclo[2.2.1]hept-2-ene, 1-methylbicyclo[2.2.1]hept-2-ene, 6-ethylbicyclo[2.2.1]hept-2-ene, 6-n-butylbicyclo[2.2.1]hept-2-ene, 6-isobutylbicyclo[2.2.1]hept-2-ene, 7-methylbicyclo[2.2.1]hept-2-ene, and tricyclo[4.3.0.1]hept-2-ene. 2,5]-3-decene, 2-methyl-tricyclo[4.3.0.1 2,5 ]-3-decene, 5-methyl-tricyclo[4.3.0.1 2,5 ]-3-decene, tricyclic [4.4.0.1 2,5 ]-3-decene and 10-methyl-tricyclo[4.4.0.1 2,5 ]-3-decene.

[0340] The polyamides that can be used are preferably polyamide 6 (also known as nylon 6) or polyamide 66 (also known as nylon 66).

[0341] For example, the thermoplastic polymer is polypropylene, preferably a propylene homopolymer.

[0342] The single-layer or multi-layer biaxially oriented polyester film comprises at least one polyester and a surface-treated filler material product containing 0.1-29.9% by weight, preferably 1-28% by weight, more preferably 2-26% by weight, even more preferably 3-25% by weight, even more preferably 4.5-23% by weight, and most preferably 4-20% by weight of the thermoplastic polymer based on the total weight of the layer.

[0343] In one embodiment, the amount of thermoplastic polymer contained in the layer of the single-layer or multi-layer biaxially oriented polyester film comprising at least one polyester and a surface-treated filler material product is less than the amount of the surface-treated filler material product. For example, the amount of thermoplastic polymer contained in the layer of the single-layer or multi-layer biaxially oriented polyester film comprising at least one polyester and a surface-treated filler material product is at least 20% less by weight, more preferably at least 30% less by weight, and most preferably less than 50% less by weight, based on the total weight of the surface-treated filler material product.

[0344] Additionally or optionally, the layer of the membrane comprising at least one polyester and a surface-treated filler material product further comprises an inorganic filler material different from the surface-treated filler material product. Preferably, the inorganic filler material different from the surface-treated filler material product is selected from alumina, silica, titanium dioxide, alkali metal salts such as barium carbonate, calcium sulfate, barium sulfate, and mixtures thereof. Barium sulfate is particularly preferred as an inorganic filler material.

[0345] It should be understood that the presence of an inorganic filler material, different from the surface-treated filler material product, in the layer comprising at least one polyester and the surface-treated filler material product of the single-layer or multi-layer biaxially oriented polyester film is advantageous because it acts as an inorganic porosimeter during the preparation of the film and thus improves the formation of voids. Furthermore, the inorganic filler material, different from the surface-treated filler material product, further increases the opacity of the film or layer.

[0346] However, if the layer of the membrane comprising at least one polyester and a surface-treated filler material product further comprises an inorganic filler material different from the surface-treated filler material product, the amount of the inorganic filler material is typically lower than the amount of the surface-treated filler material product.

[0347] For example, the layer of the membrane comprising at least one polyester and a surface-treated filler material product comprises an amount of inorganic filler material different from the surface-treated filler material product, in a weight of 1-10% based on the total weight of the layer.

[0348] In one embodiment, the amount of inorganic filler material contained in the layer of the single-layer or multi-layer biaxially oriented polyester film comprising at least one polyester and a surface-treated filler material product, which is different from the surface-treated filler material product, is at least 20% less by weight, more preferably at least 30% less by weight, and most preferably at least 50% less by weight than the amount of the surface-treated filler material product, based on the total weight of the surface-treated filler material product.

[0349] The weight median particle size d of the inorganic filler material is different from that of the surface-treated filler material product. 50 Preferably, the median particle size d is similar to that of the surface-treated filler material product. 50 Therefore, the inorganic filler material, which differs from the surface-treated filler material product, preferably has a median weight particle size d. 50 The micrometer range is 0.5μm-2.5μm, preferably 0.5μm-2μm, more preferably 0.5μm-1.8μm, and most preferably 0.6μm-1.8μm.

[0350] Additionally or optionally, the single-layer or multi-layer biaxially oriented polyester film may further contain additives, which are typically used as additives in the film to be produced. Advantageously, these additives have been added to the polymer or polymer mixture prior to melting. Alternatively, the compounds may be added to the masterbatch.

[0351] For example, the single-layer or multi-layer biaxially oriented polyester film contains additives selected from light stabilizers, fluorescent whitening agents, blue dyes, antiblocking agents, white pigments, and mixtures thereof.

[0352] Preferably, the layer comprising at least one polyester and a surface-treated filler material contains additives selected from light stabilizers, fluorescent whitening agents, blue dyes, antiblocking agents, white pigments, and mixtures thereof.

[0353] It should be understood that light stabilizers (which are UV stabilizers or UV absorbers) are chemical additives that can intervene in the physical and chemical processes of photoinduced degradation. Carbon black and other pigments can provide a certain degree of protection against the adverse effects of light, but these substances are not suitable for white films because they can cause discoloration or fading. Additives suitable only for white films are organic or organometallic compounds that do not introduce color or color change into the film to be stabilized, or introduce color or color change only at extremely low levels. The light stabilizer (which is a suitable UV stabilizer) absorbs at least 70%, preferably at least 80%, particularly preferably at least 90% of UV light in the wavelength range of 180-380 nm, preferably 280-350 nm. Particularly suitable are those that are thermally stable in the temperature range of 260-300°C, i.e., do not decompose and do not release gases. Examples of suitable UV stabilizers include 2-hydroxybenzophenone, 2-hydroxybenzotriazole, organonickel compounds, salicylates, cinnamic acid ester derivatives, resorcinol monobenzoate, oxaloyl aniline, hydroxybenzoate, sterically hindered amines, and triazines, preferably 2-hydroxybenzotriazole and triazines. Most preferably, the light stabilizer is hydroxyphenyltriazine (…). 1577, BASF, Ludwigshafen, Germany). The amount of light stabilizer used is typically 10-50,000 ppm, preferably 20-30,000 ppm, and most preferably 50-25,000 ppm, based on the total weight of the film (preferably comprising at least one layer of polyester and a surface-treated filler material).

