RU2797545C2 - Surface treated fillers for polyester films - Google Patents

Abstract

FIELD: polyester films.

SUBSTANCE: polyester films, a method for their production and use. Proposed is a film for producing products containing at least one polyester in an amount ranging from 20.0 to <70 wt.%, selected from polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polyethylene furanoate; a thermoplastic polymer selected from a polyolefin comprising polypropylene, polyethylene, polybutylene, and a surface-treated filler material product in an amount ranging from >30 to 78.0 wt% in relation to the total weight of the layer, where the surface-treated filler material product contains A) at least one ground filler material containing calcium carbonate having a weighted median particle size d₅₀ ranging from 1.7 to 2.6 mcm, and B) a treatment layer on the surface of at least one pulverized filler material containing calcium carbonate that contains stearic acid, or at least one monosubstituted succinic anhydride, consisting of succinic anhydride, the monosubstituted group of which is selected from alkenyl, where the product material surface-treated filler contains a layer of processing in an amount of from 0.6 to 2.3 wt% in relation to the total dry weight of at least one crushed filler material containing calcium carbonate. Also proposed is a method for producing the said film, the use of a surface-treated filler material in the composition of the product film, an article containing the film, and the use of the film in packaging products.

EFFECT: proposed films have a reduced density, high opacity and good mechanical properties.

21 cl, 3 tbl, 3 ex

Description

The present invention relates to a single or multilayer polyester (polyester) film, to a method for producing a single or multilayer polyester film, to the use of a surface-treated filler material product as a blowing agent in a single or multilayer polyester film, to an article containing single or multilayer polyester film, as well as the use of single or multilayer polyester film in packaging products, insulating materials, solar energy applications, marine or aviation applications, science, electronic or acoustic applications, wires, cables, RF identification, flexible circuit boards, printing, stone paper, holograms, filtration products, cosmetic products, household product imaging, information recording media or industrial products.

Polyester (also often referred to as polyester) films such as cast films, blown films, double blown films, monoaxially and biaxially oriented polyester films are used in a wide range of applications, particularly in packaging products. , insulating materials, in solar energy applications, in marine or aviation applications, in science, in electronic or acoustic applications, in wires, cables, in RFID, in flexible printed circuit boards, in printing, in stone paper, in holograms, in filtering products, in cosmetics, in imaging of household products, in information recording media or in industrial products.

It is well known that oriented polyester films can be obtained by adding blowing agents (chemicals or gas) or blowing agents. For example, in a molded article, microvoids can be formed in the film by admixing blowing agents, ie, small amounts of particles or incompatible polymers that form voids when stretched. This process is referred to as "porosity" and may also be referred to as "cavitation" or "microporation". Voids are typically formed by incorporating from about 5 to about 50% by weight of small organic or inorganic particles or "inclusions" (referred to in the art as "porogens" or "cavitating" agents) into the matrix polymer and orienting the polymer by stretching at least one direction. During stretching, small cavities or "micro-voids" form around the blowing agent. When voids are introduced into polymeric films, the resulting film with voids not only has a lower density than a film without voids, but also becomes opaque and acquires a paper-like surface. This surface also has the advantage of increasing print properties; that is, the surface is capable of accepting a variety of colors at a significantly higher capacity than a film without voids. In any case, the creation of small voids/holes in the product results in a reduction in density, an increase in opacity and insulating properties, and inherent UV blocking without the need for a separate UV absorber due to light scattering by the voids. Microvoid products have the added benefit of lowering overall film cost and increasing ease of separation/recyclability, especially when such products are used in packaging applications such as labels (see eg US 7297755 B2).

In principle, the formation of voids is based on the generation of microcracks at the interface between the polymer and the blowing agent during film formation, in particular, under longitudinal tension. During subsequent transverse stretching, these fine longitudinal cracks open with breaks to form air-filled closed hollow spaces. Therefore, it seems clear that the generation of voids during simultaneous orientation is disproportionately more complex than during sequential orientation. Indeed, it becomes apparent in practice that incompatible particles in polypropylene that are common, such as CaCO ₃ or PBT, do not generate voids at all or only generate them by selective particle shapes or particle sizes (see e.g. WO03/033574) during simultaneous orientation. For this reason, for this method, an alternative technology has been developed for generating voids by means of blowing agents.

Obviously, hollow polyester films typically contain a mixture of polyester polymers and a blowing agent (organic material or inorganic fillers such as calcium carbonate) and are obtained by forming a film from this mixture by pouring or blowing with successive stretching or drawing the film into two orthogonal directions, at two different temperatures.

Several attempts have been made in the art to improve the mechanical and optical properties of polyester films by adding inorganic filler materials and, in particular, filler materials containing calcium carbonate. For example, EP 0554654 A1 mentions a film of polyester resin that is biaxially oriented and again oriented in the machine direction, and it contains a coating layer formed on at least one surface of the film, while the coating layer contains at least 50% masses of water-soluble or water-dispersible polyester resin having a glass transition temperature of at least 20°C. To prevent adhesion of the coating layer on the heating roll during re-stretching, the coating layer may contain inorganic or organic particles. Such particles are described as acting to improve anti-blocking or sliding properties.

Similarly, DE 4313510 A1 relates to an oriented, single or multilayer film having a total thickness of ≤4 μm and a roughness on at least one surface of the film Ra <30 nm, where the surface resistance to gas flow is at least one film surface is t ≤ ad ^b [sec], where a=0-10000 [sec/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.

EP 1052269 A1 relates to a biaxially oriented film with a thickness of 1-500 µm and with a crystallizing thermoplastic as the main component, and furthermore containing UV stabilizer(s) and white pigment(s).

EP 1612237 A1 relates to a thermoplastic biaxially oriented film containing at least 500 ppm. pigment, at least 20% by weight of recycled material of the same type is added to it. The film may be single or multilayer and preferably has a thickness of 10-300 µm.

K. Nevalainen et al., "Voiding behavior and microstructure of a filled polyester film"; Materials Chemistry and Physics 92 (2005) 540-547, mentions the pore-forming behavior of a filled polyethylene terephthalate polyester film. The filler used is barium sulfate, which has an average particle size between 1 and 2 µm.

K. Nevalainen et al., ʺThe microstructure of polyethylene terephthalate matrix near to a void under uniaxial drawʺ; Materials Chemistry and Physics 101 (2007) 103-111, describes the characterization of a matrix in the immediate vicinity of a void. In particular, mention is made of a monoaxially stretched PET film and a void formed around a filler in the form of a spherical glass ball with a diameter of 5 μm.

A. Sudár et al., ʺThe mechanism and kinetics of void formation and growth and growth in particulate filled PE compositesʺ; Polymer letters, Vol. 1, no. 11 (2007), 763-772 describes that the formation of voids in PE is especially dependent on the nature of the matrices, i.e. in soft matrices the number of voids is smaller and their size is larger for the same deformation and filler content than in polymers with a higher intrinsic modulus elasticity.

However, the described films have the disadvantage that the corresponding voids during the production of polyester films with the creation of microporous films having low density and high opacity are difficult to obtain without breaks. films.

One solution to the problem discussed above is described in International Patent Application PCT/EP2016/078466 relating to a single or multilayer biaxially oriented polyester film, where at least one layer of the film contains at least one polyester in an amount in the range from 70 to 99.9 wt%, and the product of the surface-treated filler material in an amount ranging from 0.1 to 30 wt%, relative to the total weight of the layer, where the product of the surface-treated filler material contains A ), at least one ground filler material containing calcium carbonate having a weighted median particle size d ₅₀ ranging from 0.5 μm to 2.5 μm, and B) a treatment layer on the surface of at least one ground material filler containing calcium carbonate containing i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and salt reaction products thereof, and/or one or more phosphoric acid diesters, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or iii. at least one aliphatic aldehyde and/or salt reaction products thereof and/or iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline its reaction products, and/or v. at least one polydialkylsiloxane and/or vi. mixtures of materials according to i. - v., where the product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3 wt%, in relation to the dry weight, of at least one crushed filler material containing calcium carbonate.

However, International Patent Application PCT/EP2016/078466 says absolutely nothing about polyester films having a high filler content, i.e. >30% wt.

Thus, the creation of polyester films having a microporous structure at a high filler content, low density and high opacity continues to be of interest to a person skilled in the art. In addition, it is desirable to keep the mechanical and optical properties high and to create environmentally friendly films that are obtained on the one hand from renewable and/or recycled raw materials and on the other hand can be disposed of in an environmentally friendly manner.

Accordingly, it is an object of the present invention to provide a polyester (polyester) film having a microporous structure. It would also be desirable to provide a polyester film or corresponding layer having a microporous structure with a high filler content. It would also be desirable to provide a polyester film or corresponding layer having a microporous structure at a low density, in particular below the density normally achieved for the respective films or layers using barium sulfate or titanium dioxide as blowing agents. It would also be desirable to provide a polyester film or layer having an opaque appearance. It would also be desirable to provide a polyester film or layer that can be obtained without tearing the film/layer. It would also be desirable to provide a polyester film or layer having good mechanical and optical properties. It would also be desirable to provide a polyester film or layer which is environmentally friendly, which on the one hand is obtained from raw materials that are renewable and/or recycled, and on the other hand can be disposed of in an environmentally friendly manner.

Another object of the present invention is to provide an inorganic blowing agent for polyester films or layers. It would also be desirable to provide an inorganic blowing agent for polyester (polyester) films or layers that exhibits good dispersion properties and compounding performance in polyester film/layer applications. It would also be desirable to provide an inorganic blowing agent for polyester films or layers that imparts low density to the film or layer. It would also be desirable to provide an inorganic blowing agent that does not cause the film/layer to break in the production of a polyester film or layer. It would also be desirable to provide an inorganic blowing agent for polyester films or layers which allows high filler content. It would also be desirable to provide an inorganic blowing agent for polyester films or layers that imparts good mechanical properties such as tensile strength, elongation at break or modulus of elasticity. It would also be desirable to provide an inorganic blowing agent for polyester films or layers that imparts an opaque appearance to the film or layer.

The objects discussed above and other objects are achieved by the subject matter as defined herein in the independent claims.

In accordance with one aspect of the present invention, a single or multilayer polyester (polyester) film is provided. A single or multi-layer polyester film contains at least one layer containing at least one polyester in an amount ranging from 20.0 to <70 wt% and a surface-treated filler material product in an amount ranging from > 30 to 80.0% by weight, based on the total weight of the layer, where the surface-treated filler material product contains

A) at least one pulverized filler material containing calcium carbonate having a weighted median particle sized ₅₀ between 0.5 µm and 3.0 µm, and

B) a treatment layer on the surface of at least one crushed filler material containing calcium carbonate, containing

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products and/or one or more phosphoric acid diesters, and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline its reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i. -v.,

where the product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3 wt%, in relation to the dry weight, of at least one crushed filler material containing calcium carbonate.

According to another aspect, a process is provided for making a single or multilayer polyester (polyester) film as defined herein, comprising the steps of:

a) providing a composition comprising at least one polyester and a surface treated filler material product, and

b) forming a film from the composition from step a), and where the surface-treated filler material product contains

A) at least one pulverized filler material containing calcium carbonate having a weighted median particle sized ₅₀ between 0.5 µm and 3.0 µm, and

B) a treatment layer on the surface of at least one crushed filler material containing calcium carbonate, containing

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products and/or one or more phosphoric acid diesters, and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline their reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i. -v.,

where the product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3 wt%, in relation to the dry weight, of at least one crushed filler material containing calcium carbonate.

In accordance with yet another aspect of the present invention, the use of a surface treated filler material product as a blowing agent in a single or multilayer polyester (polyester) film as defined herein is provided, wherein the surface treated filler material product comprises

A) at least one pulverized filler material containing calcium carbonate having a weighted median particle sized ₅₀ between 0.5 µm and 3.0 µm, and

B) a treatment layer on the surface of at least one crushed filler material containing calcium carbonate, containing

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products, and/or one or more phosphoric acid diesters and their salt reaction products, and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline their reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i.-v.,

where the product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3 wt%, in relation to the dry weight, of at least one crushed filler material containing calcium carbonate.

In accordance with another aspect of the present invention, there is provided an article containing a single or multilayer polyester (polyester) film as defined herein, wherein the article is selected from the group consisting of packaging products, preferably flexible packaging products, applications for contact with foodstuffs, paper or glass coatings, insulating materials, from solar energy applications, preferably top or back sheets for photovoltaic devices, from marine or aeronautical applications, from scientific applications, from electronic or acoustic applications, preferably displays, from wires, cables, RFID, flexible circuit boards, printing, preferably labels, stone paper, preferably bags, packages, boxes, books, booklets, brochures, loyalty cards, business cards, greeting cards, corrugated cardboard, envelopes, pallets for food, labels, games, tags, magazines, indexes, billboards, stationery printed matter, diaries, notebooks or notepads, and holograms, filter products, cosmetic products, household products, imaging media, preferably photographic paper, x-ray film or thermal transfer media, or industrial products, preferably capacitors, release films, fiberglass panels, laminating films, hot stamping foils, or insulating trims.

In accordance with another aspect of the present invention, the use of a single or multilayer polyester (polyester) film as defined herein is provided in packaging products, preferably in flexible packaging products, in food contact applications, in paper coatings. or glass, in insulating materials, in solar energy applications, preferably in top or back sheets for photovoltaic devices, in marine or aviation applications, in scientific applications, in electronic or acoustic applications, preferably in displays, in wires, cables , in RFID, in flexible printed circuit boards, in printing, preferably in labels, in stone paper, preferably in bags, in packages, in boxes, in books, in booklets, in brochures, in loyalty cards, in business cards, in greeting cards, corrugated cardboard, envelopes, food trays, labels, games, tags, magazines, signs, billboards, printed stationery, diaries, notebooks or notebooks, and holograms, filtering products, cosmetic products, in household products, in imaging media, preferably photographic paper, x-ray film or thermal transfer media, or in industrial products, preferably in condensers, release films, fiberglass panels, laminating films, hot stamping foils, or insulating finishes.

Preferred embodiments of the present invention are defined herein as well as in the relevant dependent claims.

According to one embodiment of the present invention, at least one layer of a film containing a polyester and a surface treated filler material product contains a surface treated filler material product in an amount ranging from 30.01 to 80.0 wt%, by weight. relative to the total weight of the layer, preferably from 30.1 to 78.0 wt%, more preferably from 30.5 to 75.0 wt%, even more preferably from 31.0 to 73.0 wt%, and most preferably, from 35.0 to 70.0% of the mass.

In another embodiment, the at least one polyester is selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), bio-based polyesters, polyester recycling materials and blends thereof.

According to another embodiment, at least one layer of a film containing a polyester and a surface-treated filler material product contains at least one polyester in an amount ranging from 20.0 to 69.99 wt%, more preferably from 22.0 to 69.9% by weight, based on the total weight of the layer.

In one embodiment, the at least one calcium carbonate-comprising particulate fill material is wet or dry pulverized calcium carbonate-containing fill material, and preferably is wet pulverized calcium carbonate-containing fill material. Specifically contemplated or preferred is the use of wet ground filler materials containing calcium carbonate in connection with the above aspects of the present invention.

In another embodiment, the at least one particulate filler material comprising calcium carbonate is natural pulverized calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface treated calcium carbonate, or a mixture thereof, and preferably natural pulverized calcium carbonate.

According to another embodiment, at least one pulverized filler material containing calcium carbonate has a) a weighted median particle sized ₅₀ 0.5 µm to 2.5 µm, preferably 0.5 µm to 2.0 µm, even more preferably 0.5 µm to 1.8 µm, and most preferably 0.6 µm to 1 .8 µm, and/or b) maximum particle sized ₉₈ ≤15 µm, preferably ≤10 µm, more preferably ≤7.5 µm, even more preferably ≤7 µm, and most preferably ≤6.5 µm, and/or c) fineness such that at least , 15 wt%, preferably at least 20 wt%, even more preferably at least 25 wt%, and most preferably 30 to 40 wt% of all particles have a particle size of <0.5 µm, and/ or d) specific surface area (BET) from 0.5 to 150 m²/g, preferably from 0.5 to 50 m²/g, more preferably 0.5 to 35 m²/g, and most preferably, from 0.5 to 15 m²/g as measured using nitrogen and the BET method according to ISO 9277.

According to one embodiment, the treatment layer on the surface of at least one ground filler material containing calcium carbonate contains at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction products, preferably at least one saturated aliphatic linear or branched carboxylic acid selected from the group consisting of carboxylic acids consisting of pentanoic 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, nonadecanic acid, arachidic acid, cheneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid and mixtures thereof, and/or at least one monosubstituted succinic anhydride, consisting of succinic anhydride, monosubstituted by a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or salt reaction products thereof.

According to another embodiment, the surface-treated filler material product contains a treatment layer in an amount of 0.2 to 2.0 wt%, preferably 0.4 to 1.9 wt%, and most preferably 0.5 to 1 .8% by weight, based on the dry weight of at least one particulate filler material containing calcium carbonate.

According to another embodiment, at least one layer of the film comprising the polyester and the surface treated filler material product further comprises a thermoplastic polymer, preferably cross-linked with a cross-linking agent, the thermoplastic polymer is selected from the group consisting of a polyolefin, preferably selected from the group consisting of polypropylene, polyethylene, polybutylene and mixtures thereof, cyclic olefin copolymer (COC), polyketone, polysulfone, fluoropolymer, polyacetal, ionomer, acrylic resin, polystyrene resin, polyurethane, polyamide, polycarbonate, polyacrylonitrile and their copolymerized resin and blends that are dispersible in at least one polyester.

According to one embodiment, this at least one film layer containing the polyester and surface treated filler material product contains a thermoplastic polymer in an amount ranging from 0.1 to 29.9% by weight, preferably from 1 to 28 wt%, more preferably 2 to 26 wt%, even more preferably 3 to 25 wt%, even more preferably 4.5 to 23 wt%, and most preferably 4 to 20 wt%, according to relative to the total weight of the layer.

