RU2802804C2 - Method for obtaining coarsely dispersed surface-treated filler material - Google Patents

Abstract

FIELD: filler materials.

SUBSTANCE: present invention relates to a method for producing a surface-treated filler material, which consists in the interaction of a filler material characterized by a volume median particle size d₅₀ from 5 to 100 mcm, an upper size limit (d₉₈) from 30 to 500 mcm and a residue of 45 mcm sieve, measured in accordance with ISO 787/7, more than 0.5 wt% relative to the total weight of the filler material containing calcium carbonate, with a surface treatment agent in a molten or liquid state at a temperature of from 18 to 45°C. The interaction is carried out in an Archimedean screw, for example in a screw conveyor or in a pneumatic air conveyor system, and where the Archimedean screw is operated at an angle of 30 to 80° and/or at a temperature of 18 to 45°C.

EFFECT: reduced cost of processing coarse-grained filler materials, as well as improved operational properties.

14 cl, 1 dwg, 8 tbl, 5 ex

Description

The present invention relates to a method for producing a surface treated filler material product, a surface treated filler material product, and an article containing a surface treated filler material product.

In practice, filler materials and especially filler materials containing calcium carbonate are often used as particulate fillers in polymer products, usually made from polyethylene (PE), polypropylene (PP), polyurethane (PU), polyvinyl chloride (PVC), polyester ( PES) and/or polyamide (PA). However, additives are used to coat particles of the filler material and to improve the dispersion of said filler material in the polymer matrix of the polymer compositions, and also possibly to improve the processability of the polymer composition and/or the properties of the finished polymer product. The exclusion of such additives leads to an unacceptable reduction in the quality of the finished polymer product.

Attempts have been made in the art to improve the applicability of filler materials and especially filler materials containing calcium carbonate, for example, by treating such filler materials with surface treating agents. For example, WO 00/20336 relates to ultrafine natural calcium carbonate, which may optionally be treated with one or more fatty acids, or one or more salts or mixtures thereof, and which is used as a rheology regulator for polymer compositions.

Similarly, US 4,407,986 relates to precipitated calcium carbonate, the surface of which is treated with a dispersant, which may contain higher aliphatic acids and their metal salts, to reduce the addition of lubricants when plasticizing said calcium carbonate with crystalline polypropylene and to prevent the formation of calcium carbonate aggregates that limit the impact strength of polypropylene.

EP 0 998 522 relates to a calcium carbonate filler for breathable films having a surface treated with fatty acids containing at least 10 carbon atoms, said filler being substantially free of moisture before and after the treatment process and having a moisture content of less than 0.1% wt.

DeArmitt et al. “Improved thermoplastic composites by optimized surface treatment of the mineral fillers,” Institute for Surface Chemistry, August 2000, describes a wet processing method in which a batch of slurry containing a mineral filler is brought into contact with dispersant at room temperature for one hour. However, the disadvantage of this wet method is the need to wet the dry product for processing and subsequent drying, which requires energy consumption and money.

In the publication EP 0 325 114, which relates to non-sagging anti-corrosion compositions for road transport based on polyvinyl chloride, which has improved rheological and adhesive properties, example 7 describes a mixture of the ammonium salt of 12-hydroxystearic acid in combination with a fatty acid (in a mass ratio of 1 :1), used for processing mineral filler.

WO 03/082966 relates to a cross-linked and/or cross-linked nanofiller composition, which in optional embodiments may further comprise fillers that may or may not be coated with stearic acid, stearate, silane, siloxane and/or titanate. Such compositions of nanofillers are used to increase barrier properties, strength and thermal deformation temperature, which ensures their applicability in medicine, automotive industry, electrical engineering, construction and the food industry.

US 2002/0102404 describes dispersible calcium carbonate particles whose surface is coated with a combination of saturated and unsaturated aliphatic carboxylic acids and salts thereof together with an organic compound such as a phthalic acid ester, which are used in adhesive compositions to improve viscosity stability and adhesive properties. In addition, US 2002/0102404 requires the use of a mixture of saturated and unsaturated aliphatic carboxylic acids/salts. The presence of unsaturated aliphatic carboxylic acids/salts increases the risk of in situ adverse reactions involving the double bond during processing of any materials containing unsaturated aliphatic carboxylic acids/salts. In addition, the presence of unsaturated aliphatic carboxylic acids/salts can lead to discoloration or undesirable odor and especially rancid odor of the materials in which they are used.

Clause 11 of WO 92/02587 states that a solution of saponified sodium salt of at least one high molecular weight unsaturated fatty acid or a combination of at least one high molecular weight unsaturated fatty acid and at least one high molecular weight unsaturated fatty acid can be added to the preheated suspension of the precipitated calcium carbonate to ultimately obtain calcium carbonate with the required degree of fatty acid coating before processing it in the next technological stages.

Abstract JP54162746 describes a composition containing a specified relative amount of rigid vinyl chloride resin, fatty acid treated colloidal calcium carbonate, and barium stearate used to improve the thermal stability of the vinyl chloride composition.

US 4,520,073 describes mineral fillers with improved hydrophobic coatings obtained by coating porous minerals under pressure using steam as a carrier for the coating material. The material of such a coating can be selected from, among other options, long-chain aliphatic fatty acids and their salts.

WO 01/32787 describes a particulate material of an alkaline earth metal carbonate, the particles of which are coated with a hydrophobic material containing a composition obtained from (a) a first component that contains the reaction product of an alkaline earth metal carbonate and at least one given aliphatic carboxylic acid, and (b) a second component having a substantially higher carbonate release temperature than the first component, which contains a compound of the formula CH ₃ (CH ₂ ) _m COOR.

WO 2008/077156 A2 relates to spunbond fibers containing at least one polymer resin and at least one filler having an average particle size of less than or exactly about 5 µm, and/or having an upper particle size limit of less than about 15 µm wherein the at least one filler is present in an amount of less than about 40% by weight relative to the total weight of the fibers for the spunbond process. The coating of the fibers is described as being at least one organic material selected from fatty acids and their salts and esters, for example, stearic acid, stearate, ammonium stearate and calcium stearate.

GB 2 336 366 A relates to filled thermoplastic compositions and, in particular, to filled low-density polyethylene compositions which are intended to be molded into products or articles by extrusion. It is further described that the hydrophobizing agent is preferably an organic carboxylic acid or a partially or completely neutralized salt thereof, which contains at least one saturated or unsaturated hydrocarbon chain containing from 8 to 28 carbon atoms, if the particulate mineral, for example calcium carbonate, has surface reaction from neutral to alkaline.

EP2159258A1 relates to a processed mineral filler containing: a) at least one mineral filler; b) a treatment layer located on the surface of said mineral filler(s), wherein said treatment layer comprises: at least one saturated C8 - C24 aliphatic carboxylic acid; and at least one di- and/or trivalent cation salt of one or more saturated C8 - C24 aliphatic carboxylic acids; characterized in that: the weight ratio of all said aliphatic carboxylic acid salts to all said aliphatic carboxylic acids is from 51:49 to 75:25, and said treatment layer is present in an amount of at least 2.5 mg/m ² of said mineral filler.

EP1980588A1 relates to a process for producing a processed mineral filler which includes the following steps: (a) treating at least one dry mineral filler with at least one salt of a Group II or Group III element and a C8 to C24 aliphatic monocarboxylic acid to produce an intermediate mineral filler; then (b) treating the intermediate mineral filler obtained in step (a) with at least one C8 - C24 aliphatic monocarboxylic acid to obtain a treated mineral filler.

WO 2016/023937 A1 relates to a method for producing a breathable film, comprising the steps of: a) producing a composition comprising at least one thermoplastic polymer and a surface treated filler material product, and b) forming a film from the composition obtained on step a), and c) stretching the film obtained in step b), in at least one direction, wherein said surface treated filler material product comprises A) at least one particulate filler material containing calcium carbonate, having a weighted average particle size d ₅₀ of 0.1 µm to 7 µm, an upper particle size limit of < 15 µm, a specific surface area (BET) of 0.5 to 150 m ² /g, measured using nitrogen and the BET method in accordance with ISO 9277, and residual total moisture content < 1% wt. relative to the total dry weight of at least one ground calcium carbonate-containing filler material, and B) a treatment layer on the surface of at least one wet-ground calcium carbonate-containing filler material that contains at least one monosubstituted succinic anhydride and/or at least one monosubstituted succinic acid and/or salt product(s) of its reaction, wherein the product based on a surface-treated filler material contains a treatment layer in an amount of from 0.1 to 3% wt. relative to the total dry weight of at least one crushed filler material containing calcium carbonate.