[0354] Additional additives present in the film (preferably a layer comprising at least one polyester and a surface-treated filler material) may be optical brighteners, if desired. The optical brightener according to the invention is capable of absorbing UV radiation in the wavelength range of about 360-380 nm and re-emitting it as visible, longer-wavelength blue-violet light. Suitable optical brighteners are bisbenzo[a]benzene[b] ... Azole, phenylcoumarin, and bis-stearylbiphenyl, especially phenylcoumarin, and particularly preferably triazine-phenylcoumarin ( BASF, Ludwigshafen, Germany). The amount of fluorescent whitening agent used is typically 10-50,000 ppm, preferably 20-30,000 ppm, and most preferably 50-25,000 ppm, based on the total weight of the film (preferably comprising at least one layer of polyester and a surface-treated filler material).

[0355] Suitable white pigments are preferably titanium dioxide, barium sulfate, calcium carbonate, kaolin, and silicon dioxide, with titanium dioxide and barium sulfate being the most preferred. The titanium dioxide particles may consist of anatase, brookite, or rutile, preferably primarily rutile, which has higher hiding power than anatase. In a preferred embodiment, 95% by weight of the titanium dioxide particles are rutile. The median particle size d of this white pigment is... 50 Typically lower than the median particle size d of this surface-treated filler material product. 50 Therefore, the white pigment does not act as a porositizer. Preferably, the median weight particle size d of the white pigment is... 50 The thickness is in the range of 0.10-0.30 μm. The amount of white pigment in the film (preferably comprising a layer of at least one polyester and a surface-treated filler material) is usefully 0.3-25% by weight based on the total weight of the film (preferably comprising a layer of at least one polyester and a surface-treated filler material).

[0356] Additionally or alternatively, a blue dye, preferably a blue dye soluble in polypropylene, may be added to the membrane (preferably comprising a layer of at least one polyester and a surface-treated filler material product), if this is useful. For example, proven successful blue dyes are selected from cobalt blue, ultramarine blue, and anthraquinone dyes, especially Sudan Blue 2 (BASF, Ludwigshafen, Germany). The amount of blue dye used, based on the total weight of the membrane (preferably comprising a layer of at least one polyester and a surface-treated filler material product), is typically 10-10,000 ppm, preferably 20-5,000 ppm, and most preferably 50-1,000 ppm.

[0357] Additionally or alternatively, an anti-blocking agent may be added to the film (preferably comprising a layer of at least one polyester and a surface-treated filler material product), if this is useful. Typical anti-blocking agents are inorganic and / or organic particles, such as calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, alumina, carbon black, titanium dioxide, and kaolin, different from the surface-treated filler material product, or cross-linked polymer particles, such as polystyrene, acrylate, PMMA particles, or cross-linked silicone. Muscovite with an average particle size (weighted average) of 4.0-12 μm, preferably 6-10 μm, is also particularly suitable. As is generally known, mica consists of sheet-like silicates with an aspect ratio preferably in the range of 5 to 50. As additives, mixtures of two or more different anti-blocking agents, or mixtures of anti-blocking agents with the same composition but different particle sizes, can also be selected. The particles can be added to the polymer of each layer of the film at their respective advantageous concentrations during the extrusion process, either directly or through the masterbatch.

[0358] The antiblocking agent is preferably added to the outer layer, i.e., the layer that does not contain the surface-treated filler material product. The amount of antiblocking agent is typically 0.01-1% by weight based on the total weight of the film (preferably comprising at least one polyester and a layer of surface-treated filler material product).

[0359] It should be understood that the compound used as an additive may be present in the layer comprising at least one polyester and a surface-treated filler material. In the case of a multilayer film, the compound used as an additive may be present in the layer comprising at least one polyester and a surface-treated filler material and / or at least one of the additional layers.

[0360] The single-layer or multi-layer biaxially oriented polyester film of the present invention can be produced by any method known in the art. According to one embodiment, a method for preparing a single-layer or multi-layer biaxially oriented polyester film includes the following steps:

[0361] a) Provides a composition comprising at least one polyester and a surface-treated filler material product, and

[0362] b) A film is formed from the composition of step a), and

[0363] c) Stretching the membrane obtained in step b) in the longitudinal (MD) and transverse (TD) directions in any order, wherein the stretching in the longitudinal (MD) and transverse (TD) directions is performed sequentially or simultaneously.

[0364] The surface-treated filler material product includes

[0365] A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and

[0366] B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising

[0367] i. Phosphate blends of one or more monophosphate esters and their salt reaction products and / or one or more diphosphate esters and their salt reaction products, and / or

[0368] ii. at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or

[0369] iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or

[0370] iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C2 to C3 in the substituents. 30 Composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups, and / or

[0371] v. at least one polydialkylsiloxane, and / or

[0372] vi. To mix the materials from i. to v.

[0373] The surface-treated filler material product comprises a treated layer comprising 0.1-2.3% by weight of the total dry weight of the at least one milled calcium carbonate filler material.