According to another embodiment of the film, preferably at least one layer containing the surface-treated filler material product has a) a density in the range of 1.8 to 2.4 g/cm ³ , preferably 1.8 to 2 .35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ , and most preferably 1.9 to 2.25 g/m ² , and/or b) opacity ≥50%, preferably ≥55% and most preferably ≥60%.

In yet another embodiment, at least one layer of the film comprising the polyester and the surface treated filler material product further comprises an inorganic filler material other than the surface treated filler material product, and preferably selected from the group consisting of alumina, silicon dioxide, titanium dioxide, alkali metal salts such as barium carbonate, calcium sulfate, barium sulfate, and mixtures thereof, preferably in an amount of 1 to 10% by weight, relative to the total weight of the layer.

According to one embodiment of the film, preferably, the layer containing at least one polyester and the surface-treated filler material product contains an additive selected from the group consisting of light stabilizers, preferably 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organic compounds nickel, salicylic esters, cinnamic esters, resorcinol monobenzoates, oxanilides, hydroxybenzoic esters, hindered amines and triazines, more preferably 2-hydroxybenzotriazoles and triazines, most preferably hydroxyphenyltriazine, optical brightener, blue dyes, preferably soluble blue dyes in polyester, anti-blocking agents, white pigments and mixtures thereof.

According to another embodiment, the film is a cast film, blown film, double blown film, or monoaxially oriented polyester film.

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

According to another embodiment of the method, the composition obtained in step a) is a masterbatch or compound containing a surface-treated filler material product in an amount of >30 to 85 wt%, preferably 35 to 80 wt%, and more preferably, 40 to 70% by weight, based on the total weight of the masterbatch or compound.

According to another embodiment of the method, a composition comprising at least one polyester and a surface treated filler material product from step a) is obtained by adding a surface treated filler material product, preferably before or after a polycondensation process of at least at least one polyester.

According to one embodiment of the method, steps a) and b) of the process are carried out simultaneously, preferably wherein at least one polyester and surface treated filler material product is added directly to the extruder during step b).

According to another embodiment of the method, the method further comprises the step c) of stretching the film obtained in step b) in only one direction from machine direction (MD) or transverse direction (TD).

The at least one polyester and surface treated filler material product and, if present, other optional additives may be mixed using an appropriate mixer, for example a Henschel mixer, super mixer, tumbler mixer or the like. According to another embodiment, steps a) and b) of the process are carried out simultaneously, preferably wherein at least one polyester and surface treated filler material product is added directly to the extruder during step b). According to another embodiment, a composition comprising at least one polyester and a surface treated filler material product from step a) is obtained by adding a surface treated filler material product, preferably before or after the polycondensation process, at least , one polyester.

It is to be understood that for the purposes of the present invention, the following terms have the following meanings:

The film casting method includes extrusion of the respective molten polymers through a slotted or flat die to form a thin, molten sheet or film. This film is "pinned" or "fixed" to the surface of a chilled roll (typically water-cooled and chrome-plated) by means of forced air from an air knife or vacuum box. The film is quenched directly, and then its edges are cut off before winding. Due to the rapid quenching capabilities, cast film generally has much better optical properties than blown film and can be produced at higher line speeds. However, it has the disadvantage of more waste due to edge trimming and very little transverse orientation of the film.

The term "mono-axially oriented" polyester film indicates that the film is a mono-axially oriented film, i.e. the film is subjected to a stretching process in the machine direction (MD) or transverse direction (TD), preferably in the machine direction (MD), thereby obtaining a mono-axially oriented films.

"Film" in the meaning of the present invention is a sheet or layer of material having a median thickness that is small compared to 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 to 2000 µm, preferably 4 to 1500 µm, more preferably 5 to 1300 µm, and most preferably 6 to 1000 µm. , for example, from 8 to 500 µm. The film is in the form of a single or multilayer film.

"Single layer" film refers to a film consisting of only one layer. "Multilayer" film refers to a film consisting of two or more layers, for example two to ten layers, preferably three layers, which are adjacent to each other. If the multilayer film is a three-layer film, the film may have an A-B-A or A-B-C film structure. In a multilayer film, the core layer preferably contains voids.

The term "crushed calcium carbonate-containing filler" in the present invention means a calcium carbonate-containing filler that is produced by a process including at least one grinding step. The "crushed calcium carbonate-containing fillers" may be "wet-ground" or "dry-ground", where "wet-ground calcium carbonate-containing filler" in the meaning of the present invention is a ground filler containing calcium carbonate, which is produced by a method, comprising at least one grinding step in an aqueous suspension with a solids content ranging between 20 and 80% by weight, and "dry ground calcium carbonate-containing filler" is a ground filler containing calcium carbonate, which is produced using a method, comprising at least one stage of grinding in an aqueous suspension with a solids content of more than 80 and up to 100% of the mass.

The term "microporous film" or "microporous layer" in the meaning of the present invention refers to a polyester film or a corresponding layer which allows the passage of gases and water vapor due to the presence of micropores. The presence of "micropores" in a polyester film or layer can be measured by its water vapor transmission rate. (WVTR), which is defined in g/(m²·day). For example, a polymer film or layer may be considered "microporous" if it has a WVTR below 100 g/(m²·day). WVTR can be determined using the Lyssy L80-5000 measuring device according to ASTM E398.

The term "low density" in the meaning of the present invention refers to a single or multilayer polyester film or corresponding layer having a density of 1.8 to 2.4 g/cm ³ , preferably 1.8 to 2.35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ and most preferably 1.9 to 2.25 g/m ² .

For the purposes of the present invention, the term "calcium carbonate-containing fill material" refers to a material that contains at least 80% by weight of calcium carbonate, based on the dry weight of the calcium carbonate-containing fill material.

"Natural ground calcium carbonate" (GCC) within the meaning of the present invention is calcium carbonate obtained from natural sources such as limestone, marble, dolomite or chalk and processed by wet processing such as grinding, screening and/or fractionation, for example , using a cyclone or a classifier.

"Modified calcium carbonate" (MCC) in the meaning of the present invention can characterize natural ground or precipitated calcium carbonate with modification of the internal structure, or a surface reaction product, i.e. "surface-reacted calcium carbonate".

"Surface-reacted calcium carbonate" is a material containing calcium carbonate and insoluble, preferably at least partially crystalline salts of calcium and acid anions on the surface. Preferably, the insoluble calcium salt extends from the surface of at least a portion of the calcium carbonate. The calcium ions forming said at least partially crystalline salt of calcium and said anion originate primarily from the starting material of calcium carbonate. MCCs are described, for example, in US 2012/0031576 A1, WO 2009/074492 A1, EP 2264109 A1, EP 2070991 A1 or EP 2264108 A1.

The term "surface-treated filler material product" as used herein refers to a calcium carbonate-containing filler material that has been contacted with a surface treatment agent to form a coating layer on at least a portion of the surface of the carbonate-containing filler material. calcium.

The term "dry" filler material containing calcium carbonate is understood to be a filler material containing less than 0.3% by weight of water, based on the weight of the filler material. % water (equal to ʺtotal residual moisture contentʺ) is determined using the coulometric Karl Fischer measurement method, where the fill material is heated to 220°C, and the water content released as steam and isolated using nitrogen gas flow (at 100 ml/min) is determined as a coulometric Karl Fischer unit.

The term "polymer composition" refers to a composite material containing at least one additive (eg, at least one filler) and at least one polyester material that can be used in the preparation of a polymer product.

The term "polymer masterbatch" (= or "masterbatch") or "polymer compound" (= or "compound") as used herein refers to a composition with a relatively high filler content, which means >30% by weight (relative to the total weight of the composition). The "polymer masterbatch" or "polymer compound" may be added to unfilled or lightly filled polyester during processing to obtain higher filler levels. Accordingly, the term "polymer composition" (= "composition"), as used herein, includes both "polymer masterbatches" and "polymer compounds".

The term "specific surface area" (in m ² /g) of the mineral filler as used in the present invention is determined using the BET method with nitrogen adsorbed gas, which is well known to those skilled in the art (ISO 9277:2010). The total surface area (in m ² ) of the mineral filler is then obtained by multiplying the specific surface area by the mass (in g) of the mineral filler prior to processing.

As used herein, the "particle size" of a calcium carbonate-containing filler is described by its particle size distribution. Meaningd _x is the diameter relative to which x % mass of the particles have diameters smaller thand _x. This means that the valued ₂₀represents the particle size for which 20% of the mass of all particles is less than it, and the valued ₉₈ is the particle size for which 98% of the mass of all particles is smaller than it. Meaningd ₉₈ also referred to as ʺmaximum contentʺ. So the valued ₅₀ represents the weighted median particle size, that is, 50% of the mass of all grains is less than this particle size. For the purposes of the present invention, the particle size is reported as the weighted median particle sized ₅₀, unless otherwise noted. To determine the value of the weighted median particle sized ₅₀ or particle size values of the maximum contentd ₉₈ you can use the Sedigraph 5100 from Micromeritics, USA. The method and tools are known to those skilled in the art and are commonly used to determine the grain sizes of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt% Na₄P₂O₇. The samples are dispersed using a high speed stirrer and sonication.

For the purposes of the present invention, the "solids content" of a liquid composition is a measure of the amount of material remaining after all the solvent or water has evaporated.

"Suspension" or "slurry" within the meaning of the present invention contains insoluble solids and water, and optionally other additives, and usually contains higher amounts of solids, and thus is more viscous and may have a higher density than the liquid from which it is is formed.

A "treatment layer" in the spirit of the present invention refers to a layer, preferably a monolayer, of a surface treatment agent on the surface of at least one particulate filler material containing calcium carbonate. The "treatment layer" contains, as a surface treatment agent, that is, i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and salt reaction products thereof, and/or one or more phosphoric acid diesters and salt reaction products thereof, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof and/or iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline its reaction products, and/or v. at least one polydialkylsiloxane and/or vi. mixtures of materials according to i. -v..

When the term "comprising" is used in the present specification and claims, it does not exclude other unspecified elements of greater or lesser functional importance. For the purposes of the present invention, the term "consisting of" is considered to be the preferred embodiment of the term "comprising". If a group is defined hereinafter as containing at least a certain number of embodiments, this should also be understood as describing a group that preferably consists of only those embodiments.

When the terms "comprising" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

When designations for a noun are used in the singular, it includes, for example, the plural of that noun, unless otherwise specified.

Terms like "derived" or "determined" and "obtained" or "determined" are used interchangeably. This means, for example, that, unless the context clearly dictates otherwise, the term "obtained" does not mean indicating, for example, that an embodiment is to be obtained, for example, using the sequence of steps following the term "obtained", even if such a limited understanding is always is included using the terms "obtained" or "determined" as the preferred embodiment.

The single or multilayer polyester film of the present invention comprises at least one layer containing at least one polyester in an amount ranging from 20.0 to <70 wt% and a surface-treated filler material product in an amount of range from >30 to 80.0% of the mass, relative to the total mass of the film. The surface-treated filler material product contains (A) at least one ground filler material containing calcium carbonate having a weighted median particle sized ₅₀ ranging from 0.5 µm to 3.0 µm, and (B) a treatment layer on the surface of at least one crushed filler material containing calcium carbonate containing i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and salt reaction products thereof, and/or one or more phosphoric acid diesters, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to C_thirty in the substituent, and/or the salt products of their reaction, and/or v. at least one polydialkylsiloxane and/or vi. mixtures of materials according to i. - v.. The product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3% by weight, relative to the dry weight, of at least one crushed filler material containing calcium carbonate.

In the following, details and preferred embodiments of the present invention with respect to polyester film will be discussed in more detail. It is to be understood that these technical details and embodiments also apply to the process for producing said single or multilayer polyester film according to the present invention and to the use of the single or multilayer polyester film and surface treated filler material product of the present invention.

Complex polyester

The single or multilayer polyester (polyester) film of the present invention contains at least one layer containing at least one polyester. Obviously, this at least one polyester is not limited to a specific material, in so far as the polymer is suitable for producing a single-layer or multi-layer polyester film, in particular, a film obtained by casting, a film obtained by extrusion with extrusion, a film obtained by extrusion double blown or monoaxially oriented polyester film. The person skilled in the art will select the polyester according to the desired application of the single layer or multilayer polyester film.

One requirement of the present invention is that at least one polyester and surface treated filler material product be present in the same layer. Thus, the product of the surface-treated filler material is dispersed in this at least one polyester.

Suitably, the multilayer polyester film comprises at least one layer containing at least one polyester and a surface treated filler material product. If a multilayer polyester film contains two or more layers containing a polyester and a surface-treated filler material product, it is obvious that these two or more layers may be the same or different, for example, they may differ in the amount of this at least one complex polyester and surface treated filler material product.

Obviously, the expression "at least one" polyester means that the polyester contains, preferably consists of one or more types of polyester (s).

Accordingly, it should be noted that at least one polyester may be one kind of polyester. Alternatively, at least one polyester may be a mixture of two or more kinds of polyesters. For example, at least one polyester may be a mixture of two or three types of polyesters, like two types of polyester.

In one of the embodiments of the present invention, at least one polyester contains, preferably consists of one type of polyester.

In general, the term "polyester" means 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. Ethylene glycol, trimethylene glycol, tetramethylene glycol or cyclohexanedimethanol can be used as the diol.

Additionally or alternatively, the at least one polyester may be partially or wholly a bio-based polyester, ie a polyester in which the monomers are derived from renewable biomass sources. Examples of monomers include those that can be obtained using compounds derived from biological sources. For example, monomers include, but are not limited to, ethylene glycol (EG), furandicarboxylic acid (FDCA), polyethylene furanoate (PEF), which can be prepared using fructose, and mixtures thereof. Other monomers which are suitable for the production of bio-based polyester are described, for example, in WO2014/100265 A1, which is hereby incorporated by reference.

In addition or alternatively, the at least one polyester is a material from polyester recycling, such as material from PET recycling, for example PET bottle waste from a PET recycling stream.

Thus, the polyester of the present invention is preferably polyglycolic acid, polylactic acid, polycaprolactone, polyhydroxybutyrate (PHB), polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, poly(1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalene-2,6-dicarboxylate, polyethylene naphthalene -1,5-dicarboxylate, polytrimethylene naphthalate, polyethylene naphthalate/bibenzoate, or another combination derived from the monomers discussed above, or optionally a mixture of these polyesters. For example, polyesters that can be used are selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT ), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), bio-based polyesters, polyester recycling materials and blends thereof.

Mention should be made of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene furanoate (PEF), and mixtures thereof. Most preferably, the at least one polyester is polyethylene terephthalate (PET).

These polyesters may be either a homopolymer or a copolymer. As the copolymerization component, a diol component such as diethylene glycol, neopentyl glycol or polyalkylene glycol and a dicarboxylic acid such as adipic acid, sebacic acid, phthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid can be used .

In one preferred embodiment, the polyester also contains at least 0.5 wt%, preferably at least 1 wt%, and more preferably at least 2 wt%, based on the total weight of the polyester. , units derived from monomeric isophthalic acid by condensation with a diol.

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

In one embodiment, the polyester has a crystallization temperature (T _c ) measured by differential scanning calorimetry (DSC) of at least 120° C., preferably at least 140° C., for example, in the range of 140 up to 180°C.

Additionally or alternatively, the polyethylene terephthalate (PET) preferably contains diethylene glycol in an amount of ≤3 wt%, more preferably ≤1.5 wt%, and most preferably ≤1.2 wt%, based on the total weight of polyethylene terephthalate (PET ).

Obviously, at least one polyester is preferably an amorphous or crystalline polyester, for example crystalline polyethylene terephthalate (PET).

A layer of a single or multilayer polyester film containing at least one polyester and a surface-treated filler material product contains at least one polyester in an amount ranging from 20.0 to <70 wt%, with respect to to the total weight of the layer.

According to one embodiment, the layer of a single or multilayer polyester film containing at least one polyester and a surface-treated filler material product contains at least one polyester in an amount ranging from 20.0 to 69 .9 wt%, more preferably 22.0 to 69.9 wt%, even more preferably 25.0 to 69.5 wt%, even more preferably 27.0 to 69.0 wt%, and most preferably, from 30.0 to 65.0 wt%, based on the total weight of the layer.

In the case where at least one layer of the monolayer or multilayer polyester film further comprises a thermoplastic polymer, at least one layer of the film containing the polyester and the product of the surface-treated filler material contains at least one polyester in an amount ranging from 22.0 to 69.9 wt%, preferably from 25.0 to 69.5 wt%, even more preferably from 27.0 to 69.0 wt%, and most preferably from 30, 0 to 65.0 wt%, based on the total weight of the layer.

Surface treated filler material product

At least one layer of the single or multilayer polyester film of the present invention also comprises a surface treated filler material product, wherein the surface treated filler material product comprises at least one particulate filler material containing calcium carbonate. The surface treated filler material product has several main features which are defined in claim 1 and will be described in more detail hereinafter.

At least one particulate filler material containing calcium carbonate is ground in a wet or dry state filler material containing calcium carbonate. Preferably, the at least one particulate filler material containing calcium carbonate is a wet ground filler material containing calcium carbonate.

As a rule, the grinding step can be carried out using any conventional grinding device, for example, under such conditions that the enrichment mainly occurs as a result of collisions with the secondary body, that is, in one or more devices from: ball mill, rod mill, vibratory mill, roller crusher, centrifugal impact mill, vertical ball mill, disc mill, pin mill, hammer mill, pulverizer, pulverizer, lump breaker, knife cutter, or other such equipment known to those skilled in the art.