However, standard processing of filler materials containing calcium carbonate involves the application of fatty acids to the fine particles. Due to the high melting point of the fatty acids and the fineness of the filler material, such processing requires a complex and expensive process. For certain applications, such as polymers, one trend is to use larger particles. However, the cost of standard fatty acid treatment of coarse particles is too high to be commercially acceptable, so surface-treated coarse filler materials are rare. In addition, in modern surface treatment processes, the coarse raw material is subjected to grinding due to mechanical abrasion caused by the rotation/coating process of the equipment used, which results in the formation of a significant amount of undesirable fine particles.

Accordingly, it is an object of the present invention to provide a method for producing a coarse product based on a surface treated filler material. In addition, it is necessary to provide a method for producing a surface treated filler material product that does not produce excessive fines. In addition, it is necessary to provide a method for producing a surface treated filler material product that does not disturb the particle size distribution of the starting filler material. Additional objects will become apparent from the following description of the invention.

The above and other problems are solved using the subject matter of the invention, the definition of which is given in paragraph 1 of the claims.

Advantageous embodiments of the method for producing a product based on a filler material with a treated surface according to the present invention are defined in the corresponding subclauses of the claims.

In accordance with one aspect of the present invention, there is provided a method for producing a surface treated filler material product. The proposed method for producing a product based on a filler material with a treated surface includes at least the following stages:

a) providing at least one filler material containing calcium carbonate, which has

volumetric median particle size d ₅₀ from 5 to 100 µm,

upper size limit ( d ₉₈ ) from 30 to 500 µm, and

residue on 45 µm sieve, measured in accordance with ISO 787/7, more than 0.5% wt. relative to the total mass of filler material containing calcium carbonate,

b) providing at least one surface treatment agent in a molten or liquid state at a temperature between 18 and 45 °C,

c) bringing into contact, by mixing in one or more stages, the surface of at least one calcium carbonate containing filler material from step a) with at least one surface treatment agent from step b), such that on the surface of said at least at least one filler material containing calcium carbonate, from step a) a treatment layer is formed containing at least one surface treatment agent and/or reaction product(s) thereof,

wherein the resulting product based on the surface treated filler material has a residue on a 45 μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the product based on the filler material with a treated surface.

The inventors of the present invention have surprisingly discovered that the above-described process for producing a surface treated filler material product results in a coarse surface treated filler material product having a low content of fines generated during the process. As a result, a coarse surface treated filler material product can be obtained which has substantially the same particle size distribution as the starting filler material and is particularly suitable for applications in the polymer field.

According to one embodiment, the calcium carbonate containing filler material from step a) is selected from the group consisting of ground calcium carbonate, preferably marble, limestone, dolomite and/or chalk, precipitated calcium carbonate (PCC), preferably vaterite, calcite and/or aragonite, surface reacted calcium carbonate (MCC) and mixtures thereof, more preferably the calcium carbonate containing filler material is ground calcium carbonate.

According to another embodiment, the at least one calcium carbonate containing filler material from step a) has a) a volumetric median particle size d ₅₀ value of from 6 to 80 µm, preferably from 7 to 60 µm and most preferably from 7 .5 to 50 µm, b) upper size limit ( d ₉₈ ) from 40 to 400 µm, preferably from 50 to 300 µm, more preferably from 50 to 250 µm, and c) 45 µm sieve residue measured according to ISO 787/7, from 0.5 to 30% wt., preferably from 0.75 to 25% wt. relative to the total mass of filler material containing calcium carbonate.

According to another embodiment, the amount of 45 μm sieve residue of at least one calcium carbonate-containing filler material from step a) measured in accordance with ISO 787/7, and the 45 μm sieve residue of the base material product is surface treated filler, measured in accordance with ISO 787/7, differs by less than 20% wt.

According to one embodiment, the at least one surface treatment agent in step b) has a Brookfield viscosity of ≤1000 mPa.s at 25°C.

According to another embodiment, the at least one surface treatment agent in step b) is a mixture of phosphoric acid esters of one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters, and/or at least at least one monosubstituted succinic anhydride consisting of a succinic anhydride monosubstituted by a group selected from a linear, branched and aliphatic group having a total number of carbon atoms from at least C2 to C20 in the substituent, or a cyclic group having a total number of carbon atoms from at least from C3 to C20 in the substituent; and/or added at stage c) of bringing into contact in an amount of from 0.1 to 3 wt.%, preferably from 0.1 to 2 wt.%, and most preferably from 0.1 to 1.5 wt.%. relative to the total dry weight of the at least one calcium carbonate containing filler material from step a).

According to another embodiment, the contacting step c) is carried out such that the total energy consumption resulting from the addition of at least one surface treatment agent from step b) to the at least one calcium carbonate containing filler material from step a), is not more than 15 kWh/t, preferably from 2 to 15 kWh/t.

According to one embodiment, contacting step c) is carried out in an Archimedean screw, for example a screw conveyor, a drum mixer, a pneumatic air conveyor system, a planetary mixer or a Guedu mixer, preferably at least one surface contact agent. processing step b) is added to at least one calcium carbonate containing filler material from step a), which is loaded into an Archimedes screw, for example, a screw conveyor, a drum mixer, a pneumatic air conveyor system, a planetary mixer or into the Guedu mixer.

According to another embodiment, the Archimedes screw is operated at an angle of from 30 to 80°, and more preferably from 35 to 70°, and/or at a temperature of from 18 to 45 °C.

According to another embodiment, the at least one surface treatment agent from step b) is added to the at least one calcium carbonate containing filler material from step a) in the lower 1/3 of the Archimedean screw.

According to one embodiment, the drum mixer, planetary mixer, or Guedu mixer has a diameter to height ratio of 1:1 to 1:5.

According to another embodiment, contacting step c) is carried out such that at least one surface treatment agent from step b) is sprayed onto at least one calcium carbonate containing filler material from step a), and/ or step c) of bringing into contact is carried out in a continuous or batch mode.

In accordance with another aspect, the present invention relates to a surface treated filler material product comprising

a) at least one filler material containing calcium carbonate, which has

i) volumetric median particle size d ₅₀ from 5 to 100 µm,

ii) upper size limit ( d ₉₈ ) from 30 to 500 µm,

b) a treatment layer on the surface of at least one filler material containing calcium carbonate, which contains at least one surface treatment agent and/or reaction products thereof, wherein the surface treated filler material product contains a treatment layer in an amount from 0.1 to 3% wt. relative to the total dry weight of at least one filler material containing calcium carbonate,

wherein said product based on a surface treated filler material has a residue on a 45 µm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the product based on the filler material with a treated surface.

In accordance with one embodiment, a surface treated filler material product is produced by a process for producing a surface treated filler material product described herein.

In accordance with a further aspect of the present invention there is provided an article, preferably a polymer article, comprising a surface treated filler material product described herein.

It should be understood that, in the context of the present invention, the following terms have the meaning indicated:

In the context of the present invention, the term "surface treated filler material product" for the purpose of the present invention refers to a filler material containing calcium carbonate that is brought into contact with a surface treatment agent to produce a coating layer on at least a portion of the surface of the material. filler containing calcium carbonate.

The term "surface treatment agent" refers to an agent suitable for increasing the hydrophobicity of a filler material containing calcium carbonate.

The term "reaction products" of a surface treatment agent in the context of the present invention refers to the products obtained by contacting a filler material containing calcium carbonate with a surface treatment agent. Such reaction products are formed between the applied surface treatment agent and the reactive molecules located at the surface of the calcium carbonate containing filler material.

"Treatment layer" in the context of the present invention refers to a layer, preferably a monolayer, of a surface treatment agent on the surface of a surface treated filler material product. The "treating layer" essentially consists of a surface treatment agent and/or its reaction product(s).

The term “substantially” with respect to a treatment layer refers to a treatment layer that contains compounds other than the surface treatment agent and/or their reaction product(s) in an amount of <5% by weight, preferably <2% by weight, and most preferably <1% wt. relative to the total mass of the treatment layer.