[0374] The composition of the at least one polyester and the surface-treated filler material product provided in step a) can be a compound obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture. The at least one polyester and the surface-treated filler material product, and other optional additives, if present, can be mixed and / or kneaded using a suitable mixer such as a Henschel mixer, super mixer, drum mixer, or similar mixer. The compounding step can be performed using a suitable extruder, preferably a twin-screw extruder (co-rotating or counter-rotating), or any other suitable continuous compounding equipment such as a continuous co-kneader (Buss), continuous mixer (Farrel Pomini), annular extruder (Extricom), or similar device. The continuous polymer blocks from the extrusion can be granulated using underwater granulation, eccentric granulation, and water ring granulation (hot-cut die face), or by underwater (cold-cut) wire granulation and conventional wire granulation to form pellets from the extruded polymer blocks. Therefore, the compound can be in the form of pellets, beads, or granules.

[0375] Preferably, the composition of the at least one polyester and the surface-treated filler material product provided in step a) is a compound obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture and continuously granulating the obtained mixture. For example, continuous granulation is carried out underwater.

[0376] Optionally, the mixing step can also be carried out in a discontinuous or intermittent process using a closed (batch) mixer such as a Banburry mixer (HF Mixing Group) or a Brabender mixer (Brabender) or similar mixer.

[0377] According to one embodiment, the compound comprises ≤30% by weight, preferably 0.5-30% by weight and more preferably 5-30% by weight of the surface-treated filler material product based on the total weight of the compound.

[0378] It should be understood that the composition provided in step a) is preferably prepared using polyester sheets, such as PET sheets. In this regard, preferably, the polyester sheets, such as PET sheets, are pre-dried to remove moisture before preparing the composition in step a). For example, the polyester sheets, such as PET sheets, are pre-dried at 90°C for 6 hours.

[0379] According to one optional embodiment, the composition provided in step a) further comprises one or more of the above-described additives / compounds.

[0380] According to one embodiment, the composition provided in step a) is a masterbatch. According to a preferred embodiment, the masterbatch comprises an amount of the surface-treated filler material product in a quantity between >30% and 85% by weight, preferably 35-80% by weight and more preferably 40-70% by weight, based on the total weight of the masterbatch. The masterbatch may be in the form of pellets, beads, or granules.

[0381] It should be understood that the masterbatch can be prepared by the same method as described for the above-described blends. Therefore, the masterbatch is preferably obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture. Preferably, the composition of the at least one polyester and the surface-treated filler material product provided in step a) is a masterbatch obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture and continuously granulating the obtained mixture.

[0382] It should be noted that this compound differs from the masterbatch in that the compound is not diluted during further processing. In other words, the masterbatch is diluted during further processing.

[0383] Filtration pressure testing was performed to determine dispersion quality. This filtration pressure test was conducted on a commercially available CollinPressure Filter Test Teach-Line FT-E20T-MP-IS. The test method was performed according to European Standard EN 13900-5 for each corresponding polymer composition (11.2 g effective calcium carbonate / 200 g final sample, diluent: PET), using a filter screen (approximately 15 μm sieve size) as described in Chapter 6.64 of the mentioned European Standard EN 13900-5, with the melt pump used at 10 rpm, the extruder speed adjusted to maintain a constant pressure of 20 bar before the melt pump, and the melt temperature set at 290°C. The quality of the mineral dispersion in the polymer matrix was determined by classification as good, medium, or low, corresponding to the obtained filtration pressure values ​​classified as low, medium, or high.

[0384] According to one embodiment, the masterbatch has a filtration pressure of 0.01-0.5 bar / g, preferably 0.01-0.15 bar / g, and most preferably 0.01-0.1 bar / g.

[0385] Alternatively, the mixture may have a filtration pressure of 0.01-0.5 bar / g, preferably 0.01 to 0.15 bar / g, and most preferably 0.01-0.1 bar / g.

[0386] The inventors of this invention have discovered that the use of the surface-treated filler material product of this invention in masterbatches can result in very fine and uniformly filled single-layer or multi-layer biaxially oriented polyester membranes. Another advantage of this surface-treated filler material product is that the resulting masterbatch provides low filtration pressure values. Without being bound by any theory, it is believed that the specific properties of the surface-treated filler material product according to this invention make it particularly suitable for use in single-layer or multi-layer biaxially oriented polyester membranes, which require filler that is distributed as uniformly as possible throughout the membrane to achieve uniform distribution of barrier and vapor permeation properties throughout the membrane. Furthermore, the inventors have discovered that the surface-treated filler material product of this invention enables the preparation of biaxially oriented polyester membranes without membrane rupture, and the resulting membranes have low membrane density at high opacity.

[0387] The masterbatch is preferably mixed with the same or different polyesters (such as those used as a matrix in the masterbatch) and / or one or more of the additives described above prior to step b). According to a preferred embodiment, the masterbatch is mixed with the same polyester (such as those used as a matrix in the masterbatch) prior to step b).

[0388] In one embodiment, additives typically used as additives are added to the masterbatch, such as light stabilizers, fluorescent whitening agents, blue dyes, antiblocking agents, white pigments, and mixtures thereof.

[0389] Alternatively, steps a) and b) can be performed simultaneously. Preferably, steps a) and b) are performed simultaneously, wherein the at least one polyester, more preferably a pre-dried polyester sheet such as a pre-dried PET sheet, and the surface-treated filler material product, more preferably a dried surface-treated filler material product, are directly added to the extruder to perform step b). That is, by directly adding the surface-treated filler material product, preferably a dried surface-treated filler material product, and the at least one polyester, more preferably a pre-dried polyester sheet such as a pre-dried PET sheet, to the extruder to perform step b), the composition of the at least one polyester and the surface-treated filler material product provided in step a) is obtained.