In the case where the at least one ground calcium carbonate-containing fill material is a wet-ground calcium carbonate-containing fill material, the wet grinding step may be carried out under conditions such that autogenous grinding occurs, and/or with using a horizontal ball mill, and/or other such processes known to those skilled in the art. The processed ground filler material containing calcium carbonate thus obtained can be washed and dehydrated before drying by well-known processes, for example by flocculation, filtration or forced evaporation. The subsequent drying step may be carried out in a single step, such as spray drying, or at least two steps, such as first applying a heating step to the wet-ground calcium carbonate-containing fill material to reduce the associated moisture content to , not exceeding about 0.5% of the mass, in relation to the dry weight of at least one crushed in the wet state of the filler material containing calcium carbonate. The total residual moisture content of the fill can be measured using the coulometric Karl Fischer titration method, moisture desorption in an oven at 195°C and its continuous passage into a KF coulometer (Mettler Toledo Coulometric KF Titrator C30, combined with a Mettler DO 0337 oven) using a dry N ₂ at 100 ml/min for 10 min. The total residual moisture content can be determined using a calibration curve, and a 10 min gas flow screen without sample can also be taken into account. The total residual moisture content can be further reduced by applying a second heating stage to at least one wet ground filler material containing calcium carbonate. In case said drying is carried out in several drying stages, the first stage may be carried out by heating in a hot air stream, while the second and other drying stages are preferably carried out by indirect heating, in which the atmosphere in the corresponding container contains a surface treatment agent. . It is also common that at least one wet ground filler material containing calcium carbonate is subjected to an enrichment step (such as a flotation, bleaching or magnetic separation step) to remove impurities.

In another preferred embodiment, the at least one ground filler material containing calcium carbonate is ground in a horizontal ball mill and subsequently dried using a well-known spray drying process.

At least one ground filler material containing calcium carbonate, within the meaning of the present invention refers to a filler material selected from natural ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), modified calcium carbonate (MCC), surface-treated calcium carbonate or mixtures thereof.

In a preferred embodiment, the at least one calcium carbonate-containing particulate filler material is natural ground calcium carbonate (GCC), more preferably the calcium carbonate-containing particulate filler is wet ground natural calcium carbonate.

GCC is understood to be a naturally occurring form of calcium carbonate mined from sedimentary rocks such as limestone or chalk or from metamorphic marbles and processed through processing such as grinding, screening and/or fractionating in a wet form, for example, using a cyclone or a classifier. In one embodiment of the present invention, the GCC is selected from the group consisting of marble, chalk, dolomite, limestone, and mixtures thereof.

"Precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, usually obtained by precipitation after the reaction of carbon dioxide and lime in an aqueous environment, or by precipitation of calcium and a source of carbonate ions in water, or by precipitation of calcium and carbonate ions, for example, CaCl ₂ and Na ₂ CO ₃ from solution. Other possible routes for the production of PCC are the lime-soda process, or the Solvay process, in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three main crystalline forms: calcite, aragonite, and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms. Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic and prismatic (P-PCC). Aragonite is an orthorhombic structure with typical crystal habits of double hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved spade, truncated pyramid, wedge-shaped, branched tree, and coral or worm-shaped crystals. Vaterite belongs to the hexagonal crystal system. The resulting PCC slurry can be dehydrated and dried mechanically.

The modified calcium carbonate can be characterized as internally modified GCC or PCC or surface-reacted GCC or PCC. Surface-reacted calcium carbonate can be obtained by obtaining GCC or PCC in the form of an aqueous suspension and adding acid to this suspension. Suitable acids are, for example, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid or a mixture thereof. In the next step, the calcium carbonate is treated with carbon dioxide gas. If a strong acid such as sulfuric acid or hydrochloric acid is used in the acid treatment step, carbon dioxide will be generated automatically in situ . Alternatively, or in addition, the carbon dioxide may be supplied from an external source. Surface-reacted calcium carbonates are described, for example, in US 2012/0031576 A1, WO 2009/074492 A1, EP 2264109 A1, EP 2070991 A1 or EP 2264108 A1.

In one preferred embodiment, the at least one ground filler material containing calcium carbonate is marble, more preferably wet ground marble.

Obviously, the amount of ground calcium carbonate in at least one filler material containing calcium carbonate is at least 80% by weight, for example at least 95% by weight, preferably between 97 and 100% mass, more preferably between 98.5 and 99.95 mass%, in relation to the dry mass of at least one crushed filler material containing calcium carbonate.

The at least one particulate filler material containing calcium carbonate is preferably in the form of a particulate material and may have a particle size distribution as is commonly used for the material(s) introduced into the type of product to be produced. Generally, one of the specific requirements of the present invention is that the at least one pulverized filler material containing calcium carbonate has a weighted median particle size d ₅₀ in the range of 0.5 to 3.0 µm. For example, at least one ground filler material containing calcium carbonate has a weighted median particle size d ₅₀ from 0.5 µm to 2 µm, preferably from 0.5 µm to 2 µm, even more preferably from 0.5 µm to 1.8 µm, and most preferably 0.6 µm to 1.8 µm, such as about 0.8 µm or about 1.7 µm.

It is preferred that the at least one pulverized filler material containing calcium carbonate has a maximum content size value ( d ₉₈ ) of ≦15 µm. For example, at least one particulate filler material containing calcium carbonate has a maximum content size ( d ₉₈ ) ≤10 µm, preferably ≤7.5 µm, more preferably ≤7 µm, and most preferably ≤6.5 µm.

Obviously, the value of the weighted median particle size d ₅₀ and the size of the maximum content ( d ₉₈ ), at least one crushed filler material containing calcium carbonate, satisfies a specific relationship. For example, at least one pulverized filler material containing calcium carbonate has a ratio of weighted median particle size d ₅₀ and maximum content size ( d ₉₈ ) [ d ₅₀ / d ₉₈ ] from 0.1 to 0.4, preferably, from 0.1 to 0.3, and most preferably from 0.2 to 0.3.

Additionally or alternatively, at least one particulate filler material containing calcium carbonate has a fineness such that at least 15% by weight, preferably at least 20% by weight, even more preferably at least at least 25 wt%, and most preferably 30 to 40 wt% of all particles has a particle size of <0.5 µm.

In one embodiment, at least one particulate filler material containing calcium carbonate has

i) a weighted median particle size d ₅₀ of 0.5 to 3.0 µm, preferably 0.5 µm to 2 µm, more preferably 0.5 µm to 2 µm, even more preferably 0.5 µm up to 1.8 µm, and most preferably from 0.6 µm to 1.8 µm, and

ii) particle size maximum content d ₉₈ ≤15 µm, preferably ≤10 µm, more preferably ≤7.5 µm, even more preferably ≤7 µm, and most preferably ≤6.5 µm, and

iii) fineness such that at least 15 wt%, preferably at least 20 wt%, even more preferably at least 25 wt%, and most preferably 30 to 40 wt% of all particles has a particle size of <0.5 µm.

For example, at least one pulverized filler material containing calcium carbonate has

i) weighted median particle size from d ₅₀ from 0.6 µm to 1.8 µm, and

ii) maximum content size ( d ₉₈ ) ≤6.5 µm, and

iii) fineness such that 30 to 40% by weight of all particles has a particle size of <0.5 µm.

In addition, it is clear that at least one ground filler material containing calcium carbonate preferably has a BET specific surface area between 0.5 and 150 m ² /g, as measured using nitrogen and the BET method according to ISO 9277. For example, at least one ground filler material containing calcium carbonate has a specific surface area (BET) of 0.5 to 50 m ² /g, more preferably 0.5 to 35 m ² /g, and most preferably , from 0.5 to 15 m ² /g, as measured using nitrogen and the BET method according to ISO 9277.

In one of the embodiments of the present invention, at least one crushed filler material containing calcium carbonate, preferably is a marble having a diameter value d ₅₀median particle size 0.5 to 3.0 µm, preferably 0.5 µm to 2 µm, more preferably 0.5 µm to 2 µm, even more preferably 0.5 µm to 1.8 µm, and most preferably from 0.6 µm to 1.8 µm, for example about 0.8 µm or about 1.7 µm. In this case, at least one ground filler material containing calcium carbonate exhibits a BET specific surface area of 0.5 to 150 m²/g, preferably from 0.5 to 50 m²/g, more preferably 0.5 to 35 m²/g, and most preferably, from 0.5 to 15 m²/g as measured using nitrogen and the BET method according to ISO 9277.

According to the present invention, at least one ground filler material containing calcium carbonate has a residual moisture content of ≤1 wt %, based on the total dry weight of at least one ground filler material containing calcium carbonate. Depending on at least one ground filler material containing calcium carbonate, this at least one ground filler material containing calcium carbonate has a total residual moisture content of from 0.01 to 1% by weight, preferably from 0 .01 to 0.2 wt%, more preferably 0.02 to 0.15 wt%, and most preferably 0.04 to 0.15 wt%, based on the total dry weight of at least one crushed filler material containing calcium carbonate.

For example, in the case where crushed and spray-dried marble is used as the at least one particulate filler material containing calcium carbonate, the total residual moisture content of the at least one pulverized filler material containing calcium carbonate is preferably 0.01 to 0.1 wt %, more preferably 0.02 to 0.08 wt %, and most preferably 0.04 to 0.07 wt %, based on total dry weight, at least one crushed filler material containing calcium carbonate. If PCC is used as the at least one pulverized filler material containing calcium carbonate, the total residual moisture content of at least one pulverized filler material containing calcium carbonate is preferably 0.01 to 0.2% by mass, more preferably 0.05 to 0.17 wt %, and most preferably 0.05 to 0.10 wt %, based on the total dry weight of at least one particulate filler material containing calcium carbonate.

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

The processing layer contains

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products and/or one or more phosphoric acid diesters, and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline their reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i. -v.

According to one embodiment of the present invention, the surface-treated filler material product comprises a treatment layer on at least a portion of the surface of at least one pulverized calcium carbonate-containing filler material, where the treatment layer contains a mixture of phosphoric acid esters, one or more phosphoric acid monoesters and salt reaction products thereof and/or one or more phosphoric acid diesters.

The term "phosphoric acid monoester" as used herein refers to an o-phosphoric acid molecule monoesterified with one alcohol molecule selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon number of C6 to C30, preferably , C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

The term "phosphoric acid diester" as used herein refers to an o-phosphoric acid molecule diesterified with two alcohol molecules selected from the same or different, unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C30, preferably C8 to C22, more preferably C8 to C20 and most preferably C8 to C18 in the alcohol substituent.

The term "salt reaction products of a mixture of phosphoric acid esters, one or more monophosphoric acid esters and/or one or more phosphoric acid diesters" in the sense of the present invention refers to products obtained by contacting a filler material containing calcium carbonate with one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and optionally with phosphoric acid. Said salt reaction products are formed between the applied one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and optionally phosphoric acid, and reactive molecules located on the surface of the filler material, preferably at least one particulate filler material. containing calcium carbonate.

Phosphoric acid alkyl esters are well known in the industry, especially as surfactants, lubricants and antistatic agents (Die Tenside; Kosswig und Stache, Carl Hanser Verlag München, 1993).

The synthesis of phosphoric acid alkyl esters by various methods and the surface treatment of minerals with phosphoric acid alkyl esters are well known to those skilled in the art, for example from Pesticide Formulations and Application Systems: 15th Volume; Collins HM, Hall FR, Hopkinson M, STP1268; Published: 1996, US 3897519 A, US 4921990 A, US 4350645 A, US 6710199 B2, US 4126650 A, US 5554781 A, EP 1092000 B1 and WO 2008/023076 A1.

Obviously, the expression "one or more" phosphoric acid monoesters means that one or more kinds of phosphoric acid monoesters may be present in the mixture of phosphoric acid esters.

Accordingly, it should be noted that one or more phosphoric acid monoesters may be one kind of phosphoric acid monoester. Alternatively, one or more phosphoric acid monoesters may be a mixture of two or more kinds of phosphoric acid monoesters. For example, one or more phosphoric acid monoesters may be a mixture of two or three types of phosphoric acid monoesters, like two types of phosphoric acid monoesters.

In one embodiment of the present invention, one or more phosphoric acid monoesters are composed of o-phosphoric acid molecules esterified with a single alcohol selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C30 in the alcohol substituent. For example, one or more phosphoric acid monoesters are composed of o-phosphoric acid molecules esterified with a single alcohol selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon number of C8 to C22, more preferably , C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid monoesters are composed of o-phosphoric acid molecules esterified with a single alcohol selected from saturated and linear or branched and aliphatic alcohols having a total carbon number of C6 to C30 in alcohol substituent. For example, one or more phosphoric acid monoesters are composed of o-phosphoric acid molecules esterified with a single alcohol selected from saturated and linear or branched and aliphatic alcohols having a total carbon number of C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid monoesters are composed of o-phosphoric acid molecules esterified with a single alcohol selected from saturated and linear and aliphatic alcohols having a total carbon number of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent. Alternatively, one or more phosphoric acid monoesters are composed of o-phosphoric acid molecules esterified with a single alcohol selected from saturated and branched and aliphatic alcohols having a total carbon number of C6 to C30, preferably C8 to C22, greater than preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, the one or more phosphoric acid monoesters are selected from the group consisting of hexyl phosphoric monoester, heptyl phosphoric monoester, octyl phosphoric monoester, 2-ethylhexyl phosphoric monoester, nonyl phosphoric monoester Phosphoric Acid Decyl Monoester, Phosphoric Acid Undecyl Monoester, Phosphoric Acid Dodecyl Monoester, Phosphoric Acid Tetradecyl Monoester, Phosphoric Acid Hexadecyl Monoester, Phosphoric Acid Heptylnonyl Monoester, Phosphoric Acid Octadecyl Monoester, 2-octyl-Monoester 1-decylphosphoric acid, 2-octyl-1-dodecylphosphoric acid monoester, and mixtures thereof.

For example, one or more phosphoric acid monoesters is selected from the group consisting of 2-ethylhexyl phosphoric acid monoester, hexadecyl phosphoric monoester, heptylnonyl phosphoric monoester, octadecyl phosphoric monoester, 2-octyl-1-decylphosphoric acid monoester , a complex monoester of 2-octyl-1-dodecylphosphoric acid and mixtures thereof. In one embodiment of the present invention, the one or more phosphoric acid monoesters is a 2-octyl-1-dodecylphosphoric acid monoester.

Obviously, the expression "one or more" phosphoric acid diesters means that one or more phosphoric acid diesters may be present in the product treatment layer of the surface-treated material and/or in the mixture of phosphoric acid esters.

Accordingly, it should be noted that one or more phosphoric acid diesters may be one kind of phosphoric acid diesters. Alternatively, one or more phosphoric acid diesters may be a mixture of two or more types of phosphoric acid diesters. For example, one or more phosphoric acid diesters may be a mixture of two or three kinds of phosphoric acid diesters, like two kinds of phosphoric acid diesters.

In one embodiment of the present invention, one or more phosphoric acid diesters consist of o-phosphoric acid molecules esterified with two alcohols selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C30 in the alcohol substituent. For example, one or more diesters of phosphoric acid are composed of o-phosphoric acid molecules esterified with two fatty alcohols selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C8 to C22, more than preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

Obviously, the two alcohols used for the esterification of 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 from C6 to C30 in the alcohol substituent. In other words, one or more phosphoric acid diesters may contain two substituents derived from the same alcohols, or a phosphoric acid diester molecule may contain two substituents derived from different alcohols.

In one embodiment of the present invention, one or more phosphoric acid diesters consist of o-phosphoric acid molecules esterified with two alcohols selected from the same or different, saturated and linear or branched and aliphatic alcohols having a total number of carbon atoms from C6 to C30 in the alcohol substituent. For example, one or more phosphoric acid diesters are composed of o-phosphoric acid molecules esterified with two alcohols selected from the same or different, saturated and linear or branched and aliphatic alcohols having a total carbon number of C8 to C22, more preferably , C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid diesters are composed of o-phosphoric acid molecules esterified with two alcohols selected from the same or different, saturated and linear and aliphatic alcohols having a total carbon number of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent. Alternatively, one or more phosphoric acid diesters consist of o-phosphoric acid molecules esterified with two alcohols selected from the same or different, saturated and branched and aliphatic alcohols having a total carbon number of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, the one or more phosphoric diesters are selected from the group consisting of phosphoric acid hexyl diester, phosphoric heptyl diester, phosphoric octyl diester, 2-ethylhexyl phosphoric diester, nonyl phosphoric diester phosphoric acid decyl diester, phosphoric acid undecyl diester, phosphoric acid dodecyl diester, phosphoric acid tetradecyl diester, phosphoric acid hexadecyl diester, phosphoric acid heptylnonyl diester, octadecyl phosphoric diester, 2-octyl diester 1-decylphosphoric acid, a diester of 2-octyl-1-dodecylphosphoric acid, and mixtures thereof.

For example, one or more phosphoric acid diesters are selected from the group consisting of 2-ethylhexyl phosphoric acid diester, hexadecyl phosphoric acid diester, heptylnonyl phosphoric acid diester, octadecyl phosphoric acid diester, 2-octyl-1-decylphosphoric acid diester, a diester of 2-octyl-1-dodecylphosphoric acid; and mixtures thereof. In one embodiment of the present invention, the one or more phosphoric acid diesters is a diester of 2-octyl-1-dodecylphosphoric acid.

In one embodiment of the present invention, the one or more phosphoric acid monoesters are selected from the group consisting of phosphoric acid 2-ethylhexyl monoester, phosphoric acid hexadecyl monoester, phosphoric acid heptylnonyl monoester, phosphoric acid octadecyl monoester, 2- octyl-1-decylphosphoric acid, 2-octyl-1-dodecylphosphoric acid monoester and mixtures thereof, and one or more phosphoric acid diesters selected from the group consisting of phosphoric acid 2-ethylhexyl diester, phosphoric acid hexadecyl diester, heptylnonyl diester a diester of phosphoric acid, a diester of octadecyl phosphoric acid, a diester of 2-octyl-1-decylphosphoric acid, a diester of 2-octyl-1-dodecylphosphoric acid, and mixtures thereof.