The "specific surface area (SSA)" of a calcium carbonate-containing filler material in the context of the present invention is defined as the surface area of the calcium carbonate-containing filler material divided by its mass. In this context, specific surface area is measured using nitrogen gas absorption using the BET isotherm (ISO 9277:2010) and is reported in m ² /g.

The "particle size" of particulate materials, for example in this context a filler material containing calcium carbonate, is described by its particle size distribution d _x .

The d _x value represents the diameter relative to which x% of particles have a diameter less than d _x . This means that the d ₉₈ value represents the particle size at which 98% of all particles are smaller. A d value of ₉₈ is also described as the "upper size limit". The d _x values are presented as volume percentages. Thus, _the d50 value represents the volumetric median particle size, i.e. 50% vol. all particles are smaller than the specified particle size. The volume median particle size d ₅₀ was determined using a Malvern Mastersizer 2000 laser diffraction system. A d ₅₀ or d ₉₈ value measured using a Malvern Mastersizer 2000 laser diffraction system means a diameter value such that 50% or 98% by volume, respectively, of the particles have a diameter less than the specified value. The raw data obtained from the measurement was analyzed using Mie theory, with a particle refractive index of 1.57 and an absorption index of 0.005.

The term "molten" in the context of the present invention is defined as the state in which a material changes from a solid to a liquid, i.e. is not completely liquid at temperatures from 18 to 45 °C.

The term "liquid" in accordance with the present invention refers to a material that is completely liquid at a temperature of 18 to 45 °C.

As used in the present specification and claims, the term “comprising” does not exclude other unspecified elements of major or minor functional significance. For purposes of the present invention, the term “consisting of” is considered to be a preferred variant of the term “comprising”. If it is further stated that a group contains at least a certain number of embodiments, then it should be understood that a group is also described that preferably consists of only those embodiments.

When the terms “comprising” or “having” are used, these terms are equivalent to the term “comprising” as defined above.

When a term is used in the singular form, plural forms are also provided, unless otherwise specifically stated elsewhere.

As stated above, the method for producing a surface treated filler material product according to the present invention includes at least process steps a), b) and c). The following describes further details of the present invention and especially the above steps of the method for producing a surface treated filler material product according to the present invention.

Characteristics of step a): providing at least one filler material containing calcium carbonate

In accordance with step a) of the method according to the present invention, at least one filler material containing calcium carbonate is provided.

The expression “at least one” calcium carbonate-containing filler material means that one or more, for example two or three calcium carbonate-containing filler materials may be provided. According to a preferred embodiment, in step a) only one filler material containing calcium carbonate is provided.

According to a preferred embodiment of the present invention, the calcium carbonate containing material is selected from the group consisting of ground calcium carbonate (GCC), preferably marble, limestone, dolomite and/or chalk, precipitated calcium carbonate (PCC), preferably vaterite, calcite and/or aragonite, surface reacted calcium carbonate (MCC) and mixtures thereof.

For example, the at least one calcium carbonate containing material is ground calcium carbonate.

GCC is understood as a naturally occurring form of calcium carbonate, mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble ores, and processed by processing methods such as grinding, screening and/or fractionation into wet and/or dry forms, e.g. cyclone or classifier. In one embodiment of the present invention, GCC is selected from the group consisting of marble, chalk, dolomite, limestone, and mixtures thereof.

In contrast, PCC type calcium carbonate includes synthetic calcium carbonate products obtained by carbonating a calcium hydroxide slurry, commonly referred to in the art as lime liquor or lime milk when prepared from finely divided calcium oxide particles in water or by precipitation from an ionic salt solution. PCC may have a rhombohedral and/or irregular and/or aragonitic shape; the preferred synthetic calcium carbonate or precipitated calcium carbonate contains aragonite, vaterite or calcite mineralogy crystal forms or mixtures thereof.

"Surface reacted calcium carbonate" in the context of the present invention may be natural ground or precipitated calcium carbonate with internal structure modification or a surface reaction product.

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

It should be understood that the amount of calcium carbonate in the at least one filler material containing calcium carbonate is preferably at least 80% by weight, such as at least 95% by weight, more preferably from 97 to 100% by weight. even more preferably from 98.5 to 99.95% wt. relative to the total dry weight of at least one filler material containing calcium carbonate.

The term "dry" filler material containing calcium carbonate is understood as a filler material containing less than 0.3% wt. water relative to the weight of the filler material. The water content in % (equal to the total residual moisture content) is determined according to the Karl Fischer coulometric method, in which the filler material is heated to 220 °C and the amount of water released in the form of steam and released by a stream of nitrogen gas is determined (at 100 ml/min.), in a Karl Fischer coulometric cell.

A special requirement of the present invention is that at least one filler material containing calcium carbonate is a coarse material. That is, at least one filler material containing calcium carbonate has a volumetric median particle size d ₅₀ of 5 to 100 μm. For example, the at least one calcium carbonate-containing filler material has a volumetric median particle size d ₅₀ of 6 to 80 μm, preferably 7 to 60 μm, and most preferably 7.5 to 50 μm.

In addition, the at least one calcium carbonate- _containing filler material has an upper size limit ( d98 ) of 30 to 500 μm. For example, the at least one calcium carbonate-containing filler material has an upper size limit ( d98 ) of 40 to 400 μm _, preferably 50 to 300 μm, more preferably 50 to 250 μm.

Coarse material is material with a low content of fine particles. In particular, the degree of grinding of at least one filler material containing calcium carbonate is characterized by a residue on a 45 μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of filler material containing calcium carbonate. Preferably, the at least one calcium carbonate containing filler material has a 45 µm sieve residue, measured in accordance with ISO 787/7, from 0.5 to 30% by weight, and more preferably from 0.75 to 25% wt. relative to the total mass of filler material containing calcium carbonate. For example, at least one filler material containing calcium carbonate has a residue on a 45 μm sieve, measured in accordance with ISO 787/7, from 0.75 to 15% by weight. or from 0.75 to 10% wt. relative to the total mass of filler material containing calcium carbonate.

Thus, the at least one filler material containing calcium carbonate has

i) a volumetric median particle size d ₅₀ value of from 5 to 100 µm, preferably from 6 to 80 µm, more preferably from 7 to 60 µm, and most preferably from 7.5 to 50 µm, and

ii) an upper size limit ( d98 ) of 30 to 500 µm, preferably 40 to ₄₀₀ µm, more preferably 50 to 300 µm, and most preferably 50 to 250 µm, and

iii) residue on a 45 μm sieve, measured in accordance with ISO 787/7, greater than 0.5% by weight, preferably from 0.5 to 30% by weight, and more preferably from 0.75 to 25% by weight. relative to the total mass of filler material containing calcium carbonate.

In view of the foregoing, it is understood that the at least one calcium carbonate-containing filler material is preferably in the form of a particulate material.

It is further preferred that the at least one filler material containing calcium carbonate has a BET specific surface area of from 0.5 to 150 m ² /g as measured by the nitrogen BET method. For example, the at least one filler material containing calcium carbonate has a specific surface area (BET) of from 0.5 to 50 m ² /g, more preferably from 0.5 to 35 m ² /g, and most preferably from 0 .5 to 10 m ² /g when measured using the BET nitrogen method.

Preferably, the at least one calcium carbonate-containing filler material is a dry-ground material, a dried wet-ground material, or a mixture of the foregoing. In general, the comminution step can be carried out using any conventional comminution device, for example, under conditions where comminution occurs predominantly as a result of impacts on the secondary body, that is, in one or more of: a ball mill, a rod mill, a vibrating mill, a roller crusher , turbine mill, vertical bead mill, friction mill, pin mill, hammer mill, pulverizer, shredder, lump crusher, knife tool or other similar equipment known to those skilled in the art.