[0390] Alternatively, the composition comprising at least one polyester and the surface-treated filler material product of step a) can be obtained by adding the surface-treated filler material product to the polycondensation process of the at least one polyester. That is, the composition comprising at least one polyester and the surface-treated filler material product of step a) can be obtained by adding the surface-treated filler material product before, during, or after the polycondensation process of the at least one polyester. For example, the composition comprising at least one polyester and the surface-treated filler material product of step a) can be obtained by adding the surface-treated filler material product before, after, preferably after, the polycondensation process of the at least one polyester. Therefore, the composition comprising at least one polyester and the surface-treated filler material product of step a) can be provided in the form of a ready-to-use composition.

[0391] Step b) can be performed using any known technique for preparing polymer films. Examples of suitable film extrusion techniques are blown film extrusion or cast film extrusion. Preferably, step b) is performed by cast film extrusion.

[0392] Therefore, step b) is preferably an extrusion process.

[0393] In the preferred extrusion process for forming the film, the molten composition of the at least one polyester and the surface-treated filler material product provided in step a) is extruded through a slot die and quenched on a cooling roller in the form of a substantially amorphous prefilm.

[0394] In step c), the membrane obtained in step b) is stretched in any order along the longitudinal (MD) and transverse (TD) directions.

[0395] For example, the membrane obtained in step b) is reheated and stretched in both the longitudinal (MD) and transverse (TD) directions; or in both the transverse (TD) and longitudinal (MD) directions; or in both the longitudinal (MD) and transverse (TD) directions and also in both the longitudinal (MD) and / or transverse (TD) directions. Preferably, the membrane obtained in step b) is reheated and stretched in both the longitudinal (MD) and transverse (TD) directions.

[0396] Therefore, the stretching in the longitudinal (MD) and transverse (TD) directions in step c) can be performed sequentially, simultaneously, or using the LISIM method or a combination thereof. Preferably, the stretching in the longitudinal (MD) and transverse (TD) directions in step c) is performed sequentially.

[0397] The stretching step c) can be performed by any means known in the art. Such methods and apparatus for performing the stretching step c) are known in the art, for example, the known LISIM or MESIM methods (mechanical simultaneous stretching). The LISIM procedure is described in detail in EP 1112167 and EP 0785858, which are incorporated herein by reference. The MESIM method is described in US2006 / 0115548, which is also incorporated herein by reference. For example, the simultaneous biaxial stretching process can be performed by an intermittent type biaxial stretching machine such as the Model Maxi Grip 750S (from Dr. Collin GmbH, Germany) or the Brückner Karo IV (from Brückner Maschinenbau GmbH&Co.KG, Germany). This stretching process causes the membrane to become anisotropic due to molecular orientation.

[0398] If necessary, the first stretching in the longitudinal direction (MD) can be performed simultaneously with the stretching in the transverse direction (TD). The film is then heat-set at an oven temperature of 200-260°C, particularly 220-250°C. It is then cooled and wound into a film.

[0399] During the stretching step, the polyester can be peeled off from the surface of the surface-treated filler material product, thereby creating voids in a single or multilayer biaxially oriented polyester film.

[0400] The stretching can be performed in one step or in multiple steps. According to one embodiment, step c) is performed 1-10 times.

[0401] The stretch ratio determines the membrane rupture under high stretching and the resulting membrane's air permeability and water vapor transmission rate, and it is desirable to avoid excessively high stretch ratios as well as excessively low stretch ratios. According to one embodiment, in method step c), the membrane obtained in step b) is stretched to a stretch ratio of 1.2-6 times, more preferably 1.2-4 times, in each direction.

[0402] Preferably, the stretching step c) involves stretching the membrane obtained in step b) in the following manner:

[0403] a) with a draw ratio of 2-6, preferably 3-4.5, in the longitudinal direction (MD), and / or

[0404] b) With a draw ratio of 2-5, preferably 3-4.5, in the transverse (TD) direction, and

[0405] c) Optionally, for any second stretch in the longitudinal direction (MD), the stretch ratio is 1.1-3.

[0406] For example, stretching step c) involves stretching the membrane obtained in step b) in the following manner:

[0407] a) with a draw ratio of 2-6, preferably 3-4.5, in the longitudinal direction (MD), and

[0408] b) With a draw ratio of 2-5, preferably 3-4.5, in the transverse (TD) direction, and

[0409] c) Optionally, for any second stretch in the longitudinal direction (MD), the stretch ratio is 1.1-3.

[0410] According to one implementation scheme, method step c) is in T g +10℃ to T g +60℃(T g The stretching is carried out at the glass transition temperature (= glass transition temperature).

[0411] When the biaxially oriented polyester film is a multilayer biaxially oriented polyester film, the film can be prepared by co-extrusion or by laminating several layers before or after the stretching step c) (extrusion lamination). Preferably, the multilayer biaxially oriented polyester film is prepared by laminating several layers after the stretching step c). In one embodiment, a barrier layer is introduced between the layers of the multilayer biaxially oriented polyester film. For example, the multilayer biaxially oriented polyester film includes an aluminum layer, an Al2O3 layer, and a SiO2 layer located between two adjacent layers. x Layer, ethylene vinyl alcohol layer, poly(vinyl alcohol) layer, polyvinylidene chloride layer, polypropylene layer (preferably oriented polypropylene layer), polyethylene layer (preferably oriented polyethylene layer), polyester barrier layer (e.g., using... (Those sold under trademarks) and their mixtures. Therefore, this biaxially oriented polyester film can be prepared by adding a barrier layer during the lamination step.

[0412] The inventors of this invention have discovered that the single-layer or multi-layer biaxially oriented polyester film according to the invention, particularly the layer comprising at least one polyester and a surface-treated filler material, is highly microporous, especially with a density lower than that typically achieved by biaxially oriented films or layers using barium sulfate or titanium dioxide as porosifectants. Furthermore, the biaxially oriented polyester film, particularly the layer comprising at least one polyester and a surface-treated filler material, has an opaque appearance and can be prepared without film / layer breakage. Moreover, the single-layer or multi-layer biaxially oriented polyester film, particularly the layer comprising at least one polyester and a surface-treated filler material, provides good mechanical properties such as tensile strength, elongation at break, or modulus of elasticity, as well as optical properties such as gloss and light transmittance.