For example, at least a portion of the surface of the calcium carbonate-containing filler material contains a mixture of phosphoric acid esters, one phosphoric acid monoester and salt reaction products thereof, and one phosphoric acid diester and salt reaction products thereof. In this case, one phosphoric acid monoester is selected from the group consisting of phosphoric acid 2-ethylhexyl monoester, phosphoric acid hexadecyl monoester, phosphoric acid heptylnonyl monoester, phosphoric acid octadecyl monoester, 2-octyl-1-decylphosphoric acid monoester and a 2-octyl-1-dodecylphosphoric acid monoester, one phosphoric acid diester selected from the group consisting of 2-ethylhexyl phosphoric acid diester, hexadecyl phosphoric acid diester, heptylnonyl phosphoric acid diester, octadecyl phosphoric diester, diester 2-octyl-1-decylphosphoric acid; and a diester of 2-octyl-1-dodecylphosphoric acid.

If at least part of the surface of at least one ground filler material containing calcium carbonate contains a mixture of phosphoric acid esters, one phosphoric acid monoester and salt reaction products thereof, and one phosphoric acid diester, and their salt products reaction, it is clear that the alcohol substituents of one phosphoric acid monoester and one phosphoric diester are preferably the same. For example, at least a portion of the surface of at least one ground filler material containing calcium carbonate contains a mixture of phosphoric acid esters, complex 2-ethylhexyl phosphoric acid monoester and salt reaction products thereof and complex 2-ethylhexyl diester of phosphoric acid and salt products of its reaction. Alternatively, at least part of the surface of at least one ground filler material containing calcium carbonate contains a mixture of phosphoric acid esters, complex 2 octyl-1-decyl phosphoric acid monoester and salt products of its reaction and complex 2-octyl- 1-decyl diester of phosphoric acid and salt products of its reaction. Alternatively, at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters, hexadecyl phosphoric acid monoester and salt reaction products thereof, and hexadecyl diester phosphoric acid and salt reaction products thereof . Alternatively, at least part of the surface of at least one ground filler material containing calcium carbonate contains a mixture of phosphoric acid esters, octadecyl phosphoric acid monoester and salt reaction products thereof, and octadecyl diester phosphoric acid and salt reaction products thereof . Alternatively, at least part of the surface of at least one ground filler material containing calcium carbonate contains a mixture of phosphoric acid esters, 2-octyl-1-dodecylphosphoric acid monoester and salt reaction products thereof, and 2-octyl diester -1-dodecylphosphoric acid and salt products of its reaction.

In one embodiment of the present invention, at least a portion of the surface of at least one pulverized filler material containing calcium carbonate contains a mixture of phosphoric acid esters, two or more phosphoric acid monoesters and salt reaction products thereof, and two or more complex diesters of phosphoric acid and salt products of their reaction. In this case, the two or more phosphoric acid monoesters are selected from the group consisting of phosphoric acid 2-ethylhexyl monoester, phosphoric acid hexadecyl monoester, phosphoric acid heptylnonyl monoester, phosphoric acid octadecyl monoester, 2-octyl-1-decyl phosphoric acid monoester and 2-octyl-1-dodecylphosphoric acid monoester, two or more phosphoric acid diesters selected from the group consisting of phosphoric acid 2-ethylhexyl diester, phosphoric acid hexadecyl diester, phosphoric acid heptylnonyl diester, octadecyl diester phosphoric acid, 2-octyl-1-decyl phosphoric acid diester and 2-octyl-1-dodecyl phosphoric acid diester.

In one embodiment of the present invention, at least a portion of the surface of at least one pulverized filler material containing calcium carbonate contains a mixture of phosphoric acid esters, two phosphoric acid monoesters and their salt reaction products, and two phosphoric diesters. acids and salt products of their reaction. For example, at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters, hexadecyl phosphoric acid monoester, phosphoric acid octadecyl monoester, phosphoric acid hexadecyl diester, octadecyl diester phosphoric acid and salt products of their reaction.

According to one embodiment of the present invention, the mixture of phosphoric acid esters, at least on a part of the surface of at least one crushed filler material containing calcium carbonate, contains one or more monophosphoric acid esters and their salt reaction products and one or several diesters of phosphoric acid and salt products of their reaction in a specific molar ratio. In particular, the molar ratio of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters and their salt reaction products in the treatment layer and/or in the mixture of phosphoric acid esters can be from 1:1 to 1 :100.

The expression "the molar ratio of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters and their salt reaction products" in the sense of the present invention refers to the ratio of the sum of the molecular weights of the phosphoric acid monoester molecules and the sum of the molecular weights of the monoesters phosphoric acid in the salt products of their reaction to the sum of the molecular weights of the molecules of diesters of phosphoric acid and the sum of the molecular weights of the molecules of diesters of phosphoric acid in the salt products of their reaction.

According to one embodiment, the molar ratio of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters and their reaction salt salts in the mixture of phosphoric acid esters is from 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, still more preferably 1:1 .1 to 1:20, and most preferably from 1:1.1 to 1:10.

Additionally or alternatively, a mixture of phosphoric acid esters the treatment layer contains one or more phosphoric acid monoesters and their salt reaction products in an amount of from 1 to 50 mol%, relative to the sum of the moles of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters, and salt products of their reaction. For example, the mixture of phosphoric acid esters of the treatment layer contains one or more phosphoric acid monoesters and their salt reaction products in an amount of from 10 to 45 mol%, relative to the sum of the moles of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters and salt reaction products thereof.

According to one embodiment of the present invention,

I) one or more phosphoric acid monoesters consists of an o-phosphoric acid molecule monoesterified with one alcohol molecule selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C30, preferably , C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent, and/or

II) one or more diesters of phosphoric acid consists of an o-phosphoric acid molecule diesterified with two alcohol molecules selected from the same or different, unsaturated or saturated, branched or linear, aliphatic or aromatic fatty alcohols having a total number of carbon atoms from C6 to C30, preferably C8 to C22, more preferably C8 to C20 and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, the phosphoric acid ester mixture of the treatment layer further comprises one or more triesters of phosphoric acid and/or phosphoric acid and its reaction salts.

The term "phosphoric acid triester" as used herein refers to an o-phosphoric acid molecule triesterified with three alcohol molecules selected from the same or different, unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C30, preferably C8 to C22, more preferably C8 to C20 and most preferably C8 to C18 in the alcohol substituent.

Obviously, the expression "one or more" triesters of phosphoric acid means that one or more kinds of triesters of phosphoric acid may be present on at least part of the surface of at least one particulate filler material containing calcium carbonate.

Accordingly, it should be noted that one or more triesters of phosphoric acid may be one kind of triesters of phosphoric acid. Alternatively, one or more triesters of phosphoric acid may be a mixture of two or more kinds of triesters of phosphoric acid. For example, one or more triesters of phosphoric acid may be a mixture of two or three kinds of triesters of phosphoric acid, like two kinds of triesters of phosphoric acid.

In one embodiment of the present invention, one or more triesters of phosphoric acid are composed of o-phosphoric acid molecules esterified with three alcohols selected from the same or different, unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a common the number of carbon atoms from C6 to C30 in the alcohol substituent. For example, one or more triesters of phosphoric acid are composed of o-phosphoric acid molecules esterified with three alcohols selected from the same or different, unsaturated or saturated, branched or linear, aliphatic or aromatic fatty alcohols having a total number of carbon atoms from C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

Obviously, the three alcohols used for the esterification of phosphoric acid can be independently selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C30 in the alcohol substituent. In other words, one or more phosphoric acid triester molecules may contain three substituents derived from the same alcohols, or a phosphoric acid triester molecule may contain three substituents derived from different alcohols.

In one embodiment of the present invention, one or more triesters of phosphoric acid are composed of o-phosphoric acid molecules esterified with three alcohols selected from the same or different, saturated and linear or branched and aliphatic alcohols having a total number of carbon atoms from C6 to C30 in the alcohol substituent. For example, one or more triesters of phosphoric acid are composed of o-phosphoric acid molecules esterified with three alcohols selected from the same or different, saturated and linear or branched and aliphatic alcohols having a total carbon number of C8 to C22, more preferably , C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, one or more triesters of phosphoric acid are composed of o-phosphoric acid molecules esterified with three alcohols selected from saturated and linear and aliphatic alcohols having a total carbon number of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent. Alternatively, one or more triesters of phosphoric acid consist of o-phosphoric acid molecules esterified with three alcohols selected from saturated and branched and aliphatic alcohols having a total carbon number of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18 in the alcohol substituent.

In one embodiment of the present invention, the one or more phosphoric triesters are selected from the group consisting of phosphoric acid hexyl triesters, phosphoric heptyl triesters, phosphoric octyl triesters, 2-ethylhexyl phosphoric triesters, nonyl phosphoric triesters Phosphoric Acid Decyl Triester, Phosphoric Undecyl Triester, Phosphoric Dodecyl Triester, Phosphoric Acid Tetradecyl Triester, Phosphoric Acid Hexadecyl Triester, Phosphoric Acid Heptylnonyl Triester, Phosphoric Acid Octadecyl Triester, 2-octyl-1 Complex -decyl triester of phosphoric acid, 2-octyl-1-dodecyl triester of phosphoric acid and mixtures thereof.

For example, one or more phosphoric acid triesters are selected from the group consisting of phosphoric acid 2-ethylhexyl triester, phosphoric acid hexadecyl triester, phosphoric acid heptylnonyl triester, phosphoric acid octadecyl triester, phosphoric acid 2-octyl-1-decyl triester , complex 2-octyl-1-dodecyl triester of phosphoric acid and mixtures thereof.

In one embodiment of the present invention, at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters, one or more monophosphoric acid esters and salt reaction products thereof, and one or several phosphoric acid diesters and salt reaction products thereof; and one or more triesters of phosphoric acid, and optionally, phosphoric acid and salt reaction products thereof. For example, at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters, one or more phosphoric acid monoesters and salt reaction products thereof, and one or more phosphoric acid diesters and salt products of their reaction, and one or more triesters of phosphoric acid, and phosphoric acid and salt products of its reaction.

Alternatively, at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters, one or more phosphoric acid monoesters and salt reaction products thereof, and one or more phosphoric acid diesters and salt products of their reaction, and optionally, phosphoric acid and salt products of its reaction. For example, at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters, one or more phosphoric acid monoesters and salt reaction products thereof, and one or more phosphoric acid diesters and salt products of their reaction, and phosphoric acid, and salt products of its reaction.

If at least part of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of esters of phosphoric acid containing one or more triesters of phosphoric acid, it is preferred that the mixture of esters of phosphoric acid contains one or several triesters of phosphoric acid in an amount of ≤10% mol, relative to the sum of the moles of one or more complex monophosphates of phosphoric acid and salt products of their reaction and one or more complex diesters of phosphoric acid and salt products of their reaction, and one or more complex triesters of phosphoric acids and phosphoric acid and salt products of their reaction. For example, a mixture of phosphoric acid esters contains one or more triesters of phosphoric acid in an amount of ≤ 8 mol%, preferably ≤ 6 mol%, and more preferably ≤ 4 mol%, for example, from 0.1 to 4 mol%, according to with respect to the sum of moles of one or more phosphoric acid monoesters and salt reaction products thereof and one or more phosphoric acid diesters and salt reaction products thereof, and one or more triesters of phosphoric acid and phosphoric acid and salt reaction products thereof.

In addition or alternatively, if at least a portion of the surface of at least one particulate filler material containing calcium carbonate contains a mixture of phosphoric acid esters containing phosphoric acid and its reaction salts, it is preferred that the mixture phosphoric acid esters contained phosphoric acid and salt products of its reaction in an amount of ≤10% mol, relative to the sum of the moles of one or more complex monophosphoric acid esters and salt products of their reaction and one or more diesters of phosphoric acid and salt products of their reaction, and one or more triesters of phosphoric acid and phosphoric acid and salt reaction products thereof. For example, a mixture of phosphoric acid esters contains phosphoric acid and salt products of its reaction in an amount of ≤8 mol%, preferably ≤6% mol, and more preferably ≤4% mol, for example, from 0.1 to 4% mol, according to with respect to the sum of moles of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters and their salt reaction products, and one or more phosphoric acid triesters of phosphoric acid and their salt reaction products.

If the mixture of phosphoric acid esters additionally contains phosphoric acid and salt products thereof and one or more triesters of phosphoric acid, then it is preferred that the molar ratio of phosphoric acid and salt products thereof and one or more monoesters of phosphoric acid and salt products thereof reaction and one or more diesters of phosphoric acid and salt reaction products thereof and one or more triesters of phosphoric acid in a mixture of esters of phosphoric acid was ≤10% mol: ≤40% mol: ≥40% mol: ≤10% mol, by with respect to the sum of moles of one or more phosphoric acid monoesters and their salt reaction products and one or more phosphoric acid diesters and their salt reaction products, and one or more phosphoric acid and phosphoric acid triesters and their salt reaction products.

The expression "molar ratio of phosphoric acid and its salt reaction products and one or more phosphoric acid monoesters and their reaction salt products and one or more phosphoric acid diesters and their reaction salt salts and one or more phosphoric acid triesters" as used in the present invention refers to to the ratio of the sum of the molecular masses of phosphoric acid and the sum of the molecular masses of phosphoric acid molecules in the salt products of its reaction to the sum of the molecular masses of the molecules of phosphoric acid monoesters and to the sum of the molecular masses of the molecules of phosphoric acid monoesters in the salt products of their reaction, to the sum of the molecular masses of complex molecules diesters of phosphoric acid and to the sum of molecular weights of molecules of complex diesters of phosphoric acid in the salt products of their reaction, and to the sum of molecular weights of molecules of complex phosphoric acid diesters.

Obviously, the mixture of phosphoric acid esters may contain salt reaction products obtained by contacting at least one filler material, preferably at least one crushed filler material containing calcium carbonate, with one or more phosphoric monoesters. acid and one or more diesters of phosphoric acid, and optionally phosphoric acid. In such a case, the phosphoric acid ester mixture preferably contains reaction salts such as one or more calcium, magnesium and/or aluminum salts of phosphoric acid monoesters and one or more calcium, magnesium and/or aluminum salts of phosphoric diesters and optionally , one or more calcium, magnesium and/or aluminum salts of phosphoric acid. Preferably, the phosphoric acid ester mixture contains reaction salts such as one or more calcium and/or magnesium salts of phosphoric acid monoesters and one or more calcium and/or magnesium salts of phosphoric diesters, and optionally one or more calcium salts and/or magnesium and phosphoric acid.

In one embodiment of the present invention, one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters, and optionally, phosphoric acid can be at least partially neutralized with one or more hydroxides of one and/or of a di- and/or trivalent cation and/or one or more weak acid salts of a mono- and/or di- and/or trivalent cation before at least one filler material is obtained, preferably at least one ground filler material containing calcium carbonate. One or more hydroxides of the di and/or trivalent cation may be selected from Ca(OH) ₂ , Mg(OH) ₂ , Al(OH) ₃ and mixtures thereof.

Additionally or alternatively, if one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters, and optionally, phosphoric acid is at least partially neutralized with one or more hydroxides and/or one or more salts of a weak acid of a monovalent cation, the amount of monovalent cations is preferably ≤10 mol%, based on the sum of the moles of acid groups in one or more phosphoric acid monoesters and one or more phosphoric diesters, and optionally, in phosphoric acid, one or more hydroxides and/or one or more salts of a weak acid monovalent cation for neutralization can be selected from LiOH, NaOH, KOH, Na ₂ CO ₃ , Li ₂ CO ₃ , K ₂ CO ₃ and mixtures thereof.

In one embodiment of the present invention, the divalent cations used to partially neutralize one or more phosphoric acid monoesters and/or one or more phosphoric diesters and optional phosphoric acid are obtained from weak acid salts of such cations, preferably from carbonates and/or borates such as calcium carbonate.

The term "weak acid" as used herein refers to a Brønsted-Lowry acid, i.e. an H ₃ O ⁺ ion supplier, having a _pKa >2, preferably between 4 and 7.

Accordingly, the phosphoric ester mixture of the treatment layer may further comprise salt reaction products such as one or more calcium and/or magnesium salts of phosphoric acid monoesters and one or more calcium and/or magnesium salts of phosphoric diesters, and optionally, one or several salts of calcium and/or magnesium and phosphoric acid. In addition or alternatively, the treatment layer phosphoric acid ester mixture further comprises salt reaction products such as one or more aluminum salts of phosphoric acid monoesters and one or more aluminum salts of phosphoric diesters, and optionally one or more aluminum salts and phosphoric acid. In addition or alternatively, the treatment layer phosphoric acid ester mixture further comprises salt reaction products such as one or more lithium salts of phosphoric acid monoesters and one or more lithium salts of phosphoric diesters, and optionally one or more lithium salts and phosphoric acid. In addition or alternatively, the phosphoric ester mixture of the treatment layer further comprises salt reaction products such as one or more sodium salts of phosphoric acid monoesters and one or more sodium salts of phosphoric diesters, and optionally one or more sodium salts and phosphoric acid. In addition or alternatively, the phosphoric ester mixture of the treatment layer further comprises salt reaction products such as one or more potassium salts of phosphoric acid monoesters and one or more potassium salts of phosphoric diesters, and optionally one or more potassium salts and phosphoric acid.

If one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters, and optionally, phosphoric acid is at least partially neutralized with one or more hydroxides and/or one or more salts of a weak acid and monovalent cations, the treatment layer and/or mixture of phosphoric acid esters preferably contains an amount of monovalent cations ≤10 mol%, based on the sum of the moles of acid groups in one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and optionally in phosphoric acid .