If the at least one calcium carbonate-containing filler material is a wet-milled calcium carbonate-containing filler material, the grinding step may be carried out under conditions such that autogenous grinding and/or horizontal ball milling occurs. , and/or using other similar processes known to those skilled in the art. The thus obtained filler material containing calcium carbonate, crushed by a wet method, can be washed from and dewatered by known methods, for example, flocculation, filtration or forced evaporation followed by drying. The subsequent drying step may be carried out in a single step, such as spray drying, or in at least two steps, such as using a first step of heating the calcium carbonate containing filler material to reduce the bound moisture content to a level not exceeding about 0 .5% wt. relative to the total dry weight of at least one filler material containing calcium carbonate. The residual total moisture content of the fill can be measured by coulometric Karl Fischer titration, desorption of moisture in an oven at 195 °C and continuous passage through a KF coulometer (Mettler Toledo C30 coulometric KF titrator connected to a Mettler DO 0337 oven) using dry N ₂ at 100 ml/min. within 10 minutes. The residual total moisture content can be determined from the calibration curve and also from a blank sample, which is a gas flow without sample for 10 minutes. The residual total moisture content can be further reduced by a second step of heating the at least one calcium carbonate-containing filler material. If said drying is carried out in more than one drying step, the first step can be carried out by heating in a hot air stream, and the second and subsequent drying steps are preferably carried out by indirect heating, the atmosphere in the corresponding reactor containing a surface treatment agent. Often the at least one filler material containing calcium carbonate is also subjected to a processing step (such as a flotation, decolorization or magnetic separation step) to remove impurities).

In one embodiment of the present invention, the at least one calcium carbonate-containing filler material comprises a dry-ground calcium carbonate-containing filler material. In another preferred embodiment, the at least one calcium carbonate-containing filler material is wet-ground in a horizontal ball mill and then dried using a known spray drying method.

Depending on the at least one calcium carbonate-containing filler material, the at least one calcium carbonate-containing filler material preferably has a residual total moisture content of from 0.01 to 1% by weight, preferably from 0.01 to 0 .2% by weight, more preferably from 0.02 to 0.2% by weight, and most preferably from 0.04 to 0.2% by weight. relative to the total dry weight of at least one filler material containing calcium carbonate.

For example, in the case of using spray-dried wet-ground marble as the at least one calcium carbonate-containing filler material, the residual total moisture content of the at least one calcium carbonate-containing filler material is preferably from 0.01 to 0.1% wt., more preferably from 0.02 to 0.08% wt., and most preferably from 0.04 to 0.07% wt. relative to the total dry weight of at least one filler material containing calcium carbonate. When using PCC as the at least one calcium carbonate-containing filler material, the residual total moisture content of the at least one calcium carbonate-containing filler material is preferably 0.01 to 0.2% by weight, more preferably from 0.05 to 0.17% wt., and most preferably from 0.05 to 0.15% wt. relative to the total dry weight of at least one filler material containing calcium carbonate.

Characteristics of step b): providing at least one surface treatment agent

According to step b) of the method according to the present invention, at least one surface treatment agent is provided which is in a molten or liquid state at a temperature of from 18 to 45 °C.

It should be understood that the expression "at least one" surface treatment agent means that one or more kinds of surface treatment agents may be provided in the method according to the present invention.

Accordingly, it should be noted that the at least one surface treatment agent may be one kind of surface treatment agent. Alternatively, the at least one surface treatment agent may be a mixture of two or more types of surface treatment agents. For example, the at least one surface treatment agent may be a mixture of two or three types of surface treatment agents, for example, two types of surface treatment agents.

In one embodiment of the present invention, the at least one surface treatment agent is one type of surface treatment agent.

To avoid reduction in particle size during this process, it is stipulated that at least one surface treatment agent must be in a molten or liquid state at a temperature of 18 to 45 °C. That is, at least one filler material containing calcium carbonate is treated with at least one surface treatment agent in a molten or liquid state.

The at least one surface treatment agent preferably has a viscosity of ≤1000, preferably ≤900 mPa.s, more preferably ≤700 mPa.s, and most preferably ≤500 mPa.s at +25 °C (± 2 °C) when measured in suitable equipment, for example the Physica MCR 300 rheometer (Paar Physica) equipped with a TEZ 150 PC measuring cell and a CC 28.7 measuring system at a shear rate of 5 s ^-1 and at +25 °C (± 2 °C).

It should be understood that at least one surface treatment agent may also be present in an organic solvent to achieve the above viscosity. However, the organic solvent must have a boiling point as low as possible to avoid the energy-intensive drying steps required to remove the organic solvent. For the same reason, at least one surface treatment agent should be dissolved in as little organic solvent as possible. The amount of organic solvent is preferably less than 50% by weight, more preferably less than 30% by weight, and most preferably less than 10% by weight. relative to the total weight of the mixture containing at least one surface treatment agent and an organic solvent. The organic solvent may be selected from the group of solvents containing ester and/or ether functional groups, aromatic solvents, mineral oils and mixtures thereof. Examples of organic solvents include diethyl ether, petroleum ether, ethyl acetate, toluene, xylene, and mixtures thereof.

However, the at least one surface treatment agent is preferably presented in undiluted form, i.e. without organic solvent.

It is contemplated that the at least one surface treatment agent may be any surface treatment agent known to those skilled in the art that can form a layer of hydrophobic material on at least a portion of the available surface area of the particles of the at least one filler material, containing calcium carbonate.

In one embodiment of the present invention, the at least one surface treatment agent in step b) is a mixture of phosphoric acid esters of one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters, and/or at least one monosubstituted succinic anhydride consisting of succinic anhydride monosubstituted by a group selected from a linear, branched and aliphatic group having a total number of carbon atoms from at least C2 to C20 in the substituent, or a cyclic group having a total number of carbon atoms from at least C3 to C20 in substituent.

Preferably, the at least one surface treatment agent in step b) is a mixture of phosphoric acid esters of one or more monoesters of phosphoric acid and/or one or more diesters of phosphoric acid, and/or at least one monosubstituted succinic anhydride , consisting of a succinic anhydride monosubstituted by a group selected from a linear, branched and aliphatic group having a total number of carbon atoms from at least C2 to C20 in the substituent, or a cyclic group having a total number of carbon atoms from at least C3 to C20 in Deputy

In one embodiment, the at least one surface treatment agent in step b) is a mixture of phosphoric acid esters of one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters.

The term "phosphoric acid monoester" in the context of the present invention refers to an orthophosphoric acid molecule monoesterified with an alcohol molecule selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C21, preferably from C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

The term "phosphoric acid diester" in the context of the present invention refers to an orthophosphoric 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 C21 , preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

Phosphoric acid alkyl esters are well known in industry, particularly 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, as well as 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: Volume 15; 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.

The expression “one or more” phosphoric acid monoesters is intended to mean that one or more kinds of phosphoric acid monoesters may be present in the phosphoric acid ester mixture.

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

In one embodiment of the present invention, one or more phosphoric acid monoesters consist of an orthophosphoric acid molecule 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 C21 in the alcohol substituent . For example, one or more phosphoric acid monoesters consist of an orthophosphoric acid molecule 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 C20, more preferably C8 to C18 , and most preferably from C8 to C16 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid monoesters consist of an orthophosphoric acid molecule esterified with a single alcohol selected from saturated and linear or branched and aliphatic alcohols having a total number of carbon atoms from C6 to C21 in the alcohol substituent. For example, one or more phosphoric acid monoesters consist of an orthophosphoric acid molecule esterified with a single alcohol selected from saturated and linear or branched and aliphatic alcohols having a total carbon number of C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

In one embodiment of the present invention, the one or more phosphoric acid monoesters consist of an orthophosphoric acid molecule esterified with one alcohol selected from saturated and linear and aliphatic alcohols having a total carbon number of C6 to C21, more preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent. Alternatively, the one or more phosphoric acid monoesters consist of an orthophosphoric acid molecule esterified with one alcohol selected from saturated and branched and aliphatic alcohols having a total carbon number of C6 to C21, more preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 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 acid monoester, heptyl phosphoric acid monoester, octyl phosphoric acid monoester, 2-ethylhexyl phosphoric acid monoester, nonyl phosphoric acid monoester, decyl phosphoric acid monoester, undecyl monoester of phosphoric acid, dodecyl monoester of phosphoric acid, tetradecyl monoester of phosphoric acid, hexadecyl monoester of phosphoric acid and mixtures thereof.

For example, the one or more phosphoric acid monoesters are selected from the group consisting of 2-ethylhexyl phosphoric acid monoester, hexadecyl phosphoric acid monoester, heptylnonyl phosphoric acid monoester, and mixtures thereof.

The expression “one or more” phosphoric acid diesters is intended to mean that one or more kinds of phosphoric acid diesters may be present in the phosphoric acid ester mixture.