[0413] The single-layer or multi-layer biaxially oriented polyester film according to the invention can be used in many different applications. According to one embodiment, the single-layer or multi-layer biaxially oriented polyester film is used in: packaging products, preferably flexible packaging products, food contact applications, paper and glass coverings, insulating or heat-insulating materials, solar energy, preferably photovoltaic front and back sheets, marine and aerospace applications, scientific, electronic and acoustic applications, preferably displays, wires, cables, radio frequency identification, flexible circuits, graphic art, preferably labels, paper alternatives and holograms, filtration products, cosmetics, household products, imaging and recording media, preferably photographic paper, X-ray film and thermal transfer imaging or industrial products, preferably capacitors, release sheets, fiberglass boards, laminates, hot-stamped foils and insulating or heat-insulating finishes.

[0414] According to a further aspect of the invention, articles comprising a single or multiple biaxially oriented polyester film according to the invention are provided, wherein the articles are selected from packaging products, preferably flexible packaging products, food contact applications, paper and glass coverings, insulating or heat-insulating materials, solar energy, preferably photovoltaic front and back sheets, marine and aerospace applications, scientific, electronic and acoustic applications, preferably displays, wires, cables, radio frequency identification, flexible circuits, graphic art, preferably labels, paper alternatives and holograms, filtration products, cosmetics, household products, imaging and recording media, preferably photographic paper, X-ray film and thermal transfer imaging and industrial products, preferably capacitors, release sheets, fiberglass boards, laminates, hot stamping foils and insulating or heat-insulating finishes. Detailed Implementation

[0415] 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.

[0416] Example

[0417] 1. Determination methods and materials

[0418] The measurement methods and materials implemented in the examples are described below.

[0419] Intrinsic viscosity

[0420] Intrinsic viscosity was measured according to DIN ISO 1628 / 1 and DIN ISO 1628 / 5 (October 1999) (in naphthalene at 135°C).

[0421] MFR2

[0422] MFR2 was measured according to ISO 1133 (230°C, 2.16 kg load).

[0423] Crystallization temperature T c

[0424] Crystallization temperatures were measured by differential scanning calorimetry (DSC) on a Mettler-Toledo Polymer DSC Instrument (Mettler-Toledo (Schweiz) GmbH, Switzerland). Crystallization profiles were obtained during cooling at 10 °C / min and heating between 30 °C and 225 °C. Crystallization temperatures were obtained as endothermic and exothermic peaks.

[0425] Particle size

[0426] The particle distribution of the untreated filler material containing ground calcium carbonate was measured using a Sedigraph 5120 from Micromeritics, USA. The methods and instruments are known to those skilled in the art and commonly used to determine the particle size of fillers and pigments. Measurements were performed in an aqueous solution containing 0.1% by weight of Na₄P₂O₇. The sample was dispersed using a high-speed stirrer and ultrasonication.

[0427] Specific surface area (BET)

[0428] Throughout this document, the specific surface area (in m²) of the filler material is determined using the BET method (using nitrogen as the adsorption gas), which is well-known to those skilled in the art. 2 (in g) (ISO 9277:2010).

[0429] Filter pressure value

[0430] Filtration pressure tests were conducted on the commercially available Collin Pressure Filter Test Teach-LineFT-E20T-MP-IS (Dr. Collin GmbH, Germany). The test method was performed according to European Standard EN 13900-5 for each corresponding polymer composition (11.2 g effective calcium carbonate / 200 g final sample, diluent: PET), using a filter screen (approximately 15 μm sieve size) as described in Chapter 6.64 of the mentioned European Standard EN 13900-5, with the melt pump used at 10 rpm, the extruder speed adjusted to maintain a constant pressure of 20 bar before the melt pump, and the melt temperature set at 290 °C. The quality of the mineral dispersion in the polymer matrix was determined by classification as good, medium, or low, corresponding to the obtained filtration pressure values ​​classified as low, medium, and high.

[0431] Ash content

[0432] The ash content of the masterbatch and membrane, expressed as a percentage by weight, was determined by incinerating the sample in an incineration crucible placed in an incinerator at 570°C for 2 hours. The ash content was measured as the total amount of remaining inorganic residue.

[0433] Film thickness

[0434] Film thickness was determined using a digital measuring slider, Mitutoyo IP 66 (Mitutoyo Europe GmbH, Neuss, Germany). Measurements are expressed in μm.

[0435] Density of membrane or layer

[0436] Density was determined by a test piece, from which a precise area of ​​the membrane (100 mm × 100 mm) was cut and weighed on an analytical balance. The average membrane thickness was determined by obtaining nine thickness measurements taken across the entire membrane surface. Density was calculated and expressed in g / cm³. 3 This can be represented as ) . It can also be calculated from these values ​​in m 2 Average yield in units of / kg and in units of g / m 2 Unit weight is expressed in units of 1.

[0437] Whiteness Ry

[0438] Colorimetric values ​​were measured using a Datacolor Elrepho spectrometer (Datacolor AG, Switzerland), Ry was measured according to DIN 53163, and CIELAB color differences L*, a*, and b* were determined according to DIN 6174.

[0439] 60° (20°, 85°) gloss

[0440] Gloss was measured at 60°, but could also be measured at 20° or 85°. All measurements were performed according to ISO 2813 using a triangular gloss meter (Byk-Gardner GmbH, Germany).

[0441] Opacity

[0442] Opacity measurements were performed according to DIN 53146 using the Byk-Gardner Spectro-Guide (Byk-Gardner GmbH, Germany) to measure the whiteness of film samples on black and white substrates. Opacity is a comparison of the two measurements. The unit is percentage (%), and a completely opaque material will have an opacity value of 100%.