In one embodiment of the present invention, the treatment layer phosphoric acid ester blend may further comprise additional surface treatment agents that do not correspond to one or more phosphoric acid monoesters, one or more phosphoric acid diesters, and optional one or more phosphoric triesters. acid and/or phosphoric acid of the present invention.

In one embodiment, the molar ratio of one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters and salt reaction products thereof is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.

The expression "the molar ratio of one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters to their salt reaction products" in the sense of the present invention refers to the sum of the molecular weights of phosphoric acid monoesters and/or the sum of the molecular weights of phosphoric acid diesters to the sum of the molecular weights of the phosphoric acid monoesters in the salt products of their reaction and/or the sum of the molecules of the diesters of phosphoric acid in the salt products of their reaction.

Processes for preparing a surface-treated filler material product treated with at least one mixture of phosphoric acid esters and corresponding coating compounds are described, for example, in EP 2770017 A1, which is hereby incorporated by reference.

According to another embodiment of the present invention, the surface-treated filler material product comprises a treatment layer on at least a portion of the surface of at least one pulverized calcium carbonate-containing filler material, where the treatment layer contains at least one saturated aliphatic linear or branched carboxylic acid and salt products of its reaction.

For example, the treatment layer contains a saturated aliphatic linear or branched carboxylic acid having a total number of carbon atoms from C4 to C24 and/or salt reaction products thereof.

The term "salt reaction products" of a saturated aliphatic linear or branched carboxylic acid as used herein refers to products obtained by contacting at least one particulate filler material containing calcium carbonate with at least one saturated aliphatic linear or a branched carboxylic acid. Said reaction products are formed between at least a portion of the deposited at least one saturated aliphatic linear or branched carboxylic acid and reactive molecules located on the surface of at least one crushed filler material containing calcium carbonate.

The aliphatic carboxylic acid within the meaning of the present invention may be selected from one or more straight chain, branched chain, saturated, unsaturated and/or alicyclic carboxylic acids. Preferably, the aliphatic carboxylic acid is a monocarboxylic acid, ie the aliphatic carboxylic acid is characterized in that a carboxyl group is present. Said carboxyl group is at the end of the carbon skeleton.

In one embodiment of the present invention, the aliphatic linear or branched carboxylic acid is selected from saturated straight chain carboxylic acids, this so to speak aliphatic carboxylic acid is preferably selected from the group of carboxylic acids consisting of pentanoic 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, nonadecanic acid, arachidic acid, cheneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid and mixtures thereof .

In another embodiment of the present invention, the aliphatic linear or branched carboxylic acid is selected from the group consisting of octanoic acid, decanoic 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 the group consisting of octanoic acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof.

For example, an aliphatic linear or branched carboxylic acid is octanoic acid or stearic acid. Preferably, the aliphatic linear or branched carboxylic acid is stearic acid.

In one embodiment, the molar ratio of at least one saturated aliphatic linear or branched carboxylic acid and the salt reaction product(s) thereof is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.

The expression "the molar ratio of at least one saturated aliphatic linear or branched carboxylic acid and the salt product(s) of their reaction" in the meaning of the present invention refers to the ratio of the sum of the molecular weights of a saturated aliphatic linear or branched carboxylic acid to the sum of the molecular weights of a saturated aliphatic linear or branched carboxylic acid in the salt products of its reaction.

According to another embodiment of the present invention, the surface-treated filler material comprises a treatment layer on at least a portion of the surface of at least one crushed calcium carbonate-containing filler material, where the treatment layer contains at least one aliphatic aldehyde and /or salt products of its reaction.

In this regard, at least one aliphatic aldehyde is a surface treating agent and may be selected from any linear, branched or alicyclic, substituted or unsubstituted, saturated or unsaturated aliphatic aldehyde. Said aldehyde is preferably selected such that the number of carbon atoms is equal to or greater than 6, and more preferably equal to or greater than 8. In addition, said aldehyde generally has a carbon number equal to or less than 14 , preferably equal to or less than 12, and more preferably equal to or less than 10. In one of the preferred embodiments, the number of carbon atoms of the aliphatic aldehyde is between 6 and 14, preferably between 6 and 12, and more preferably , between 6 and 10.

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

The aliphatic aldehyde may be selected from the group of aliphatic aldehydes consisting of hexanal, (E)-2-hexenal, (Z)-2-hexenal, (E)-3-hexenal, (Z)-3-hexenal, (E)-4 -hexenal, (Z)-4-hexenal, 5-hexenal, heptanal, (E)-2-heptenal, (Z)-2-heptenal, (E)-3-heptenal, (Z)-3-heptenal, ( 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, (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-decenal, (Z) -5-decenal, (E)-6-decenal, (Z)-6-decenal, (E)-7-decenal, (Z)-7-decenal, (E)-8-decenal, (Z)-8 -decenal, 9-decenal, undecenal, (E)-2-undecenal, (Z)-2-undecenal, (E)-3-undecenal, (Z)-3-undecenal, (E)-4-undecenal, ( Z)-4-undecenal, (E)-5-undecenal, (Z)-5-undecenal, (E)-6-undecenal, (Z)-6-undecenal, (E)-7-undecenal, (Z) -7-undecenal, (E)-8-undecenal, (Z)-8-undecenal, (E)-9-undecenal, (Z)-9-undecenal, 10-undecenal, dodecanal, (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-tridecenal , (Z)-2-tridecenal, (E)-3-tridecenal, (Z)-3-tridecenal, (E)-4-tridecenal, (Z)-4-tridecenal, (E)-5-tridecenal, ( Z)-5-tridecenal, (E)-6-tridecenal, (Z)-6-tridecenal, (E)-7-tridecenal, (Z)-7-tridecenal, (E)-8-tridecenal, (Z) -8-tridecenal, (E)-9-tridecenal, (Z)-9-tridecenal, (E)-10-tridecenal, (Z)-10-tridecenal, (E)-11-tridecenal, (Z)-11 -tridecenal, 12-tridecenal, butadecanal, (E)-2-butadecenal, (Z)-2-butadecenal, (E)-3-butadecenal, (Z)-3-butadecenal, (E)-4-butadecenal, ( Z)-4-butadecenal, (E)-5-butadecenal, (Z)-5-butadecenal, (E)-6-butadecenal, (Z)-6-butadecenal, (E)-7-butadecenal, (Z) -7-butadecenal, (E)-8-butadecenal, (Z)-8-butadecenal, (E)-9-butadecenal, (Z)-9-butadecenal, (E)-10-butadecenal, (Z)-10 -butadecenal, (E)-11-butadecenal, (Z)-11-butadecenal, (E)-12-butadecenal, (Z)-12-butadecenal, 13-butadecenal and mixtures thereof. In one preferred embodiment, the aliphatic aldehyde is selected from the group consisting of hexanal, (E)-2-hexenal, (Z)-2-hexenal, (E)-3-hexenal, (Z)-3-hexenal, ( E)-4-hexenal, (Z)-4-hexenal, 5-hexenal, heptanal, (E)-2-heptenal, (Z)-2-heptenal, (E)-3-heptenal, (Z)-3 -heptenal, (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, ( Z)-6-nonenal, (E)-7-nonenal, (Z)-7-nonenal, 8-nonenal and mixtures thereof.

In another preferred embodiment, at least one aliphatic aldehyde is a saturated aliphatic aldehyde. In this case, the aliphatic aldehyde is selected from the group consisting of hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, butadecanal, and mixtures thereof. Preferably, at least one aliphatic aldehyde in the form of a saturated aliphatic aldehyde is selected from the group consisting of hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, and mixtures thereof. For example, at least one aliphatic aldehyde in the form of a saturated aliphatic aldehyde is selected from octanal, nonanal, and mixtures thereof.

If a mixture of two aliphatic aldehydes, for example two saturated aliphatic aldehydes such as octanal and nonanal, is used in accordance with the present invention, the weight ratio of octanal and nonanal is from 70:30 to 30:70, and more preferably from 60:40 to 40:60. In one particularly preferred embodiment of the present invention, the weight ratio of octanal and nonanal is about 1:1.

The term "salt reaction products" of at least one aliphatic aldehyde as used in the present invention refers to products obtained by contacting at least one particulate filler material containing calcium carbonate with at least one aliphatic aldehyde . Said reaction products are formed between at least a portion of the applied at least one aliphatic aldehyde and reactive molecules located on the surface of at least one filler material, preferably at least one crushed filler material containing carbonate calcium.

In one embodiment, the molar ratio of at least one aliphatic aldehyde and the salt reaction product(s) thereof is 99.9:0.1 to 0.1:99.9, preferably 70:30 to 90 :10.

The expression "molar ratio of at least one aliphatic aldehyde and its salt reaction product(s") as used in the present invention refers to the ratio of the sum of the molecular weights of the aliphatic aldehyde to the sum of the molecular weights of the aliphatic aldehyde in its salt reaction products.

Processes for preparing a surface-treated filler material product treated with at least one aliphatic aldehyde and a corresponding coating compound are described, for example, in EP 2390285 A1, which is hereby incorporated herein by reference.

According to another embodiment of the present invention, the surface-treated filler material comprises a treatment layer on at least a portion of the surface of at least one pulverized calcium carbonate-containing filler material, where the treatment layer contains at least one monosubstituted succinic anhydride , consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or salt reaction products thereof.

The term "succinic anhydride", also referred to as dihydro-2,5-furandione, succinic anhydride or succinyl oxide, has the molecular formula C ₄ H ₄ O ₃ and is succinic acid anhydride.

The term "mono-substituted" succinic anhydride as used herein refers to succinic anhydride wherein the hydrogen atom is replaced by another substituent.

The term "mono-substituted" succinic acid as used herein refers to succinic acid where the hydrogen atom has been replaced by another substituent.

The term "salt reaction products" of at least one monosubstituted succinic anhydride refers to products obtained by contacting at least one particulate filler material containing calcium carbonate with one or more monosubstituted succinic anhydrides. Said salt reaction products are formed between monosubstituted succinic acid, which is formed from the monosubstituted succinic anhydride used, and reactive molecules located on the surface of at least one crushed filler material containing calcium carbonate. Alternatively, said salt reaction products are formed between monosubstituted succinic acid, which may optionally be present at least one monosubstituted succinic anhydride, and reactive molecules located on the surface of at least one particulate filler material containing calcium carbonate.

For example, the treatment layer on the surface of at least one pulverized filler material containing calcium carbonate contains at least one monosubstituted succinic anhydride, consisting of succinic anhydride, monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group, having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or salt reaction products thereof. More preferably, the treatment layer on the surface of at least one particulate filler material containing calcium carbonate contains at least one monosubstituted succinic anhydride, consisting of succinic anhydride, monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C ₃ to C ₃₀ , even more preferably at least C ₃ to C ₂₀ , and most preferably C ₄ to C ₁₈ in the substituent and/or in salt its reaction products.

More specifically, the treatment layer on the surface of at least one particulate filler material containing calcium carbonate contains at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group representing a linear or aliphatic group having a total number of atoms carbon at least C ₂ to C ₃₀ , preferably at least C ₃ to C ₃₀ , more preferably at least C ₃ to C ₂₀ and most preferably C ₄ to C ₁₈ in the substituent, and/or salt products of its reaction. In addition or alternatively, the surface treatment layer of at least one particulate filler material containing calcium carbonate contains at least one monosubstituted succinic anhydride, consisting of succinic anhydride, monosubstituted with a group representing a branched or aliphatic group containing a total number of carbon atoms of at least C ₃ to C ₃₀ , preferably at least C ₄ to C ₃₀ , more preferably at least C ₄ to C ₂₀ , and most preferably from C ₄ to C ₁₈ in the substituent, and/or salt reaction products thereof. In addition or alternatively, the surface treatment layer of at least one particulate filler material containing calcium carbonate contains at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group representing an aliphatic or cyclic group containing a total number of carbon atoms of at least C ₅ to C ₃₀ , preferably at least C ₅ to C ₂₀ , and most preferably C ₅ to C ₁₈ in the substituent and/or in its salt products reactions.

Methods for preparing a surface-treated filler material product treated with at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic, or cyclic group having a total number of carbon atoms of at least , C2 to C ₃₀ in the substituent, and the corresponding coating compounds are described, for example, in WO 2016/023937 A1, which is thus incorporated herein by reference.

According to another embodiment of the present invention, the surface-treated filler material product comprises a treatment layer on at least a portion of the surface of at least one pulverized calcium carbonate-containing filler material, where the treatment layer contains at least one polydialkylsiloxane.

Preferred polydialkylsiloxanes are described, for example, in US 2004/0097616 A1. Most preferred are polydialkylsiloxanes which are selected from the group consisting of polydimethylsiloxane, preferably dimethicone, polydiethylsiloxane and polymethylphenylsiloxane and/or mixtures thereof.

For example, at least one polydialkylsiloxane is preferably a polydimethylsiloxane (PDMS).

At least one polydialkylsiloxane is preferably present in such an amount that the total amount of said polydialkylsiloxane on at least part of the surface of at least one particulate filler material containing calcium carbonate is less than 1000 ppm, more preferably , less than 800 ppm, and most preferably less than 600 ppm. is from 100 to 1000 ppm, more preferably from 200 to 800 ppm, and most preferably from 300 to 600 ppm, for example, from 400 to 600 ppm.

The treatment layer on the surface of at least one crushed filler material containing calcium carbonate preferably contains at least one saturated aliphatic linear or branched carboxylic acid and its salt reaction products, and/or at least one monosubstituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or salt reaction products thereof. More preferably, the treatment layer on the surface of at least one particulate filler material containing calcium carbonate contains at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof.

In one embodiment, the treatment layer, on at least part of the surface of at least one pulverized filler material containing calcium carbonate, contains a mixture of the above materials, preferably a mixture of two materials.

Thus, an additional processing layer may be present on the processing layer.

The "post-treatment layer" in the meaning of the present invention refers to a layer, preferably a monolayer of surface treatment agent, which may be different from the treatment layer, the "post-treatment layer" being located on the "treatment layer".

In one of the preferred embodiments, the surface treatment of at least one particulate filler material containing calcium carbonate is carried out in two stages, the first stage includes treatment with a mixture of phosphoric acid esters, one or more phosphoric acid monoesters and/or one or more diesters of phosphoric acid or at least one saturated aliphatic linear or branched carboxylic acid or at least one aliphatic aldehyde or at least one monosubstituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic or cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent to form a treatment layer, and the second step includes treatment with at least one polydialkylsiloxane to form a layer additional processing.

In another embodiment, the surface treatment is carried out by treating at least one particulate filler material containing calcium carbonate simultaneously with a mixture of phosphoric acid esters, one or more monophosphoric acid esters and/or one or more phosphoric acid 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, consisting of succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic and cyclic a group having a total number of carbon atoms of at least C2 to _C30 in the substituent and at least one polydialkylsiloxane to form a treatment layer.

In addition, surface treatment can be carried out by treating at least one particulate filler material containing calcium carbonate, first with a polydialkylsiloxane, and then with a mixture of phosphoric acid esters, one or more monophosphate esters of phosphoric acid and/or one or several diesters of phosphoric acid or at least one saturated aliphatic linear or branched carboxylic acid or at least one aliphatic aldehyde or at least one monosubstituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from linear , a branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent.

Preferably, the post-treatment layer contains at least one polydialkylsiloxane.

Thus, the treatment layer, on at least part of the surface of at least one particulate filler material containing calcium carbonate, preferably contains a mixture of phosphoric acid esters, one or more monophosphoric acid esters and salt reaction products thereof and/or one or more diesters of phosphoric acid and salt reaction products thereof, and the post-treatment layer contains at least one polydialkylsiloxane.

Alternatively, the treatment layer, at least on a part of the surface, of at least one crushed filler material containing calcium carbonate contains at least one saturated aliphatic linear or branched carboxylic acid and salt products of its reaction, and an additional treatment layer contains at least one polydialkylsiloxane.

Alternatively, the treatment layer, on at least part of the surface of at least one crushed filler material containing calcium carbonate, contains at least one aliphatic aldehyde and/or salt products of its reaction, and the post-treatment layer contains at least at least one polydialkylsiloxane.

Alternatively, the treatment layer, on at least a portion of the surface of at least one pulverized filler material containing calcium carbonate, contains at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from linear, branched , an aliphatic and a cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or salt reaction products thereof, and the post-treatment layer contains at least one polydialkylsiloxane.

More preferably, the treatment layer on at least part of the surface of at least one pulverized filler material containing calcium carbonate contains, most preferably, consists of at least one saturated aliphatic linear or branched carboxylic acid and salt products reaction thereof or at least one monosubstituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent and /or in salt products of its reaction, and the post-treatment layer contains, more preferably, consists of at least one polydialkylsiloxane. For example, the treatment layer on at least a portion of the surface of at least one pulverized filler material containing calcium carbonate contains, most preferably, consists of at least one saturated aliphatic linear or branched carboxylic acid and its salt products. reaction, and the post-treatment layer contains, more preferably, consists of at least one polydialkylsiloxane.

According to one embodiment, the salt product(s) of their reaction for a phosphoric acid ester, a mixture of one or more phosphoric acid monoesters, one or more phosphoric diesters, or at least one saturated aliphatic linear or branched carboxylic acid, at least one aliphatic aldehyde, or at least one monosubstituted succinic anhydride are one or more of their calcium and/or magnesium salts.

Thus, it is clear that at least one particulate filler material containing calcium carbonate contains, and preferably consists of at least one particulate filler material containing calcium carbonate, and a treatment layer containing

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products and/or one or more phosphoric acid diesters, and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline its reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i. -v.

A treatment layer is formed on the surface of said at least one crushed filler material containing calcium carbonate.

One of the requirements of the present invention is that the product of surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3% by weight, in relation to the total dry weight, of at least one crushed filler material containing calcium carbonate .