Accordingly, it should be noted that one or more phosphoric acid diesters may be one type of phosphoric acid diester. Alternatively, the 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 types of phosphoric acid diester, for example, two types of phosphoric acid diesters.

In one embodiment of the present invention, one or more phosphoric acid diesters consist of an orthophosphoric acid molecule 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 C21 in the alcohol substituent . For example, one or more phosphoric acid diesters consist of an orthophosphoric acid molecule esterified with two fatty alcohols selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total carbon number of C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

It is contemplated that the two alcohols used for the esterification of phosphoric acid may 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 C21 in the alcohol substituent. In other words, one or more phosphoric acid diesters may contain two substituents derived from the same alcohol, 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 an orthophosphoric acid molecule 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 C21 in the alcohol substituent . For example, one or more phosphoric acid diesters consist of an orthophosphoric acid molecule 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 C20, more preferably C8 to C18 , and most preferably from C8 to C16 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid diesters consist of an orthophosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and linear and aliphatic alcohols having a total carbon number of C6 to C21, more preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent. Alternatively, one or more phosphoric acid diesters consist of an orthophosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and branched and aliphatic alcohols having a total carbon number of C6 to C21, more preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

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

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

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

For example, a mixture of phosphoric acid esters contains one phosphoric acid monoester and one phosphoric acid diester. In such a case, one phosphoric acid monoester is selected from the group consisting of 2-ethylhexyl phosphoric acid monoester and hexadecyl phosphoric acid monoester, and one phosphoric acid diester is selected from the group consisting of 2-ethylhexyl phosphoric acid diester and hexadecyl phosphoric acid diester.

If the mixture of phosphoric acid esters contains one phosphoric acid monoester and one phosphoric acid diester, it is provided that the alcohol substituents in one phosphoric acid monoester and in one phosphoric acid diester are preferably the same. For example, a mixture of phosphoric acid esters contains one 2-ethylhexyl phosphoric acid monoester and one 2-ethylhexyl phosphoric acid diester. Alternatively, the phosphoric acid ester mixture contains a hexadecyl phosphoric acid monoester and a hexadecyl phosphoric acid diester.

In one embodiment of the present invention, the phosphoric ester mixture contains two or more phosphoric acid monoesters and two or more phosphoric acid diesters. In such a case, the two or more phosphoric acid monoesters are selected from the group consisting of 2-ethylhexyl phosphoric acid monoester and hexadecyl phosphoric acid monoester, and the two or more phosphoric acid diesters are selected from the group consisting of 2-ethylhexyl phosphoric acid diester and hexadecyl phosphoric acid diester.

In accordance with one embodiment of the present invention, the phosphoric ester mixture contains one or more phosphoric acid monoesters and one or more phosphoric acid diesters in a specified molar ratio. In particular, the molar ratio of one or more phosphoric acid monoesters to one or more phosphoric acid diesters in the phosphoric acid ester mixture may be from 1:1 to 1:100.

The expression "molar ratio of one or more phosphoric acid monoesters to one or more phosphoric acid diesters" in the context of the present invention refers to the sum of the molecular weights of the phosphoric acid monoester molecules divided by the sum of the molecular weights of the phosphoric acid diester molecules.

According to one embodiment, the molar ratio of one or more phosphoric acid monoesters to one or more phosphoric acid diesters in the phosphoric ester mixture is from 1:1 to 1:100, preferably from 1:1.1 to 1:80, more preferably from 1:1.1 to 1:60, even more preferably from 1:1.1 to 1:40, even more preferably from 1:1.1 to 1:20, and most preferably from 1:1.1 until 1:10.

According to one embodiment of the present invention,

i) one or more monoesters of phosphoric acid consist of a molecule of orthophosphoric acid monoesterified with one molecule of alcohol selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C21, preferably from C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent, and/or

ii) one or more phosphoric acid diesters consist of a molecule of orthophosphoric acid diesterified with two molecules of alcohol 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 C21, preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

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

The term "phosphoric acid triester" in the context of the present invention refers to an orthophosphoric acid molecule tryesterified 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 C21 , preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

The expression “one or more” phosphoric acid triesters is intended to mean that one or more kinds of phosphoric acid triesters may be present in the phosphoric acid ester mixture.

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

In one embodiment of the present invention, one or more phosphoric acid triesters consist of an orthophosphoric acid molecule esterified with three alcohols 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 C21 in the alcohol substituent. For example, one or more phosphoric acid triesters consist of an orthophosphoric acid molecule 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 C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

It is contemplated that the three alcohols used for the esterification of phosphoric acid may be independently selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total number of carbon atoms from C6 to C21 in the alcohol substituent. In other words, one or more phosphoric acid triester molecules may contain three substituents derived from the same alcohol, or a phosphoric acid triester molecule may contain three substituents derived from different alcohols.

In one embodiment of the present invention, one or more phosphoric acid triesters consist of an orthophosphoric acid molecule 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 C21 in the alcohol substituent . For example, one or more phosphoric acid triesters consist of an orthophosphoric acid molecule 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 C20, more preferably C8 to C18 , and most preferably from C8 to C16 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid triesters consist of an orthophosphoric acid molecule esterified with three alcohols selected from saturated and linear and aliphatic alcohols having a total carbon number of C6 to C21, more preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent. Alternatively, one or more phosphoric acid triesters consist of an orthophosphoric acid molecule esterified with three alcohols selected from saturated and branched and aliphatic alcohols having a total carbon number of C6 to C21, more preferably C8 to C20, more preferably C8 to C18, and most preferably C8 to C16 in the alcohol substituent.

In one embodiment of the present invention, one or more phosphoric acid triesters is selected from the group consisting of hexyl phosphoric acid triesters, heptyl phosphoric acid triesters, octyl phosphoric acid triesters, 2-ethylhexyl phosphoric acid triesters, nonyl phosphoric acid triesters, decyl phosphoric acid triesters, undecyl triester of phosphoric acid, dodecyl triester of phosphoric acid, tetradecyl triester of phosphoric acid, hexadecyl triester of phosphoric acid and mixtures thereof.

For example, one or more phosphoric acid triesters are selected from the group consisting of 2-ethylhexyl phosphoric acid triesters and hexadecyl phosphoric acid triesters, and mixtures thereof.

In one embodiment of the present invention, the phosphoric acid ester mixture contains one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and one or more phosphoric acid triesters, and optionally phosphoric acid. For example, a mixture of phosphoric acid esters contains one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and one or more phosphoric acid triesters, and phosphoric acid.

Alternatively, the phosphoric acid ester mixture contains one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and optionally phosphoric acid. For example, a mixture of phosphoric acid esters contains one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and phosphoric acid.

If the phosphoric acid ester mixture contains one or more phosphoric acid triesters, then it is preferable that the phosphoric acid ester mixture contains one or more phosphoric acid triesters in an amount of ≤10 mol%. relative to the sum of the moles of one or more monoesters of phosphoric acid and one or more diesters of phosphoric acid, and one or more triesters of phosphoric acid, and phosphoric acid. For example, the phosphoric ester mixture contains one or more phosphoric acid triesters in an amount of ≤8 mol%, preferably ≤6 mol%, and more preferably ≤4 mol%, such as 0.1 to 4 mol%. relative to the sum of the moles of one or more monoesters of phosphoric acid and one or more diesters of phosphoric acid, and one or more triesters of phosphoric acid, and phosphoric acid.

Additionally or alternatively, if the phosphoric ester mixture contains phosphoric acid, it is preferable that said phosphoric ester mixture contains phosphoric acid in an amount of ≤10 mol%. relative to the sum of the moles of one or more monoesters of phosphoric acid and one or more diesters of phosphoric acid, and one or more triesters of phosphoric acid, and phosphoric acid. For example, the phosphoric acid ester mixture contains phosphoric acid in an amount of ≤8 mol%, preferably ≤6 mol%, and more preferably ≤4 mol%, such as 0.1 to 4 mol%. relative to the sum of the moles of one or more monoesters of phosphoric acid and one or more diesters of phosphoric acid, and one or more triesters of phosphoric acid, and phosphoric acid.