[0443] transmittance

[0444] Transmittance (transparency) is the ratio of total transmitted light to incident light. Transmittance is measured using the haze-guardplus testing equipment (Byk Gardener, Germany) according to ASTM D1003.

[0445] Tensile strength

[0446] The tensile properties of the produced membrane samples were tested according to ISO 527-3 on a Zwick / Roell Allround Z020 device (Zwick GmbH & Co. KG, Germany). Tensile tests were performed on samples obtained in the longitudinal (MD) and transverse (TD) directions. At least five samples were tested for each formulation, and the average value was calculated. The tensile modulus [MPa], tensile strength [MPa], and elongation at break [%) were recorded. The membrane sample dimensions were 15 mm × 170 mm, and the test length was 5 cm.

[0447] Maximum elongation at break

[0448] The elongation at break was determined according to ISO 527-3. The membrane sample width was 15 mm and the test length was 5 cm.

[0449] Tensile E-modulus (elastic modulus)

[0450] The tensile E-modulus was determined according to ISO 527-3. The membrane specimen width was 15 mm and the test length was 5 cm. The E-modulus corresponds to the angle of inclination of the tensile test curve between the points of 0.02% and 2% elongation.

[0451] Water vapor transmission rate (WVTR)

[0452] The WVTR value of the polyester film was measured according to ASTM E398 using a Lyssy L80-5000 measuring device (PBI-Dansensor A / S, Denmark).

[0453] 2 materials

[0454] CC1 (This invention): Naturally ground calcium carbonate, a stone available commercially from Omya International AG, Switzerland (d 50 : 0.8μm; d 98 : 3μm, particle content <0.5μm = 35%), surface treated with 1.7% by weight stearic acid (available from Sigma-Aldrich, Croda), based on the total weight of the natural milled calcium carbonate. BET: 8.5m 2 / g.

[0455] CC2 (This invention): Naturally ground calcium carbonate, a stone available commercially from Omya International AG, Switzerland (d 50 : 1.7μm; d 98 : 6μm, particle content <0.5μm = 12%), surface treated with 0.7% by weight of alkenyl succinic anhydride (CAS [68784-12-3], concentration >93%), based on the total weight of the natural ground calcium carbonate. BET: 3.4m 2 / g.

[0456] CC3 (comparison): Naturally ground calcium carbonate, available commercially from Omya International AG in Switzerland (d 50 3μm; d 98 : 12.5μm, particle content <2μm = 33%), surface treated with 0.5% by weight of alkenyl succinic anhydride (CAS [68784-12-3], concentration >93%), based on the total weight of the natural ground calcium carbonate. BET: 2m 2 / g.

[0457] CC4 (comparison): Naturally ground calcium carbonate, available commercially from Omya International AG in Switzerland (d 50 : 6.5μm; d 98 : 32μm, particle content <2μm = 20%), surface treated with 0.4% by weight of stearic acid (available from Sigma-Aldrich, Croda), based on the total weight of the natural milled calcium carbonate. BET: 1m 2 / g.

[0458] CC5 (comparison): Naturally ground calcium carbonate, available commercially from Omya International AG in Switzerland (d 50 : 0.8μm; d 98 : 3μm, particle content <0.5μm = 35%), surface treated with 2.4% by weight of stearic acid (available from Sigma-Aldrich, Croda), based on the total weight of the natural milled calcium carbonate. BET: 8.5m 2 / g.

[0459] CC6 (This Invention): Naturally ground calcium carbonate, a stone available commercially from Omya International AG, Switzerland (d 50 : 0.8μm; d 98: 3μm, particle content <0.5μm = 35%), surface treated with 1.7% by weight of alkenyl succinic anhydride (CAS [68784-12-3], concentration >93%), based on the total weight of the natural ground calcium carbonate. BET: 8.5m 2 / g.

[0460] Surface treatment of CC1 to CC6 is performed using the method described in EP 2 722 368 A1.

[0461] CMB1: White masterbatch for PET. T cc S528, available commercially from Sukano AG in Switzerland, is 50% barium sulfate in PET.

[0462] CMB2: White masterbatch for PET. T cc S204, commercially available from Sukano AG in Switzerland, contains 65% titanium dioxide in PET.

[0463] CMB3: Fluorescent whitening agent masterbatch for PET. To ob S354-OB is available from Sukano AG in Switzerland.

[0464] P1: Polyethylene terephthalate (PET), Plastivrd Global PET, available from PLASTIVERD, PET Reciclado, SA, El Prat del Llobregat, Spain (intrinsic viscosity: 0.78-0.82 dl / g, crystalline polymer, according to technical data sheet).

[0465] P2: Polypropylene homopolymer Polypropylene PPH 3060 (MFR2: 1.8 g / 10 min (230℃, 2.16 kg), density: 0.905 g / cm³) 3 (Based on the technical data sheet), it is available commercially from Total Petrochemicals.

[0466] 3 Examples

[0467] Example 1 - Preparation of Masterbatch

[0468] A masterbatch containing P1 and one of the calcium carbonate fillers CC1-CC6 was prepared on a laboratory-scale twin-screw extruder (ZSE27HP-40D from Leistritz, Germany). The polymer PET was pre-dried in an oven at 90°C for 6 hours prior to processing. The composition of the prepared masterbatch and the filler content are summarized in Table 1 below. The precise filler content was determined by the ash content.