According to one embodiment, the surface-treated filler material product contains a treatment layer in an amount of 0.2 to 2.0 wt%, preferably 0.4 to 1.9 wt%, and most preferably 0.5 to 1 .8 wt %, based on the total dry weight of at least one pulverized filler material containing calcium carbonate.

The treatment layer is preferably characterized in that the total weight of the mixture of phosphoric acid esters of one or more monophosphoric acid esters and salt products thereof and/or one or more diesters of phosphoric acid and salt products thereof, and/or at least , one saturated aliphatic linear or branched carboxylic acid and salt products of its reaction, and / or at least one aliphatic aldehyde and / or salt products of its reaction, and / or at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C ₂ to C ₃₀ in the substituent and/or in the salt reaction products thereof, and/or at least , one polydialkylsiloxane and/or a mixture of these materials on the product surface of the surface-treated filler material is from 0.05 to 1% w/m ² , more preferably from 0.1 to 0.5% w/m ² , and most preferably , from 0.15 to 0.25 wt%/m ² of at least one crushed filler material containing calcium carbonate.

In one embodiment of the present invention, the treatment layer is characterized in that the total weight of the mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt products and/or one or more phosphoric acid diesters and their salt products, and/or at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or at least one aliphatic aldehyde and/or salt reaction products thereof, and/or at least one monosubstituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent and/or in the salt products of its reaction, and /or at least one polydialkylsiloxane, and/or a mixture of these materials on the product surface of the surface-treated filler material is from 0.1 to 5 mg/m ² , more preferably from 0.25 to 4.5 mg/m ² , and most preferably, from 1.0 to 4.0 mg/m ² , at least one material containing calcium carbonate.

Obviously, the surface-treated filler material product preferably has a flash point of ≥250°C. For example, a surface-treated filler material product has a flash point of ≥260°C or ≥270°C. In one embodiment, the surface-treated filler material product has a flashpoint of 250°C to 400°C, preferably 260°C to 400°C, and most preferably 270°C to 400°C.

In addition or alternatively, the surface-treated filler material product is characterized by a total volatile content between 25 and 350° C. of less than 0.25 wt. %, and preferably less than 0.23 wt. %, for example, from 0.04 to 0.21 wt%, preferably 0.08 to 0.15 wt%, more preferably 0.1 to 0.12 wt%.

In addition, the product of the surface-treated filler material has a low tendency to entrain water. It is preferred that the moisture entrapping propensity of the surface-treated filler material product is such that its total surface moisture level is less than 1 mg/g dry calcium carbonate-containing filler material at a temperature of about +23°C (±2° C). For example, a surface-treated filler material product has a moisture pickup propensity of 0.1 to 1 mg/g, more preferably 0.2 to 0.9 mg/g, and most preferably 0.2 to 0.8 mg/g dry material containing calcium carbonate after exposure to +23°C (± 2°C).

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

Obviously, at least one layer of the single or multilayer polyester film contains the product of the surface-treated filler material at a particularly high content. Thus, at least one layer of a single or multilayer polyester film contains a surface-treated filler material product in an amount of >30 to 80.0 wt %, based on the total weight of the layer.

According to one of the embodiments, at least one layer of a single-layer or multi-layer polyester film contains a surface-treated filler material product in an amount of from 30.01 to 80.0% by weight, relative to the total weight of the layer, preferably from 30. 1 to 78.0 wt%, more preferably 30.5 to 75.0 wt%, even more preferably 31.0 to 73.0 wt%, and most preferably 35.0 to 70.0% mass.

In accordance with one aspect of the present invention, the surface-treated filler material product described above is used as a blowing agent for a single or multilayer polyester film.

Single or multilayer polyester (polyester) film

The present invention provides a single or multilayer polyester film wherein at least one film layer contains at least one polyester in an amount ranging from 20.0 to <70 wt% and a surface treated filler material product of in an amount ranging from >30 to 80.0 wt%, based on the total weight of the layer, where the surface-treated filler material product contains

A) at least one pulverized filler material containing calcium carbonate having a weighted median particle sized ₅₀ between 0.5 µm and 3.0 µm, and

B) a treatment layer on the surface of at least one crushed filler material containing calcium carbonate, containing

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products and/or one or more phosphoric acid diesters and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii. at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic or cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline its reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i. - v.,

where the product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3 wt%, in relation to the total dry weight of at least one crushed filler material containing calcium carbonate.

As discussed above, it has advantageously been found that it is possible to obtain a single or multi-layer polyester film containing a particularly high filler content, ie a high content of surface-treated filler material product. Thus, it is clear that a layer containing at least one polyester and a surface treated filler material product contains a surface treated filler material product in an amount of >30 to 80.0 wt %, based on the total weight. layer, preferably from 30.01 to 80.0 wt%, more preferably from 30.1 to 78.0 wt%, even more preferably from 30.5 to 75.0 wt%, even more preferably from 31 0 to 73.0% of the mass, and most preferably, from 35.0 to 70.0% of the mass.

The single or multilayer polyester film may be any kind of polyester film. Preferably, the single or multilayer polyester film is a cast film, a blown film, a double blown film, or a monoaxially oriented polyester film. More preferably, the single or multilayer polyester film is a cast film or a monoaxially oriented polyester film. Most preferably, the single or multilayer polyester film is a monoaxially oriented polyester film.

For example, the term "mono-axially oriented" polyester film refers to a film that is made by stretching a cast film in only one direction from the machine direction (MD) or the transverse direction (TD).

Single or multi-layer polyester film is particularly characterized by low density; especially when compared to a film containing no surface-treated filler material product. Thus, a single or multilayer polyester film, especially a layer containing at least one polyester and a surface-treated filler material product, preferably has a density of from 1.8 to 2.4 g/cm ³ , preferably from 1.8 to 2.35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ , and most preferably 1.9 to 2.25 g/m ^{2 ,}

According to one embodiment, the median thickness of a single or multilayer polyester film, especially a layer containing at least one polyester and a surface treated filler material product, is from 0.5 to 2000 µm, preferably from 4 to 1500 µm, more preferably 5 to 1300 µm, and most preferably 6 to 1000 µm, such as 8 to 500 µm.

According to one embodiment, a single or multilayer polyester film, especially a layer containing at least one polyester and a surface treated filler material product, has a median thickness of 0.5 to 2000 µm, preferably 4 to 1500 µm, more preferably from 5 to 1300 µm, and most preferably from 6 to 1000 µm, for example, from 8 to 500 µm, and a density from 1.8 to 2.4 g/cm ³ , preferably from 1, 8 to 2.35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ , and most preferably 1.9 to 2.25 g/m ^{2 ,}

Obviously, the polyester film is a single or multilayer film.

In the case of a multilayer polyester film, the film consists of two or more layers, for example two to ten layers, preferably three layers, which are adjacent, ie in direct contact with each other. If the multilayer film is a three-layer film, the film preferably has an A-B-A or A-B-C film structure. In a multilayer film, the core layer preferably contains voids, that is, it is a layer containing at least one polyester and a surface-treated filler material product. In one embodiment, the multilayer film comprises a barrier layer that is sandwiched between two adjacent layers. "Barrier layer" in the meaning of this application refers to a diffusion barrier, for example, an oxygen and/or water vapor barrier, which is used to protect packaged goods from various external influences.

The barrier layer may be any material known in the art to be suitable for this purpose. For example, the barrier layer may be an aluminum layer, an Al ₂ O ₃ layer, a SiO _x layer, an ethylene vinyl alcohol layer, a poly(vinyl alcohol) layer, a polyvinylidene chloride layer, a polypropylene layer, preferably an oriented polypropylene layer, a polyethylene layer, preferably an oriented polyethylene, a barrier layer of polyester, for example sold under the trade name HOSTAPHAN®, and mixtures thereof.

Obviously, the median thickness of a single or multilayer polyester film, especially the layer containing the product of the surface treated filler material, can vary widely depending on the product being produced.

For example, a layer containing at least one polyester and a surface-treated filler material product preferably has a higher thickness than the other individual layers, i.e. layers not containing at least one polyester and/or product surface treated filler material. Alternatively, the at least one polyester and the layer containing the at least one polyester and the surface-treated filler material product is about the same thickness as all other layers together, i.e. all layers not containing at least at least one polyester and/or surface treated filler material product, preferably at least one polyester and surface treated filler material product.

Preferably, the single or multilayer polyester film, especially the layer containing at least one polyester and surface treated filler material product, has a median thickness of 0.5 to 2000 µm, preferably 4 to 1500 µm, more preferably 5 to 1300 µm, and most preferably 6 to 1000 µm, for example 8 to 500 µm.

A single or multilayer polyester film, especially a layer containing at least one polyester and a surface treated filler material product, is advantageous when it is a well balanced microporous film/layer. That is, so to speak, a microporous film or layer is created by controlling the formation of voids, it has a low density and an opaque appearance at a high filler content.

Thus, a single or multilayer polyester film, especially a layer containing at least one polyester and a surface-treated filler material product, preferably has

a) a density in the range of 1.8 to 2.4 g/cm ³ , preferably 1.8 to 2.35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ , and most preferably from 1.9 to 2.25 g/m ² , and/or

b) opacity ≥50%, preferably ≥55%, and most preferably ≥60%.

For example, a single or multilayer polyester film, especially a layer containing at least one polyester and a surface treated filler material product, preferably has

a) a density in the range of 1.8 to 2.4 g/cm ³ , preferably 1.8 to 2.35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ , and most preferably 1.9 to 2.25 g/m ² , or

b) opacity ≥50%, preferably ≥55%, and most preferably ≥60%.

Unless otherwise stated, the mechanical and optical properties described herein refer to a layer or film containing a polyester and a surface-treated filler material product, determined according to the Examples section of this document below, i.e. using a laboratory device. for biaxial stretching (Model Maxi Grip 750S Bi-axial Laboratory Stretching Frame, from Dr. Collin GmbH, Germany) under the described conditions. Thus, it is clear that results for a layer or film containing a polyester and a surface-treated filler material product obtained under different conditions may differ from the mechanical and optical properties defined herein.

In addition, a single or multilayer polyester film, especially a layer containing at least one polyester and a surface-treated filler material product, is advantageous because the mechanical properties of the film, especially of this layer, are maintained at a high level.

In addition, it is obvious that a single or multi-layer polyester film, preferably at least one layer containing the surface-treated filler material product, is microporous and has good optical properties.

According to one embodiment, the layer containing at least one polyester and a surface-treated filler material product, the single or multilayer polyester film further comprises a thermoplastic polymer, preferably cross-linked with a cross-linking agent. The thermoplastic polymer is preferably selected from the group consisting of polyolefin, cyclic olefin (COC) copolymer, polyketone, polysulfone, fluoropolymer, polyacetal, ionomer, acrylic resin, polystyrene resin, polyurethane, polyamide, polycarbonate, polyacrylonitrile, and their copolymerized resin and mixtures.

Thus, if the single or multilayer polyester film contains a thermoplastic polymer, that thermoplastic polymer is present in the same layer as at least one polyester and surface treated filler material product.

Obviously, the presence of a thermoplastic polymer in a layer containing at least one polyester and a surface-treated filler material product, a single or multi-layer polyester film, is advantageous because it acts as an organic blowing agent and thus improves the formation of voids during production. film or layer. However, the thermoplastic polymer generally does not help increase the opacity of the appearance of the film or layer.

It should be noted that the thermoplastic polymer is insoluble in at least one polyester. Thus, at least one polyester forms a continuous phase, i.e. a matrix, and the thermoplastic polymer is dispersed in it, i.e. it forms a dispersed phase.

The polyolefins that can be used are preferably selected from the group consisting of polypropylene, polyethylene, polybutylene and mixtures thereof.

The polyolefin may be a copolymer or a homopolymer, the latter being particularly preferred.

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

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

The thermoplastic polymer, which is a polyolefin, preferably has a melt flow rate MFR ₂ (230°C; 2.16 kg), measured according to ISO 1133, in the range from 1 to 20 g/10 min, preferably from 1 to 15 g/10 min , more preferably 1 to 10 g/10 min, and most preferably 1 to 5 g/10 min.

Additionally or alternatively, the polyolefin thermoplastic polymer preferably has a density of <0.920 g/cm ³ , more preferably <0.910 g/cm ³ , still more preferably in the range of 0.800 to 0.920 g/cm ³ , still more preferably from 0.850 to 0.910 g/cm ³ , and most preferably from 0.880 to 0.910 g/cm ^{3 ,}

If polyolefins, such as polypropylene, are used as a blowing agent, it should be noted that polyolefins often do not disperse properly and may require a compatibilizer, such as carboxylated polyethylene, to obtain a uniform void distribution. When used together with at least one polyester to form void films, the polyolefins also tend to lower the surface tension of the polyester film and thereby reduce the printability of the film. Polyolefins are softer than at least one polyester at room temperature, which sometimes lowers the overall modulus of the film to unacceptable levels. Finally, polyolefins are relatively inefficient converters and large amounts are required to achieve the desired density reduction, resulting in poor surface roughness and printing problems, thus making it difficult to use polyolefins in single layer films.

Cyclic olefin copolymer (COC) as used herein refers to a copolymer of ethylene and at least one cyclic olefin selected from the group consisting of bicycloalkene and tricycloalkene.

Representative examples of the cyclic olefin copolymer (COC) 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, tricyclo[4.3.0.1 ^2.5 ]-3-decene, 2-methyltricyclo[4.3.0.1 ^{2, 5} ]-3-decene, 5-methyl-tricyclo[4.3.0.1 ^2.5 ]-3-decene, tricyclo[4.4.0.1 ^2.5 ]-3-decene and 10-methyl-tricyclo[4.4.0.1 ^{2, 5} ]-3-decene.

The polyamide that can be used is preferably polyamide 6 (also referred to as nylon 6) or polyamide 66 (also referred to as nylon 66).

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

A layer of a single or multilayer polyester film containing at least one polyester and a surface-treated filler material product contains a thermoplastic polymer in an amount ranging from 0.1 to 29.9% by weight, preferably from 1 to 28% mass, more preferably from 2 to 26 wt%, even more preferably from 3 to 25 wt%, even more preferably from 4.5 to 23 wt%, and most preferably from 4 wt% to 20 wt%, according to relative to the total weight of the layer.

In one embodiment, the single or multilayer polyester film layer comprising at least one polyester and surface treated filler material product contains a thermoplastic polymer in an amount less than the amount of surface treated filler material product. For example, a layer containing at least one polyester and a surface-treated filler material product, a single or multilayer polyester film, contains a thermoplastic polymer in an amount of at least 20% by weight, more preferably at least by at least 30 wt %, and most preferably at least 50 wt %, based on the total weight of the surface treated filler material product, which is lower than the amount of surface treated filler material product.

In addition or alternatively, at least one layer of the film comprising the polyester and the surface treated filler material product further comprises an inorganic filler material different from the surface treated filler material product. Preferably, the inorganic filler material other than the surface treated filler material product is selected from the group consisting of alumina, silica, titanium dioxide, alkali metal salts such as barium carbonate, calcium sulfate, barium sulfate, and mixtures thereof. Barium sulfate is particularly preferred as the inorganic filler material.

Obviously, the presence of an inorganic filler material other than the surface-treated filler material product in the layer containing at least one polyester and the surface-treated filler material product of a single or multilayer polyester film is advantageous because it acts as an inorganic blowing agent and thus further improves the formation of voids during film production. In addition, an inorganic filler material other than the surface-treated filler material product further enhances the opacity of the appearance of the film or layer.

However, if the film layer comprising at least one polyester and surface treated filler material product further comprises an inorganic filler material different from the surface treated filler material product, the amount of inorganic filler material is generally less than the amount of surface treated material product. - processed filler.

For example, a film layer containing at least one polyester and a surface treated filler material product contains an inorganic filler material different from the surface treated filler material product in an amount of 1 to 10 wt %, based on the total weight of the layer.

In one embodiment, the layer containing at least one polyester and the surface treated filler material product of the single or multilayer polyester film contains an inorganic filler material other than the surface treated filler material product in an amount of at least 20 wt %, more preferably at least 30 wt %, and most preferably at least 50 wt %, based on the total weight of the surface treated filler material product, which is less than the amount of surface treated material product filler.

The weighted median particle size d ₅₀ of the inorganic filler material other than the surface treated filler material product is preferably similar to the weighted median particle size d ₅₀ of the surface treated filler material product. Thus, the inorganic filler material other than the surface-treated filler material product preferably has a weighted median particle size d ₅₀ in the range of 0.5 µm to 3.0 µm, preferably 0.5 µm to 2.5 µm, more preferably 0.5 µm to 2 µm, even more preferably 0.5 µm to 1.8 µm, and most preferably 0.6 µm to 1.8 µm.

In addition, or alternatively, the single or multilayer polyester film may further contain additives that are commonly used as additives in films to be made. Preferably, they are added to the polymer or polymer mixture prior to melting. Alternatively, these compounds may be added to the masterbatch.

For example, the single or multilayer polyester film contains an additive selected from the group consisting of light stabilizers, optical brighteners, cyan dyes, antiblocking agents, white pigments, and mixtures thereof.

Preferably, the layer containing at least one polyester and surface-treated filler material product contains an additive selected from the group consisting of light stabilizers, optical brighteners, blue dyes, anti-blocking agents, white pigments, and mixtures thereof.