If the phosphoric acid ester mixture further contains phosphoric acid and one or more phosphoric acid triesters, then preferably the molar ratio of phosphoric acid to one or more phosphoric acid monoesters and to one or more phosphoric acid diesters and to one or more phosphoric acid triesters in said mixture of phosphoric acid esters is ≤10 mol%. :≤40 mol% :≥40% mol. :≤10% mol. relative to the sum of the moles of one or more phosphoric acid monoesters and one or more phosphoric acid diesters, and one or more phosphoric acid triesters, and phosphoric acid.

The expression "molar ratio of phosphoric acid to one or more monoesters of phosphoric acid and to one or more diesters of phosphoric acid, and to one or more triesters of phosphoric acid" in the context of the present invention refers to the ratio of the sum of the molecular weights of phosphoric acid to the sum of the molecular weights of the molecules of phosphoric monoesters acid and to the sum of the molecular weights of the molecules of phosphoric acid diesters, and to the sum of the molecular weights of the molecules of phosphoric acid triesters.

Methods for preparing a product based on a surface treated filler material treated with a mixture of at least one phosphoric ester and suitable coating compounds are described, for example, in EP 2 770 017 A1, the contents of which are incorporated herein by reference.

Additionally or alternatively, the at least one surface treatment agent in step b) is at least one monosubstituted succinic anhydride, consisting of a succinic anhydride monosubstituted by a group selected from linear, branched, aliphatic and cyclic group containing total carbon atoms from at least C2 to C20 in said substituent.

In one embodiment, the at least one surface treatment agent in step b), which is at least one monosubstituted succinic anhydride, is present in a solvent, preferably an organic solvent. Alternatively, the at least one surface treatment agent in step b), which is at least one monosubstituted succinic anhydride, is present in water as a solvent.

The at least one monosubstituted succinic anhydride is provided as a surface treatment agent and consists of a succinic anhydride monosubstituted with a group selected from any linear, branched, aliphatic and cyclic group containing a total number of carbon atoms from C2 to C20 in said substituent.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted by a group selected from linear, branched, aliphatic and cyclic group containing a total number of carbon atoms from C3 to C20 in the specified substituent. For example, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic and cyclic group containing a total number of carbon atoms from C4 to C20 in the specified substituent.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with one group that is a linear and aliphatic group containing a total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in the indicated substituent. Additionally or alternatively, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with one group that is a branched and aliphatic group containing a total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in the specified substituent.

Thus, it is preferred that the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with one group that is a linear or branched alkyl group containing a total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in the indicated substituent.

For example, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with one group that is a linear alkyl group containing a total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in said substituent . Additionally or alternatively, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with one group that is a branched alkyl group containing a total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in the specified deputy.

The term "alkyl" as used herein refers to a linear or branched saturated organic compound consisting of carbon and hydrogen. In other words, "monoalkyl succinic anhydride" consists of a linear or branched saturated hydrocarbon chain containing a pendant succinic anhydride group.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is at least one monosubstituted linear or branched alkyl succinic anhydride. For example, at least one alkyl monosubstituted succinic anhydride is selected from the group consisting of ethyl succinic anhydride, propyl succinic anhydride, butyl succinic anhydride, triisobutyl succinic anhydride, pentyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride anhydride, octyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, hexadecanyl succinic anhydride, octadecanyl succinic anhydride and mixtures thereof.

Accordingly, it is intended that, for example, the term “butyl succinic anhydride” includes linear and branched butyl succinic anhydrides. One specific example of linear butyl succinic anhydrides is n-butyl succinic anhydride. Specific examples of branched butyl succinic anhydrides are iso-butyl succinic anhydride, sec-butyl succinic anhydride and/or tert-butyl succinic anhydride.

It is further intended that, for example, the term “hexadecanyl succinic anhydride” includes linear and branched hexadecanyl succinic anhydrides. One specific example of linear hexadecanyl succinic anhydrides is n-hexadecanyl succinic anhydride. Specific examples of branched hexadecanyl succinic anhydrides include 14-methylpentadecanyl succinic anhydride, 13-methylpentadecanyl succinic anhydride, 12-methylpentadecanyl succinic anhydride, 11-methylpentadecanyl succinic anhydride, 10-methylpentadecanyl succinic anhydride, 9-methylpentade Canyl succinic anhydride , 8-methylpentadecanyl succinic anhydride, 7-methylpentadecanyl succinic anhydride, 6-methylpentadecanyl succinic anhydride, 5-methylpentadecanyl succinic anhydride, 4-methylpentadecanyl succinic anhydride, 3-methylpentadecanyl succinic anhydride, 2-methylpentadecanyl succinic anhydride, 1-methylpentadecanyl succinic anhydride, 13-ethylbutadecanyl succinic anhydride, 12-ethylbutadecanyl succinic anhydride, 11-ethylbutadecanyl succinic anhydride, 10-ethylbutadecanyl succinic anhydride, 9-ethylbutadecanyl succinic anhydride, 8-ethylbutadecanyl- succinic anhydride, 7 -ethylbutadecanyl succinic anhydride, 6-ethylbutadecanyl succinic anhydride, 5-ethylbutadecanyl succinic anhydride, 4-ethylbutadecanyl succinic anhydride, 3-ethylbutadecanyl succinic anhydride, 2-ethylbutadecanyl succinic anhydride, 1-ethylbutadecanyl succinic anhydride ID, 2- butyldodecanyl succinic anhydride, 1-hexyldecanyl succinic anhydride, 1-hexyl-2-decanyl succinic anhydride, 2-hexyldecanyl succinic anhydride, 6,12-dimethylbutadecanyl succinic anhydride, 2,2-diethyldodecanyl succinic anhydride, 4, 8,12-trimethyltridecanyl succinic anhydride, 2,2,4,6,8-pentamethylundecanyl succinic anhydride, 2-ethyl-4-methyl-2-(2-methylpentyl)heptyl succinic anhydride and/or 2-ethyl- 4,6-dimethyl-2-propylnonylsuccinic anhydride.

It is further intended that, for example, the term “octadecanyl succinic anhydride” includes linear and branched octadecanyl succinic anhydrides. One specific example of linear octadecanyl succinic anhydrides is n-octadecanyl succinic anhydride. Specific examples of branched hexadecanyl succinic anhydrides are 16-methylheptadecanyl succinic anhydride, 15-methylheptadecanyl succinic anhydride, 14-methylheptadecanyl succinic anhydride, 13-methylheptadecanyl succinic anhydride, 12-methylheptadecanyl succinic anhydride, 11-methylhept adecanyl succinic anhydride , 10-methyl heptadecanyl-amber anhydride, 9-methyl heptadecanyl-amber tonsillitis, 8-methyl heptadecanist-amendary anhydride, 7-methyl heptadarinal anhydride, 6-methyl heptadecanyl anhydride, 5-methyl-methadadacani-anger, 4- 4- methyl heptadadecanist-amber anhydrid, 3-methylheptadecanyl succinic anhydride, 2-methylheptadecanyl succinic anhydride, 1-methylheptadecanyl succinic anhydride, 14-ethylhexadecanyl succinic anhydride, 13-ethylhexadecanyl succinic anhydride, 12-ethylhexadecanyl succinic anhydride, 11-ethylhexadecanyl succinic anhydride nic anhydride, 10 -ethylhexadecanyl succinic anhydride, 9-ethylhexadecanyl succinic anhydride, 8-ethylhexadecanyl succinic anhydride, 7-ethylhexadecanyl succinic anhydride, 6-ethylhexadecanyl succinic anhydride, 5-ethylhexadecanyl succinic anhydride, 4-ethylhexadecanyl succinic anhydride ID, 3- ethylhexadecanyl succinic anhydride, 2-ethylhexadecanyl succinic anhydride, 1-ethylhexadecanyl succinic anhydride, 2-hexyl-dodecanyl succinic anhydride, 2-heptylundecanyl succinic anhydride, iso-octadecanyl succinic anhydride and/or 1-octyl-2-decanyl- succinic anhydride.

In one embodiment of the present invention, at least one alkyl monosubstituted succinic anhydride is selected from the group consisting of butyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, hexadecanyl succinic anhydride, octadecanyl succinic anhydride and mixtures thereof.