[0469] Table 1 The composition and filler content of the prepared masterbatch

[0470] Masterbatch filler Filler content [% by weight] Ash content [% by weight] Mineral dispersion quality MB1 (This invention) CC1 45 37.4 good MB2 (This invention) CC2 45 39.3 good MB3 (Comparison) CC3 45 39.3 Low MB4 (Comparison) CC4 45 39.8 Low MB5 (Comparison) CC5 45 39.5 Low MB6 (This invention) CC6 45 40.1 good

[0471] The results shown in Table 1 confirm the production of MB1, MB2, and MB6, which are of good quality and have minerals that are well dispersed in the polymer.

[0472] Example 2 - Preparation of Polyester Cast Film

[0473] Cast films were prepared at the Collin Laboratory Film Line (Dr. Collin GmbH, Germany) using a twin-screw extruder with a 30 mm wide T-die and a winding system with temperature-controlled cooling rollers. The cooling rollers were kept 20 mm away from the T-die to produce polyester sheets with a thickness of approximately 500 μm. The extruder and die temperatures were maintained consistently throughout the experiment. The die temperature was set at 270 °C; the line speed was 0.5 m / min. Masterbatch or polymer was mixed with pure, pre-dried polymer P1 to receive cast films with the concentrations provided in Table 2.

[0474] Table 2: Composition and properties of the prepared cast film

[0475]

[0476] All the films shown in Table 2 are cast films, which are produced with good quality and have a visually appealing appearance.

[0477] Example 3 - Preparation of biaxially oriented polyester film

[0478] The cast film was stretched using a biaxial laboratory stretching frame (Model Maxi Grip 750S, Dr. Collin GmbH, Germany). The cast film, measuring 135mm × 135mm and approximately 500μm thick (precise values ​​provided in Table 2), was held in a 9×9 clamp and heated to 90°C (measured on the cast film surface) using an infrared system. A fixed preheating time of 2 minutes was applied before stretching, followed by a stretching speed of 6000mm / s, resulting in a speed of 345mm / s x 345mm / s. 2 x 6000mm / s 2 The film was stretched to the final draw ratio using simultaneous biaxial stretching. After stretching to the final size, the film was immediately air-cooled to room temperature by a fan and then removed from the stretching machine. The film was stretched to the target draw ratio of 3.3 × 3.3 (230% × 230%). The draw ratio and temperature remained constant for all samples.

[0479] The physical, optical, and barrier properties of the obtained alignment films are summarized in Table 3.

[0480] The mechanical properties of the obtained oriented films, such as tensile strength at break, E-modulus, and elongation at break (in the longitudinal (MD) and transverse (TD) directions), are summarized in Table 4.

[0481] The results shown in Tables 3 and 4 confirm that the oriented polyester film of the present invention has good quality, reduced density, and high opacity. The film of the present invention also has high whiteness, good barrier properties, and good mechanical properties.

[0482] By comparing the results shown in Table 3, from membrane sample 3 (comparison, containing 18% CMB1) to membrane sample 8 (in this invention, 18% MB1), membrane sample 12 (in this invention, 18% MB2), and membrane sample 16 (in this invention, 18% MB6), all oriented membranes contained the same amount (filler content) of porosifectant. The density of the membranes of this invention (membrane samples 8, 12, and 16) was reduced to 1.19-1.23 g / cm³. 3 The density of the control membrane (membrane sample 3) was 1.38 g / cm³. 3 These membranes (even with such significant porosity) exhibit reduced density, high opacity, and low light transmittance. The membranes of the present invention (membrane samples 8, 12, and 16) have an opacity of 92-97%, which is comparable to or better than the 92% opacity of the comparative membrane (membrane sample 3).

[0483] By comparing the results shown in Table 3, from membrane sample 2 (comparison, containing 10% CMB1) to membrane sample 6 (in this invention, 10% MB1), membrane sample 10 (in this invention, 10% MB2), and membrane sample 14 (in this invention, 10% MB6), all oriented membranes contain the same amount (filler content) of porosifectant. The membranes of this invention (membrane samples 6, 10, and 14) have a density of 1.26-1.32 g / cm³. 3 The density of the control membrane (membrane sample 2) was 1.29 g / cm³. 3 This means that, at the same level, the opacity of the membranes of the present invention (membrane samples 6, 10 and 14) is 82-89%, which is much higher than the opacity of the control membrane (membrane sample 2) (only 44%).

[0484] Table 3 The physical, optical, and barrier properties of the prepared biaxially stretched polyester film

[0485]

[0486] # Gloss unit

[0487] Table 4 Mechanical properties of the prepared biaxially stretched polyester film: film samples obtained in the longitudinal (MD) and transverse (TD) directions.

[0488]

Claims

1. A single-layer or multi-layer biaxially oriented polyester film, wherein at least one layer of the film comprises at least one polyester in an amount of 80-96% by weight based on the total weight of the layer and 4-20% by weight of a surface-treated filler material product, wherein the surface-treated filler material product comprises A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C4 to C6 in the substituents. 20 It is composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups. The surface-treated filler material product comprises a treated layer comprising 0.5-1.8% by weight of the total dry weight of the at least one milled calcium carbonate filler material, and The membrane has the following properties: a) 0.8-1.4 g / cm³ 3 a) density, and / or b) opacity ≥ 50%.

2. The single-layer or multi-layer biaxially oriented polyester film of claim 1, wherein the at least one polyester is selected from polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanate (PEF), bio-based polyesters, recycled PET materials, and mixtures thereof.

3. The single-layer or multi-layer biaxially oriented polyester film according to claim 1 or 2, wherein the at least one milled calcium carbonate-containing filler material is a wet-milled or dry-milled calcium carbonate-containing filler material.

4. The single-layer or multi-layer biaxially oriented polyester film according to claim 1 or 2, wherein the at least one milled calcium carbonate-containing filler material is natural milled calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface-treated calcium carbonate, or a mixture thereof.