Obviously, light stabilizers, which are UV stabilizers or UV absorbers, are chemical additives that can interfere with the physical and chemical processes of light-induced degradation. Carbon black and other pigments can provide some degree of protection from the negative effects of light, but these substances are unsuitable for white films because they can cause yellowing or discolouration. The only additives suitable for white films are organic or organometallic compounds which do not, or only very little, impart color or discoloration to the film to be stabilized. Light stabilizers, which are suitable UV stabilizers, absorb at least 70%, preferably 80%, particularly preferably 90%, of UV light in the wavelength range from 180 to 380 nm, preferably from 280 to 350 nm. Particularly useful stabilizers are those compounds which, in the temperature range from 260 to 300° C., are thermally stable, ie do not decompose and do not cause the release of gases. Examples of light stabilizers which are useful UV stabilizers are 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo nickel compounds, salicylic esters, cinnamon esters, resorcinol monobenzoates, oxanilides, hydroxybenzoic esters, hindered amines and triazines, preferably , 2-hydroxybenzotriazoles and triazines. Most preferably, the light stabilizer is hydroxyphenyltriazine (Tinuvin®1577, BASF, Ludwigshafen, Germany). The amounts of light stabilizers used are typically 10 to 50,000 ppm, preferably 20 to 30,000 ppm, and most preferably 50 to 25,000 ppm. in relation to the total weight of the film, preferably the layer containing at least one polyester and the product of the surface-treated filler material.

An additional additive present in the film, preferably in the layer containing at least one polyester and the surface-treated filler material product, if desired, is an optical brightener. The optical brighteners of the present invention can absorb UV radiation in the wavelength range of about 360 to 380 nm and emit it again as longer wavelength visible blue-violet light. Suitable optical brighteners are bisbenzoxazoles, phenylcoumarins and bissterylbiphenyls, in particular phenylcoumarin, and particularly preferably triazine-phenylcoumarin (Tinopal®, BASF, Ludwigshafen, Germany). The amounts of optical brightener used are typically from 10 to 50,000 ppm, preferably from 20 to 30,000 ppm, and most preferably from 50 to 25,000 ppm. in relation to the total weight of the film, preferably the layer containing at least one polyester and the product of the surface-treated filler material.

Suitable white pigments are preferably titanium dioxide, barium sulfate, calcium carbonate, kaolin and silica, and preference is given to titanium dioxide and barium sulfate. The titanium dioxide particles may consist of anatase or brookite or rutile, preferably mainly rutile, which has a higher hiding power than anatase. In one preferred embodiment, 95% by weight of the titanium dioxide particles are rutile. The weighted median particle size d ₅₀ of the white pigment is generally less than the weighted median particle size d ₅₀ of the surface treated filler material product and thus the white pigment does not act as a blowing agent. Preferably, the weighted median particle size d ₅₀ of the white pigment is in the range of 0.10 to 0.30 µm . The amount of white pigment in the film, preferably in the layer containing at least one polyester and surface-treated filler material product, is advantageously 0.3 to 25% by weight, based on the total weight of the film, preferably the layer containing at least one polyester and the product of the surface-treated filler material.

Additionally or alternatively, blue dyes, preferably polyester soluble blue dyes, may also be added to the film, preferably the layer containing at least one polyester and a surface treated filler material product, if healthy. For example, blue dyes that have proven to be successful are selected from cobalt blue, ultramarine blue and anthraquinone dyes, in particular Sudan blue 2 (BASF, Ludwigshafen, Germany). The amounts of blue dyes used are typically 10 to 10,000 ppm, preferably 20 to 5,000 ppm and most preferably 50 to 1,000 ppm. in relation to the total weight of the film, preferably the layer containing at least one polyester and the product of the surface-treated filler material.

In addition or alternatively, antiblocking agents may also be added to the film, preferably in a layer containing at least one polyester and a surface treated filler material product, if useful. Typical anti-blocking agents are inorganic and/or organic particles, for example, calcium carbonate other than the product of surface-treated filler material, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, phosphate magnesium, alumina, carbon black, titanium dioxide, kaolin, or cross-linked polymer particles such as polystyrene particles, acrylate particles, PMMA particles, or cross-linked silicones. Muscovite mica having an average particle size (weighted average) of 4.0 to 12.0 µm, preferably 6.0 to 10.0 µm, is also particularly suitable for use. As is generally known, mica consists of platelet-shaped silicates, in which the aspect ratio is preferably in the range of 5.0 to 50.0. Mixtures of two or more different antiblocking agents or mixtures of antiblocking agents having the same composition but different particle sizes can also be selected as additives. The particles can be added directly or via masterbatches to the polymers of the individual film layers at appropriate preferred concentrations during extrusion.

The anti-blocking agents are preferably added to the outer layer(s), i.e. the layer containing no product of the surface treated filler material. The amounts of anti-blocking agent are typically from 0.01 to 1 wt %, based on the total weight of the film, preferably the layer containing at least one polyester and the surface treated filler material product.

Obviously, compounds that are used as additives may be present in a layer containing at least one polyester and a surface-treated filler material product. In the case of a multilayer film, compounds that are used as additives may be present in the layer containing at least one polyester and surface treated filler material product and/or at least one additional layer(s).

The single or multilayer polyester film of the present invention may be produced by any method known in the art. According to one of the embodiments, the method for producing a single or multilayer polyester film includes the steps:

a) providing a composition comprising at least one polyester and a surface treated filler material product, and

b) forming a film from the composition from step a),

where the surface-treated filler material product contains

A) at least one pulverized filler material containing calcium carbonate having a weighted median particle sized ₅₀ between 0.5 µm and 3.0 µm, and

B) a treatment layer on the surface of at least one pulverized filler material containing calcium carbonate, which contains

i. a mixture of phosphoric acid esters, one or more monophosphoric acid esters and their salt reaction products and/or one or more phosphoric acid diesters, and/or

ii. at least one saturated aliphatic linear or branched carboxylic acid and salt reaction products thereof, and/or

iii at least one aliphatic aldehyde and/or salt reaction products thereof, and/or

iv. at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total number of carbon atoms of at least C2 to _C30 in the substituent, and/or saline their reaction products, and/or

v. at least one polydialkylsiloxane and/or

vi. mixtures of materials according to i. -v.,

where the product of the surface-treated filler material contains a treatment layer in an amount of from 0.1 to 2.3 wt%, in relation to the total dry weight of at least one crushed filler material containing calcium carbonate.

The composition of at least one polyester and surface-treated filler material product obtained in process step a) may be a masterbatch or compound obtained by mixing and/or kneading at least one polyester and material product surface-treated filler to form a mixture. The at least one polyester and surface treated filler material product, and if present, other optional additives, may be blended and/or kneaded using an appropriate mixer, such as a Henschel mixer, super mixer, tumble mixer, or whatever. similar. The compounding step can be carried out with a suitable extruder, preferably with a twin screw extruder (corotating or counter-rotating) or with any other suitable continuous compounding equipment, e.g. continuous mixer (Buss), continuous mixer (Farrel Pomini ), ring extruder (Extricom) or something similar. A solid mass of polymer from extrusion can either be pelletized with (hot cut) die edge, pelletized with underwater pelletization, eccentric pelletization and water ring pelletization, or with (cold cut) strand pelletization, with underwater and conventional strand pelletization, with the formation extruded polymer mass in the form of granules. Thus, the compound may be in the form of pellets, beads or granules.

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

Optionally, the compounding step may also be carried out in a batch or batch process using an internal (batch) mixer such as a Banburry mixer (HF Mixing Group) or a Brabender mixer (Brabender) or the like.

According to one embodiment, the masterbatch or compound contains a surface-treated filler material product in an amount of >30 wt%, preferably >30 to 85.0 wt%, more preferably 30.01 to 85.0 wt%, even more preferably from 30.1 to 85.0 wt%, even more preferably from 30.5 to 85.0 wt%, even more preferably from 31.0 to 85.0 wt%, and most preferably from 35.0 to 80.0% by weight, for example 40 to 70% by weight, based on the total weight of the masterbatch or compound.

Obviously, the composition obtained in step a) of the process is preferably obtained using polyester flakes, such as PET flakes. In this regard, it is preferable that the polyester flakes, for example PET flakes, are pre-dried before preparing the composition of step a) to remove moisture. For example, polyester flakes such as PET flakes are pre-dried at 90°C for 6 hours.

According to an optional embodiment, the composition obtained in step a) of the process further comprises one or more of the additives/compounds described above.

The masterbatch or compound is preferably blended with the same or a different polyester (as used as the matrix in the masterbatch or compound) and/or with one or more of the additives described above prior to step b) of the process. According to a preferred embodiment, the masterbatch or compound is mixed with the same polyester (as used as the matrix in the masterbatch or compound) prior to step b) of the process.

In one embodiment, additives that are commonly used as additives, such as light stabilizers, optical brighteners, cyan dyes, anti-blocking agents, white pigments, and mixtures thereof, are added to the masterbatch.

Alternatively, steps a) and b) of the process are carried out simultaneously. Preferably, steps a) and b) of the process are carried out simultaneously, wherein at least one polyester, more preferably pre-dried polyester flakes, such as pre-dried PET flakes, and the surface treated filler material product, more preferably dry the surface-treated filler material product is added directly to the extruder during step b) of the process. That is to say, the composition of at least one polyester and surface treated filler material product obtained in process step a) is obtained by directly adding a surface treated filler material product, preferably a dry surface treated material product. treated filler, and at least one polyester, more preferably pre-dried polyester flakes, for example pre-dried PET flakes, into the extruder in step b) of the process.

Alternatively, a composition comprising at least one polyester and the surface treated filler material product from step a) is obtained by adding the surface treated filler material product to the polycondensation process of at least one polyester. That is, so to speak, a composition comprising at least one polyester and a surface treated filler material product from step a) is obtained by adding a surface treated filler material product either before, during or after the polycondensation process, at least one polyester. For example, a composition comprising at least one polyester and a surface treated filler material product from step a) is obtained by adding a surface treated filler material product either before or after, preferably after, a polycondensation process of at least , one polyester. Thus, a composition containing at least one polyester and the surface-treated filler material product from step a) can be obtained as a ready-to-use composition.

Obviously, materials such as recycled polyester material may already contain the product of the surface treated filler material of the present invention. In this embodiment, the product amount of surface treated filler material further added to step a) of the process can thus be adapted according to a smaller amount to obtain the desired product content of surface treated filler material in a single or multilayer polyester film.

Step b) of the process can be carried out using any of the well-known technologies used to obtain polymer films. Examples of suitable film extrusion technologies are blown film extrusion or cast film extrusion.

Accordingly, step b) of the process is preferably an extrusion process.

In a preferred extrusion process for film formation, the molten composition of at least one polyester and surface-treated filler material product obtained in process step a) is extruded through a slot die and, in the form of a substantially amorphous pre-film, is quenched on a cooling roll.

In one embodiment, the method further comprises the step c) of stretching the film obtained in step b) in only one direction from the machine direction (MD) or the transverse direction (TD).

If a monoaxially oriented film is obtained, the stretching of the film obtained in step b) is carried out in the machine direction (MD) or transverse direction (TD), preferably in the machine direction (MD).

Step c) stretching can be carried out by any means known in the art. Such methods and devices for carrying out stretching step c) are known in the art, for example as LISIM. The LISIM procedures are described in detail in EP 112167 and EP 0785858, which are hereby incorporated by reference.

During the stretching step, the polyester can delaminate from the surface of the surface treated filler material product, leaving voids in the single or multilayer polyester film.

Stretching can be carried out in one stage or using several stages. According to one embodiment, step c) of the method is carried out 1 to 10 times.

The stretch factor determines the breakage of the film at high stretch, as well as the breathability and the passage of water vapor through the resulting film, and thus an excessively high stretch factor and an excessively low stretch factor are desirably avoided. According to one embodiment, in step c) of the process, the film obtained in step b) is stretched to a stretch factor of 1.2-6 times, more preferably 1.2-4 times, in each direction.

Preferably, stretching step c) is carried out and the film obtained in step b) is stretched.

a) in machine direction (MD) at a stretch ratio of 2 to 6, preferably 3 to 4.5, or

b) in the transverse direction (TD) at a stretch ratio of 2 to 5, preferably 3 to 4.5.

According to one embodiment, step c) of the process is carried out at a stretching temperature ranging from T _g +10° C. to T _g +60° C. (T _g = glass transition temperature).

The present inventors have found that the single or multilayer polyester film of the present invention, in particular the layer containing at least one polyester and a surface treated filler material product, has a particularly high filler content. In addition, a polyester film, in particular a layer containing at least one polyester and a surface-treated filler material product, is very highly microporous at low density, in particular, its density is lower than the density usually achieved for films or layers. when using barium sulfate or titanium dioxide as a blowing agent. In addition, a polyester film, especially a layer containing at least one polyester and a surface-treated filler material product, has an opaque appearance and can be obtained without film/layer breaks. In addition, a single or multilayer polyester film, in particular a layer containing at least one polyester and a surface treated filler material product, provides good mechanical properties such as tensile strength, elongation at break or modulus of elasticity, and optical properties such as gloss and transmission.

The single or multilayer polyester film of the present invention can be used in a variety of different applications. According to one embodiment, single or multilayer polyester film is used in packaging products, preferably flexible packaging products, food contact applications, paper or glass coatings, insulating materials, solar energy applications, preferably upper or backing sheets for photovoltaic devices, in marine or aviation applications, in science, in electronic or acoustic applications, preferably in displays, in wires, cables, in RF identification, in flexible printed circuit boards, in printing, preferably in labels, in stone paper, preferably in bags, packages, boxes, books, booklets, brochures, loyalty cards, business cards, greeting cards, corrugated cardboard, envelopes, food trays, labels, games, tags, magazines, signs, billboards, stationery products, diaries, notebooks or notebooks, and in holograms, in filtering products, cosmetic products, household products, imaging media, preferably photographic paper, x-ray film or thermal imaging media, or industrial products, preferably , capacitors, release films, fiberglass panels, laminating films, hot stamping foils or insulating finishes.

According to a further aspect of the present invention, there is provided an article comprising the single or multilayer polyester film of the present invention, wherein the article is selected from the group consisting of packaging products, preferably flexible packaging products, food contact applications, paper or glass coatings. , insulating materials, solar energy applications, preferably top or backing sheets for photovoltaic devices, marine or aviation applications, scientific applications, electronic or acoustic applications, preferably displays, wires, cables, RFID, flexible printed circuit boards, printing, preferably labels, stone paper, preferably bags, packages, boxes, books, booklets, brochures, loyalty cards, business cards, greeting cards, corrugated board, envelopes, food trays, labels, games, tags, magazines, signs , billboards, printed stationery, diaries, notebooks or notepads and for holograms, filtering products, cosmetic products, household products, in imaging media, preferably photographic paper, X-ray film or thermal imaging media, or industrial products, preferably, capacitors, release films, fiberglass panels, laminating films, hot stamping foils or insulating finishes.

The scope and advantages of the present invention will be better understood on the basis of the following examples, which are intended to illustrate certain embodiments of the present invention and are non-limiting.

Examples

1 Measurement methods and materials

The following describes the measurement methods and materials used in the examples.

Own viscosity

The intrinsic viscosity is measured according to DIN ISO 1628/1 and DIN ISO 1628/5, October 1999 (in decalin at 135°C).

MFR ₂

MFR ₂ is measured according to ISO 1133 (230°C, load 2.16 kg).

Crystallization temperature T _c

The crystallization temperature is measured by differential scanning calorimetry (DSC) on a Mettler-Toledo ʺPolymer DSC instrument (Mettler-Toledo (Schweiz) GmbH, Switzerland). The crystallization curve is obtained during scanning with cooling and heating at 10°C/min between 30°C and 225°C. Crystallization temperatures are taken as the peaks of endotherms and exotherms.

Particle size

The particle distribution of the raw pulverized filler material containing calcium carbonate is measured using a Sedigraph 5100 from Micromeritics, USA. The method and tools are known to those skilled in the art and are widely used to determine the grain size of fillers and pigments. The measurement is carried out in an aqueous solution containing 0.1 wt % Na ₄ P ₂ O ₇ . The samples are dispersed using a high speed stirrer and ultrasound.

Specific surface area (BET)

Herein, the specific surface area (in m ² /g) of the filler material is determined using the BET method (using nitrogen as adsorbed gas), which is well known to those skilled in the art (ISO 9277:2010).

Ash content

Ash content [wt %] in masterbatches and films determined by incineration of the sample in an incineration crucible, which is placed in an incineration oven at 570° C. for 2 hours. The ash content is measured as the total amount of inorganic residues remaining.

Film thickness

The film thickness was determined using a Mitutoyo IP 66 digital rheocord (Mitutoyo Europe GmbH, Neuss, Germany). The measured values are given in µm.

Film or layer density

Density is determined from a fragment for research, while the exact area of the film (100 mm × 100 mm) is cut out and weighed on an analytical balance. The average film thickness is determined by taking nine thickness measurements over the entire surface of the film. Density is calculated and given in [g/cm ³ ]. Also, from these values, the average yield in m ² /kg and the surface weight in g/m ² can be calculated.

Moisture Capture

The term "moisture trapping propensity" in the meaning of the present invention refers to the amount of moisture absorbed on the surface of the filler, and is defined as mg moisture/g dry product of the treated mineral filler after exposure to an atmosphere at 10 and 85% relative humidity, respectively, for 2 .5 hours at +23°C (±2°C). The treated mineral filler product is first exposed to an atmosphere at 10% relative humidity for 2.5 hours, then the atmosphere is changed to 85% relative humidity where the sample is kept for another 2.5 hours. The increase in mass for changes in relative humidity between 10% and 85% is then used to calculate the moisture uptake in mg moisture/g dry product of the treated filler. The blank value for equipment is defined as 0.15-0.2 mg/g, for example 0.19 mg/g. The results in this application are full values, that is, the measured value minus the blank value.

hydrophilicity

The "hydrophilicity" of the filler is evaluated at +23°C by determining the minimum ratio of water and ethanol as volume/volume in relation to the water/ethanol mixture necessary to deposit the majority of said filler, where said filler is deposited on the surface of said water/ethanol mixture by passing through homemade tea strainer. The volume/volume ratio refers to the volumes of both separate liquids before mixing them together and does not include reduction in the volume of the mixture. The rating at +23°C refers to a temperature of +23°C±2°C.