In one embodiment of the present invention, the at least one monosuccinic anhydride is one type of monoalkyl succinic anhydride. For example, one succinic anhydride that is monosubstituted with an alkyl is butyl succinic anhydride. Alternatively, one succinic anhydride monosubstituted with alkyl is hexyl succinic anhydride. Alternatively, one mono-alkyl succinic anhydride is heptyl succinic anhydride or octyl succinic anhydride. Alternatively, one mono-alkyl succinic anhydride is hexadecanyl succinic anhydride. For example, one mono-alkyl succinic anhydride is a linear hexadecanyl succinic anhydride such as n-hexadecanyl succinic anhydride or a branched hexadecanyl succinic anhydride such as 1-hexyl-2-decanyl succinic anhydride. Alternatively, one mono-alkyl succinic anhydride is octadecanyl succinic anhydride. For example, one mono-alkyl succinic anhydride is a linear octadecanyl succinic anhydride such as n-octadecanyl succinic anhydride or a branched octadecanyl succinic anhydride such as iso-octadecanyl succinic anhydride or 1-octyl-2-decanyl succinic anhydride anhydride.

In one embodiment of the present invention, one mono-alkyl succinic anhydride is butyl succinic anhydride, such as n-butyl succinic anhydride.

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

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride consists of a succinic anhydride monosubstituted with one group, which is a linear or branched alkenyl group containing a total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in the indicated substituent.

The term "alkenyl" as used herein refers to a linear or branched unsaturated organic compound consisting of carbon and hydrogen. Said organic compound further contains at least one double bond in said substituent, preferably one double bond. In other words, "mono-alkenyl succinic anhydride" consists of a linear or branched unsaturated hydrocarbon chain containing a pendant succinic anhydride group. The term "alkenyl" as used herein is intended to include cis and trans isomers.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is at least one succinic anhydride monosubstituted with linear or branched alkenyl. For example, at least one succinic anhydride monosubstituted with alkenyl is selected from the group consisting of ethenyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, triisobutenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride and mixtures thereof.

Accordingly, it is intended that, for example, the term “hexadecenyl succinic anhydride” includes linear and branched hexadecenyl succinic anhydrides. One specific example of linear hexadecenyl succinic anhydrides is n-hexadecenyl succinic anhydride, such as 14-hexadecenyl succinic anhydride, 13-hexadecenyl succinic anhydride, 12-hexadecenyl succinic anhydride, 11-hexadecenyl succinic anhydride, 10-hexadecenyl succinic anhydride. succinic anhydride, 9-hexadecenyl succinic anhydride, 8-hexadecenyl succinic anhydride, 7-hexadecenyl succinic anhydride, 6-hexadecenyl succinic anhydride, 5-hexadecenyl succinic anhydride, 4-hexadecenyl succinic anhydride, 3-hexadecenyl succinic anhydride anhydride and/or 2-hexadecenylsuccinic anhydride. Specific examples of branched hexadecenyl succinic anhydrides include 14-methyl-9-pentadecenyl succinic anhydride, 14-methyl-2-pentadecenyl succinic anhydride, 1-hexyl-2-decenyl succinic anhydride and/or iso-hexadecenyl succinic anhydride .

It is further intended that, for example, the term “octadecenyl succinic anhydride” includes linear and branched octadecenyl succinic anhydrides. One specific example of linear octadecenyl succinic anhydrides is n-octadecenyl succinic anhydride, such as 16-octadecenyl succinic anhydride, 15-octadecenyl succinic anhydride, 14-octadecenyl succinic anhydride, 13-octadecenyl succinic anhydride, 12-octadecenyl succinic anhydride. succinic anhydride, 11-octadecenyl succinic anhydride, 10-octadecenyl succinic anhydride, 9-octadecenyl succinic anhydride, 8-octadecenyl succinic anhydride, 7-octadecenyl succinic anhydride, 6-octadecenyl succinic anhydride, 5-octadecenyl succinic anhydride anhydride, 4-octadecenyl succinic anhydride, 3-octadecenyl succinic anhydride and/or 2-octadecenyl succinic anhydride. Specific examples of branched octadecenyl succinic anhydrides are 16-methyl-9-heptadecenyl succinic anhydride, 16-methyl-7-heptadecenyl succinic anhydride, 1-octyl-2-decenyl succinic anhydride and/or iso-octadecenyl succinic anhydride .

In one embodiment of the present invention, at least one succinic anhydride monosubstituted with alkenyl is selected from the group consisting of hexenyl succinic anhydride, octenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and mixtures thereof.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is one monosubstituted alkenyl succinic anhydride. For example, one succinic anhydride monosubstituted with alkenyl is hexenyl succinic anhydride. Alternatively, one succinic anhydride monosubstituted with alkenyl is octenyl succinic anhydride. Alternatively, one succinic anhydride monosubstituted with alkenyl is hexadecenyl succinic anhydride. For example, one succinic anhydride monosubstituted with alkenyl is a linear hexadecenyl succinic anhydride such as n-hexadecenyl succinic anhydride or a branched hexadecenyl succinic anhydride such as 1-hexyl-2-decenyl succinic anhydride. Alternatively, one succinic anhydride monosubstituted with alkenyl is octadecenyl succinic anhydride. For example, one alkyl monosubstituted succinic anhydride is a linear octadecenyl succinic anhydride such as n-octadecenyl succinic anhydride or a branched octadecenyl succinic anhydride such as iso-octadecenyl succinic anhydride or 1-octyl-2-decenyl succinic anhydride anhydride.

In one embodiment of the present invention, one mono-alkyenyl succinic anhydride is a linear octadecenyl succinic anhydride, such as n-octadecenyl succinic anhydride. In one embodiment of the present invention, one mono-alkenyl succinic anhydride is a linear octenyl succinic anhydride, such as n-octenyl succinic anhydride.

If at least one monosubstituted succinic anhydride is one succinic anhydride monosubstituted by alkenyl, then it is provided that one specified succinic anhydride monosubstituted by alkenyl is present in an amount of ≥95% by weight. and preferably ≥96.5% wt. relative to the total weight of at least one monosubstituted succinic anhydride presented in step b).

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is a mixture of two or more types of succinic anhydrides monosubstituted with alkenyl. For example, the at least one monosubstituted succinic anhydride is a mixture of two or three types of succinic anhydrides monosubstituted with alkenyl.

If the at least one monosubstituted succinic anhydride is a mixture of two or more types of monosubstituted alkenyl succinic anhydrides, then one monosubstituted alkenyl succinic anhydride is a linear or branched octadecenyl succinic anhydride, and each additional monosubstituted alkenyl succinic anhydride is selected from ethenyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl succinic anhydride and mixtures thereof. For example, the at least one monosubstituted succinic anhydride is a mixture of two or more types of monosubstituted alkenyl succinic anhydride, wherein one monosubstituted alkenyl succinic anhydride is a linear octadecenyl succinic anhydride, and each additional monosubstituted alkenyl succinic anhydride is selected from ethenyl -succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl succinic anhydride and mixtures thereof. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of two or more types of monosubstituted alkenyl succinic anhydrides, wherein the one monosubstituted alkenyl succinic anhydride is a branched octadecenyl succinic anhydride, and each additional monosubstituted alkenyl succinic anhydride is selected from ethenyl -succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl succinic anhydride and mixtures thereof.

For example, the at least one monosubstituted succinic anhydride is a mixture of two or more types of succinic anhydrides, monosubstituted alkenyl, containing one or more hexadecenyl-succinic anhydrides, such as linear or branched hexadecenyl-succinic anhydride(s), and one or more octadecenyl-succinic anhydride(s). succinic anhydrides such as linear or branched octadecenyl succinic anhydride(s).

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is a mixture of two or more types of monosubstituted alkenyl succinic anhydrides containing linear hexadecenyl succinic anhydride(s) and linear octadecenyl succinic anhydride(s). Alternatively, the at least one monosubstituted succinic anhydride is a mixture of two or more types of succinic anhydrides, monosubstituted alkenyl, containing branched hexadecenyl succinic anhydride(s) and branched octadecenyl succinic anhydride(s). For example, the one or more hexadecenyl succinic anhydrides are a linear hexadecenyl succinic anhydride, such as n-hexadecenyl succinic anhydride, and/or a branched hexadecenyl succinic anhydride, such as 1-hexyl-2-decenyl succinic anhydride. Additionally or alternatively, the one or more octadecenyl succinic anhydrides are linear octadecenyl succinic anhydride such as n-octadecenyl succinic anhydride and/or branched octadecenyl succinic anhydride such as iso-octadecenyl succinic anhydride or 1-octyl-2 -decenyl succinic anhydride.