5. The single-layer or multi-layer biaxially oriented polyester film according to claim 1 or 2, wherein the at least one milled calcium carbonate-containing filler material has a) Median particle size d 50 0.5μm-2μm, and / or b) Top-cut particle size d 98 ≤15μm, and / or c) Ensuring that at least 15% of the weight of all particles has a particle size of <0.5 μm, and / or d) Specific surface area (BET) is 0.5-150 m² 2 / g, as measured using the nitrogen and BET method according to ISO 9277.

6. The single-layer or multi-layer biaxially oriented polyester film of claim 1 or 2, wherein the layer of the film comprising at least one polyester and a surface-treated filler material product further comprises a thermoplastic polymer selected from polyolefins, cyclic olefin copolymers (COC), polyketones, polysulfones, fluoropolymers, polyacetals, ionomers, acrylic resins, polystyrene resins, polyurethanes, polyamides, polycarbonates, polyacrylonitrile, and copolymer resins, and mixtures thereof, dispersed in the at least one polyester.

7. The single-layer or multi-layer biaxially oriented polyester film of claim 6, wherein the layer of the film comprising at least one polyester and a surface-treated filler material comprises 0.1-29.9% by weight of the thermoplastic polymer based on the total weight of the layer.

8. The single-layer or multi-layer biaxially oriented polyester film according to claim 1 or 2, wherein the film has a) 0.8-1.38 g / cm³ 3 density, and / or b) Opacity ≥ 55%.

9. The single-layer or multi-layer biaxially oriented polyester film of claim 1 or 2, wherein the layer of the film comprising at least one polyester and a surface-treated filler material product further comprises an inorganic filler material different from the surface-treated filler material product.

10. The single-layer or multi-layer biaxially oriented polyester film of claim 1 or 2, wherein the film contains additives selected from light stabilizers, fluorescent whitening agents, blue dyes, anti-blocking agents, white pigments, and mixtures thereof.

11. A method for producing single-layer or multi-layer biaxially oriented polyester films, comprising the following steps: a) Provides a composition comprising at least one polyester and a surface-treated filler material product, and b) A film is formed from the composition of step a), and c) Stretching the membrane obtained in step b) in the longitudinal (MD) and transverse (TD) directions in any order, wherein the stretching in the longitudinal (MD) and transverse (TD) directions is performed sequentially or simultaneously. The surface-treated filler material product includes A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C4 to C6 in the substituents. 20 It is composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups. The surface-treated filler material product comprises a treated layer comprising 0.5-1.8% by weight of the total dry weight of the at least one milled calcium carbonate filler material; and The membrane comprises at least one polyester comprising 80-96% by weight of the total weight of the layer and 4-20% by weight of a surface-treated filler material product.

12. The method of claim 11, wherein the composition provided in step a) is a masterbatch obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture and continuously granulating the obtained mixture.

13. The method of claim 11 or 12, wherein the composition provided in step a) is a masterbatch having a filtration pressure of 0.01-0.5 bar / gram.

14. The method of claim 11, wherein the composition provided in step a) is obtained by mixing and / or kneading the at least one polyester and the surface-treated filler material product to form a mixture and continuously granulating the obtained mixture.

15. The method of claim 11 or 14, wherein the composition provided in step a) is a mixture having a filtration pressure of 0.01-0.5 bar / gram.

16. The method of claim 13, wherein the composition provided in step a) is a masterbatch comprising an amount of the surface-treated filler material product in an amount of >30 to 85% by weight based on the total weight of the masterbatch.

17. The method of claim 13, wherein method steps a) and b) are performed simultaneously.

18. The method of claim 15, wherein method steps a) and b) are performed simultaneously.

19. The method of claim 13, wherein the composition comprising at least one polyester and a surface-treated filler material product in step a) is obtained by adding the surface-treated filler material product to the polycondensation process of the at least one polyester.

20. The method of claim 15, wherein the composition comprising at least one polyester and a surface-treated filler material product in step a) is obtained by adding the surface-treated filler material product to the polycondensation process of the at least one polyester.

21. Use of a surface-treated filler material product as a porosimeter in a single-layer or multi-layer biaxially oriented polyester film, wherein the surface-treated filler material product comprises A) At least one milled calcium carbonate-containing filler material with a median weight particle size d 50 The range is 0.5μm-2.5μm, and B) A treatment layer on the surface of the at least one milled calcium carbonate filler material, comprising iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, wherein the monosubstituted succinic anhydride is produced by using a mixture selected from those having a total carbon atom count of at least C4 to C6 in the substituents. 20 It is composed of monosubstituted succinic anhydrides with linear, branched, aliphatic, and cyclic groups. The surface-treated filler material product comprises a treated layer comprising 0.5-1.8% by weight of the total dry weight of the at least one milled calcium carbonate filler material, and The membrane comprises at least one polyester comprising 80-96% by weight of the total weight of the layer and 4-20% by weight of a surface-treated filler material product.

22. Articles comprising a single-layer or multi-layer biaxially oriented polyester film according to any one of claims 1-10, wherein the article is selected from packaging products, food contact applications, paper and glass coverings, insulating or heat-insulating materials, solar energy, marine and aerospace applications, scientific, electronic and acoustic applications, graphic arts, paper alternatives and holograms, filtration products, cosmetics, household products, imaging and recording media, industrial products, release sheets, fiberglass boards, laminates, hot-stamped foils and insulating or heat-insulating finishes.

23. Use of single-layer or multi-layer biaxially oriented polyester films according to any one of claims 1-10 in the following areas: packaging products, food contact applications, paper and glass coverings, insulating or heat-insulating materials, solar energy, marine and aerospace applications, scientific, electronic and acoustic applications, graphic arts, paper substitutes and holograms, filtration products, cosmetics, household products, imaging and recording media, industrial products, release sheets, fiberglass boards, laminates, hot-stamped foils and insulating or heat-insulating finishes.

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