A water/ethanol volume ratio of 8:2 typically corresponds to a surface tension of 41 mN/m, and a water/ethanol volume ratio of 6:4 typically corresponds to a surface tension of 26 mN/m measured at +23°C ( ±2°C) as described in "Handbook of Chemistry and Physics", ^84th edition, David R. Lide, 2003 (first edition 1913).

Measurement of total volatile matter

For the purposes of this application, the "total volatiles" associated with fillers and evolved over a temperature range of 25-350°C is characterized according to the % weight loss of a filler sample over a certain temperature range as recorded on a thermogravimetric (TGA) curve.

TGA analytical methods provide information on mass loss and flashpoints with great accuracy and are well known; this is described, for example, in "Principles of Instrumental analysis", fifth edition, Skoog, Holler, Nieman, 1998 (first edition 1992) in Chapter 31, pp. 798-800, and in other well known reference works. According to the present invention, thermogravimetric analysis (TGA) is performed using a Mettler Toledo TGA 851 based on a 500 +/- 50 mg sample and scan temperatures from 25 to 350°C at a rate of 20°C/min in an air flow of 70 ml/min.

A person skilled in the art will be able to determine the "volatilization point" by analyzing the TGA curve as follows: take the first derivative of the TGA curve and identify inflection points between 150 and 350°C. From the inflection points having a tangent slope greater than 45° relative to the horizontal line, the point having the lowest corresponding temperature above 200°C is identified. The temperature value associated with this lowest inflection point temperature of the first derivative curve is the "volatility onset temperature".

The "total volatile matter" released on the TGA curve is determined using the software Star ^e SW 9.01. Using this software, the curve is first normalized to the original sample weight to obtain weight loss in % values relative to the original sample. The temperature range from 25 to 350°C is then selected and the horizontal step option (German: "Stufe horizontal") is selected to obtain the % weight loss in the selected temperature range.

Opacity

Opacity measurement is carried out according to DIN 53146 by measuring the whiteness of a film sample on a black and white substrate using a Byk-Gardner Spectro-Guide (Byk-Gardner GmbH, Germany). Opacity is the ratio of contrast for two dimensions. The units are percentages of %, and a completely opaque material will have an opacity value of 100%.

Water Vapor Transmission Rate (WVTR)

The WVTR value of polyester films is measured using a Lyssy L80-5000 measuring device (PBI Dansensor A/S, Denmark) according to ASTM E398.

2 Materials

CC1 (according to the present invention): natural ground calcium carbonate, rock raw materials commercially available from Omya International AG, Switzerland ( d ₅₀ : 0.8 µm; d ₉₈ : 3 µm, particle content <0.5 µm=35% ), surface-treated with 1.7% by weight of stearic acid (commercially available from Sigma-Aldrich, Croda), based on total weight of natural ground calcium carbonate. BET: 8.5 m ² /g.

CC2 (according to the present invention): natural ground calcium carbonate, rock raw materials commercially available from Omya International AG, Switzerland ( d ₅₀ : 0.8 µm; d ₉₈ : 3 µm, particle content <0.5 µm=35% ), surface-treated with 1.7 wt % alkenyl succinic anhydride (CAS [68784-12-3], >93% concentration) based on total weight of natural ground calcium carbonate. BET: 8.5 m ² /g.

CC3 (according to the present invention): natural ground calcium carbonate, rock raw materials commercially available from Omya International AG, Switzerland ( d ₅₀ : 1.7 µm; d ₉₈ : 6 µm, particle content <0.5 µm=12% ), surface-treated with 1.0 wt % stearic acid (commercially available from Sigma-Aldrich, Croda), based on total weight of natural ground calcium carbonate. BET: 3.4 m ² /g.

CC4 (according to the present invention): natural ground calcium carbonate, rock raw materials commercially available from Omya International AG, Switzerland ( d ₅₀ : 1.7 µm; d ₉₈ : 6 µm, particle content <0.5 µm=12% ), surface-treated with 0.7% by weight of alkenyl succinic anhydride (CAS [68784-12-3], >93% concentration) based on total weight of natural ground calcium carbonate. BET: 3.4 m ² /g.

CC5 (according to the present invention): natural ground calcium carbonate, rock raw materials commercially available from Omya International AG, Switzerland ( d ₅₀ : 1.7 µm; d ₉₈ : 6.5 µm, particle content <2 µm=57% ), surface-treated with 1% by weight of stearic acid (commercially available from Sigma-Aldrich, Croda), relative to the total weight of natural milled calcium carbonate. BET: 4 m ² /g.

CC6 (according to the present invention): natural ground calcium carbonate, rock raw materials commercially available from Omya International AG, Switzerland ( d ₅₀ : 2.6 µm; d ₉₈ : 15 µm, particle content <2 µm=38%), surface-treated with 0.6% by weight of stearic acid (commercially available from Sigma-Aldrich, Croda), based on total weight of natural ground calcium carbonate. BET: 2.5 m ² /g.

CC7 (comparative): natural ground calcium carbonate commercially available from Omya International AG, Switzerland ( d ₅₀ : 5 µm; d ₉₈ : 20 µm) surface treated with 0.5 wt % stearic acid (commercially available from Sigma- Aldrich, Croda), relative to the total mass of natural ground calcium carbonate. BET: 2.1 m ² /g.

CC8 (comparative): natural ground calcium carbonate commercially available from Omya International AG, Switzerland ( d ₅₀ : 5 µm; d ₉₈ : 30 µm), without surface treatment. BET: 2.1 m ² /g.

Surface treatment CC1-CC7 is carried out using the methods described in EP 2722368 A1.

P1: polyethylene terephthalate (PET), Lighter C93 PET, commercially available from Equipolymers GmbH, Germany (intrinsic viscosity: 0.8 ± 0.02 dl/g, crystallinity min 50%, melting point 247°C, according to specification supplied by the supplier).

3 Examples

Example 1 - Preparation of masterbatches

Polyethylene terephthalate (PET) masterbatches containing CC1-CC8 fillers with calcium carbonate and polymer P1 are continuously prepared in a Buss mixer (Buss PR46 from Buss AG, Switzerland) on a laboratory scale. The polymer P1 is pre-dried before being processed in an oven at 160° C. for 4 hours. The compositions and filler contents for the prepared masterbatch are shown in Table 1 below. The exact filler content is determined from the ash content.

Table 1: Composition and filler content of prepared masterbatches.

Masterbatch Filler Filler content
[wt%] MB1 (according to the present invention) CC1 50 MB2 (according to the present invention) CC2 50 MB3 (according to the present invention) CC3 50 MB4 (according to the present invention) CC4 50 MB5 (according to the present invention) CC5 50 MB6 (according to the present invention) CC6 50 MB7 (comparative) CC7 50 MB8 (comparative) CC8 50

Masterbatches MB1-MB6 can be obtained in good quality, while Masterbatches MB7 and MB8 are difficult to compound and the resulting granules are of poor quality.

Example 2 - Preparation of polyester cast films using a masterbatch

Cast films were prepared on a Collin Laboratory Film Line (Dr. Collin GmbH, Germany) using a 30 mm diameter twin screw extruder with a wide T-die and a take-off system which has temperature controlled chill rolls. The chill roll is 20 mm away from the T-die to produce a polyester sheet having a thickness of about 1000 µm. The temperatures of the extruder and die are consistent during the experiment. The die temperature is set at 270°C; line speed is 0.5 m/min. The masterbatch or polymer is mixed with pure polymer P1 to produce cast films at the concentrations shown in Table 2.

Table 2: Compositions and properties of the produced cast films

Film sample Masterbatch Filler content
[wt%] 1 (compar.) No 0 2 (according to the present invention) MB1 35 3 (according to the present invention) MB1 45 4 (according to the present invention) MB2 35 5 (according to the present invention) MB2 45 6 (according to the present invention) MB3 35 7 (according to the present invention) MB3 45 8 (according to the present invention) MB4 35 9 (according to the present invention) MB4 45 10 (according to the present invention) MB5 35 11 (according to the present invention) MB5 45 12 (according to the present invention) MB6 35 13 (according to the present invention) MB6 45

All films shown in Table 2 are cast films, which are obtained in good quality and good appearance.

Example 3 - Preparation of polyester films obtained by direct extrusion

Cast films were prepared on a Collin Laboratory Film Line (Dr. Collin GmbH, Germany) using a 30 mm diameter twin screw extruder with a wide T-die and a take-off system which has temperature controlled chill rolls. The chill roll is supported at a distance of 20 mm from the T-die to obtain a polyethylene terephthalate sheet having a thickness of about 1000 µm. The extruder is equipped with a vacuum ventilation system to remove during the extrusion of volatile substances and moisture from the raw materials. The temperatures of the extruder and die are consistent during the experiment. The die temperature is set at 270°C; line speed is 0.5 m/min. The masterbatch or polymer is mixed with pure polymer P1 to produce cast films at the concentrations shown in Table 2.

Table 3: Compositions and properties of prepared cast films

Film sample Filler Filler content
[wt%] 1 (compar.) No 0 2 (according to the present invention) CC1 60 3 (according to the present invention) CC1 70 4 (according to the present invention) CC2 60 5 (according to the present invention) CC2 70 6 (according to the present invention) CC3 60 7 (according to the present invention) CC3 70 8 (according to the present invention) CC4 60 9 (according to the present invention) CC4 70 10 (according to the present invention) CC5 60 11 (according to the present invention) CC5 70 12 (according to the present invention) CC6 60 13 (according to the present invention) CC6 70

Claims (50)

1. A film for producing products, containing at least one polyester in an amount ranging from 20.0 to <70% wt., selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), a thermoplastic polymer selected from a polyolefin including polypropylene, polyethylene, polybutylene, and surface-treated filler material product in an amount ranging from >30 to 78.0 wt%, based on the total weight of the layer, where the surface-treated filler material product contains A) at least one ground filler material containing calcium carbonate having a weighted median particle size d ₅₀ ranging from 1.7 to 2.6 microns, and B) a treatment layer on the surface of at least one pulverized filler material containing calcium carbonate, which contains - stearic acid, or - at least one monosubstituted succinic anhydride, consisting of succinic anhydride, the monosubstituted group of which is selected from alkenyl, where the product material surface-treated filler contains a layer of treatment in an amount of from 0.6 to 2.3 wt. -%, in relation to the total dry weight of at least one crushed filler material containing calcium carbonate. 2. The film of claim 1, wherein the film layer comprising at least one polyester and a surface treated filler material product contains a surface treated filler material product in an amount ranging from 30.01 to 78.0 wt%. ., relative to the total weight of the layer, preferably from 30.5 to 75.0 wt. -%, more preferably, from 31.0 to 73.0 wt. -%, and most preferably, from 35.0 to 70.0 % wt. 3. A film according to any one of the preceding claims, wherein the film layer comprising at least one polyester and the surface-treated filler material product contains at least one polyester in an amount ranging from 20.0 to 69, 99 wt%, more preferably 22.0 to 69.9 wt%, based on the total weight of the layer. 4. The film according to any one of the preceding claims, wherein at least one particulate filler material containing calcium carbonate is a wet or dry pulverized filler material containing calcium carbonate, and preferably is a wet pulverized filler containing calcium carbonate. 5. A film according to any one of the preceding claims, wherein at least one particulate filler material comprising calcium carbonate is natural pulverized calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface treated calcium carbonate, or a mixture thereof, and preferably , natural ground calcium carbonate. 6. Film according to any one of the preceding claims, wherein at least one particulate filler material containing calcium carbonate has a) particle size maximum content d ₉₈ ≤15 µm preferably ≤10 µm, more preferably ≤7.5 µm, even more preferably ≤7 µm, and most preferably ≤6.5 µm, and/or b) fineness such that at least 15 wt%, preferably at least 20 wt%, even more preferably at least 25 wt%, and most preferably from 30 to 40 wt% . of all particles has a particle size <0.5 µm, and/or c) a specific surface area (BET) from 0.5 to 150 m ² /g, preferably from 0.5 to 50 m ² /g, more preferably from 0.5 to 35 m ² /g, and most preferably, 0.5 to 15 m ² /g as measured using nitrogen and the BET method according to ISO 9277. 7. Film according to any one of the preceding claims, wherein the surface-treated filler material product contains a treatment layer in an amount of 0.5 to 1.8% by weight, based on the total dry weight, of at least one crushed filler material containing calcium carbonate. 8. A film according to any one of the preceding claims, wherein the film comprising at least one polyester and a surface-treated filler material product contains a thermoplastic polymer in an amount ranging from 0.1 to 29.9% by weight, preferably from 1 to 28 wt%, more preferably from 2 to 26 wt%, even more preferably from 3 to 25 wt%, even more preferably from 4.5 to 23 wt%, and most preferably from 4 to 20% wt., relative to the total weight of the layer. 9. The film according to any one of the preceding claims, where the film has a) a density in the range of 1.8 to 2.4 g/cm ³ , preferably 1.8 to 2.35 g/cm ³ , more preferably 1.85 to 2.3 g/cm ³ , and most preferably, from 1.9 to 2.25 g/cm ³ , and/or b) opacity ≥50%, preferably ≥55%, and most preferably ≥60%. 10. The film according to any one of the preceding claims, wherein the film further comprises an inorganic filler material other than the product of the surface-treated filler material, and is preferably selected from the group consisting of alumina, silica, titanium dioxide, alkali metal salts such as carbonate barium, calcium sulfate, barium sulfate, and mixtures thereof, preferably in an amount of from 1 to 10% of the mass. relative to the total weight of the layer. 11. The film according to any one of the preceding claims, wherein the film contains an additive selected from the group consisting of light stabilizers, preferably 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organic nickel compounds, salicylic esters, cinnamon ester derivatives, resorcinol monobenzoates, oxanilides, hydroxybenzoic complex esters, hindered amines and triazines, more preferably 2-hydroxybenzotriazoles and triazines, most preferably hydroxyphenyltriazine, optical brightener, blue dyes, preferably polyester-soluble blue dyes, anti-blocking agents, white pigments and mixtures thereof. 12. The film of any one of the preceding claims, wherein the film is a cast film, a blown film, a double blown film, or a monoaxially oriented polyester film. 13. A method for producing a film according to any one of claims 1 to 12, including the steps: a) providing a composition comprising at least one polyester, a thermoplastic polymer, and a surface-treated filler material product, and b) forming a film from the composition from step a), Where the polyester is selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), the thermoplastic polymer is selected from a polyolefin including polypropylene, polyethylene, polybutylene, surface-treated filler material product contains A) at least one ground filler material containing calcium carbonate having a weighted median particle size d ₅₀ ranging from 1.7 to 2.6 microns, and B) a treatment layer on the surface of at least one crushed filler material containing calcium carbonate, containing - stearic acid, or - at least one monosubstituted succinic anhydride, consisting of succinic anhydride, the monosubstituted group of which is selected from alkenyl, where the product material surface-treated filler contains a layer of treatment in an amount of from 0.6 to 2.3 wt. -%, in relation to the total dry weight of at least one crushed filler material containing calcium carbonate. 14. The method of claim 13, wherein the composition obtained in step a) is a masterbatch obtained by mixing and/or kneading at least one polyester, a thermoplastic polymer and a surface-treated filler material product to form a mixture and continuously granulating the resulting mixture or a compound obtained by mixing and/or kneading at least one polyester, thermoplastic polymer and surface-treated filler material product to form a mixture; and continuously granulating the resulting mixture. 15. The method according to claim 13 or 14, where the composition obtained in step a) is a masterbatch or compound containing a surface-treated filler material product in an amount of from >30 to 85% wt., preferably from 35 to 80% wt., and more preferably, from 40 to 70 wt. -%, relative to the total mass of the masterbatch or connection. 16. The method according to any one of claims 13 to 15, wherein the composition comprising at least one polyester, a thermoplastic polymer and a surface treated filler material product from step a) is obtained by adding a surface treated filler material product, preferably , before or after the polycondensation process of at least one polyester. 17. A process according to any one of claims 13 to 16, wherein steps a) and b) of the process are carried out simultaneously, preferably wherein at least one polyester and surface treated filler material product is added directly to the extruder during step b ). 18. The method according to any one of claims 13 to 17, wherein the method further comprises the step c) of stretching the film obtained in step b) in only one machine direction (MD) or transverse direction (TD). 19. Use of a surface-treated filler material product as a blowing agent in a film according to any one of paragraphs. 1-12, where the surface-treated filler material product contains A) at least one ground filler material containing calcium carbonate having a weighted median particle size d ₅₀ ranging from 1.7 to 2.6 microns, and B) a treatment layer on the surface of at least one pulverized filler material containing calcium carbonate, which contains - stearic acid or - at least one monosubstituted succinic anhydride, consisting of succinic anhydride, the monosubstituted group of which is selected from alkenyl, where the product material surface-treated filler contains a layer of treatment in an amount of from 0.6 to 2.3 wt. -%, in relation to the total dry weight of at least one crushed filler material containing calcium carbonate. 20. An article containing a film according to any one of claims 1 to 12, wherein the article is selected from the group consisting of packaging products, preferably flexible packaging products, food contact applications, paper or glass coatings, insulating materials, applications for solar energy, preferably top or backing sheets for photovoltaic devices, marine or aviation applications, scientific applications, electronic or acoustic applications, preferably displays, wires, cables, RFID, flexible circuit boards, printing, preferably labels, stone paper, preferably bags, packages, boxes. 21. The use of the film according to any one of claims 1 to 12 in packaging products, preferably in flexible packaging products, in food contact applications, paper or glass coatings, in insulating materials, in solar energy applications, preferably in top or backing sheets for photovoltaic devices, in marine or aeronautical applications, in science, in electronic or acoustic applications, preferably in displays, in wires, cables, in RFID, in flexible printed circuit boards, in printing, preferably in labels , in stone paper, preferably bags, packages, boxes.