If the at least one monosubstituted succinic anhydride is a mixture of two or more types of succinic anhydrides monosubstituted by alkenyl, then it is provided that one specified succinic anhydride monosubstituted by alkenyl is present in an amount of from 20 to 60% by weight. and preferably from 30 to 50% wt. relative to the total weight of at least one monosubstituted succinic anhydride presented in step b).

For example, if the at least one monosubstituted succinic anhydride is a mixture of two or more types of succinic anhydrides, monosubstituted alkenyl, containing one or more hexadecenyl succinic anhydrides, such as linear or branched hexadecenyl succinic anhydride(s), and one or more octadecenyl -succinic anhydrides, such as linear or branched hexadecenyl-succinic anhydride(s), it is preferable that one or more octadecenyl-succinic anhydrides are present in an amount of from 20 to 60 wt.%. and preferably from 30 to 50% wt. relative to the total weight of at least one monosubstituted succinic anhydride presented in step b).

It is also contemplated that the at least one monosubstituted succinic anhydride may be a mixture of at least one monosubstituted alkyl succinic anhydride and at least one monosubstituted alkenyl succinic anhydride.

If the at least one monosubstituted succinic anhydride is a mixture of at least one monosubstituted alkyl succinic anhydride and at least one monosubstituted alkenyl succinic anhydride, then it is provided that said alkyl substituent of at least one monosubstituted alkyl succinic anhydride and The alkenyl substituent of at least one succinic anhydride monosubstituted with alkenyl is preferably the same. For example, the at least one monosubstituted succinic anhydride is a mixture of ethyl succinic anhydride and ethenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of propyl succinic anhydride and propenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of butyl succinic anhydride and butenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of triisobutyl succinic anhydride and triisobutenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of pentyl succinic anhydride and pentenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of hexyl succinic anhydride and hexenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of heptyl succinic anhydride and heptenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of octyl succinic anhydride and octenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of nonyl succinic anhydride and nonenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of decyl succinic anhydride and decenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of dodecyl succinic anhydride and dodecenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of hexadecanyl succinic anhydride and hexadecenyl succinic anhydride. For example, the at least one monosubstituted succinic anhydride is a mixture of linear hexadecanyl succinic anhydride and linear hexadecenyl succinic anhydride or a mixture of branched hexadecanyl succinic anhydride and branched hexadecenyl succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride is a mixture of octadecanyl succinic anhydride and octadecenyl succinic anhydride. For example, the at least one monosubstituted succinic anhydride is a mixture of linear octadecanyl succinic anhydride and linear octadecenyl succinic anhydride or a mixture of branched octadecanyl succinic anhydride and branched octadecenyl succinic anhydride.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is a mixture of nonyl succinic anhydride and nonenyl succinic anhydride

If the at least one monosubstituted succinic anhydride is a mixture of at least one monosubstituted alkyl succinic anhydride and at least one monosubstituted alkenyl succinic anhydride, then the weight ratio between at least one monosubstituted alkyl succinic anhydride and at least one succinic anhydride, monosubstituted alkenyl, is from 90:10 to 10:90 (% wt./% wt.). For example, the weight ratio between at least one mono-alkyl succinic anhydride and at least one mono-alkenyl succinic anhydride is from 70:30 to 30:70 (wt.%/wt.%) or from 60:40 to 40:60.

Optionally, at least one monosubstituted succinic anhydride is presented in combination with at least one monosubstituted succinic anhydride in step b) of the method according to the present invention.

It should be understood that the expression "at least one" monosubstituted succinic acid means that one or more types of monosubstituted succinic acid may be present in step b) according to the present invention.

Accordingly, it should be noted that the at least one monosuccinic acid may be one type of monosuccinic acid. Alternatively, the at least one monosuccinic acid may be a mixture of two or three types of monosuccinic acid. For example, the at least one monosuccinic acid may be a mixture of two or three types of monosuccinic acid, such as two types of monosuccinic acid.

In one embodiment of the present invention, the at least one monosuccinic acid is one type of monosuccinic acid.

The at least one monosubstituted succinic acid is provided as a surface treatment agent and consists of succinic acid monosubstituted by a group selected from any linear, branched, aliphatic and cyclic group containing a total number of carbon atoms from C2 to C20 in the specified substituent.

In one embodiment of the present invention, the at least one monosubstituted succinic acid consists of succinic acid, a monosubstituted group selected from linear, branched, aliphatic and cyclic group containing a total number of carbon atoms from C3 to C20 in the specified substituent. For example, the at least one monosubstituted succinic acid consists of succinic acid monosubstituted by a group selected from linear, branched, aliphatic and cyclic group containing a total number of carbon atoms from C4 to C20 in the specified substituent.

If in step b) of the proposed method at least one monosubstituted succinic anhydride is presented with at least one monosubstituted succinic acid, it is provided that the at least one monosubstituted succinic anhydride and the at least one monosubstituted succinic acid can contain the same or different substituents.

In one embodiment of the present invention, the succinic acid molecule of at least one monosubstituted succinic acid and the succinic anhydride molecule of at least one monosubstituted succinic anhydride are monosubstituted by the same group selected from any linear, branched and aliphatic group containing the total number of carbon atoms from C2 to C20, preferably from C3 to C20, and most preferably from C4 to C20 in the specified substituent, or from a cyclic group containing a total number of carbon atoms from C3 to C20, and most preferably from C4 to C20 in the specified substituent.

If at least one monosubstituted succinic anhydride is present in combination with at least one monosubstituted succinic acid, then the at least one monosubstituted succinic acid is present in an amount of ≤10 mol%. relative to the sum of moles of at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid. For example, at least one monosubstituted succinic acid is present in an amount of ≤5 mol%, preferably ≤2.5 mol%, and most preferably ≤1 mol%. relative to the sum of moles of at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid.

In one embodiment of the present invention, step b) of the proposed process provides at least one monosubstituted succinic anhydride and at least one monosubstituted succinic acid.

If the at least one monosubstituted succinic anhydride is presented in combination with at least one monosubstituted succinic acid, then the at least one monosubstituted succinic anhydride and the at least one monosubstituted succinic acid are preferably presented in the form of a mixture.

It is preferable that the at least one surface treatment agent in step b) is present in a total amount of from 0.1 to 3% by weight. relative to the total dry weight of the at least one calcium carbonate containing filler material from step a).

For example, the at least one surface treatment agent in step b) is present in a total amount of from 0.1 to 2% by weight, and most preferably from 0.1 to 1.5% by weight. relative to the total dry weight of the at least one calcium carbonate containing filler material from step a).

Additionally or alternatively, the at least one surface treatment agent in step b) is preferably present in an amount such that the total weight of said surface treatment agent on the surface of the at least one calcium carbonate containing filler material is less than 35 mg/m ² at least one filler material containing calcium carbonate presented in step a).

In one embodiment of the present invention, the at least one surface treatment agent in step b) is preferably present in such an amount that the total weight of said surface treatment agent on the surface of the at least one calcium carbonate containing filler material is less than 20 mg /m ² , even more preferably less than 15 mg/m ² , and most preferably less than 5 mg/m ² of at least one calcium carbonate-containing filler material presented in step a).

For example, the at least one surface treatment agent in step b) is preferably present in such an amount that the total weight of said surface treatment agent on the surface of the at least one calcium carbonate containing filler material is from 0.1 to 35 mg / ^m2 , more preferably from 0.2 to 20 mg/ ^m2 , even more preferably from 0.5 to 15 mg/ ^m2 , and most preferably from 0.1 to 5 mg/ ^m2 of at least one material filler containing calcium carbonate presented in step a).

Characteristics of step c): Contacting at least one filler material containing calcium carbonate with at least one surface treatment agent

According to step c) of the method according to the present invention, the surface of at least one calcium carbonate containing filler material from step a) is brought into contact by stirring in one or more steps, in any order, with at least one agent for surface treatment from step b), such that on the surface of said at least one filler material containing calcium carbonate from step a) a treatment layer is formed containing at least one surface treatment agent and/or reaction product(s) thereof .

Step c) of contacting at least one filler material containing calcium carbonate with at least one surface treatment agent is carried out under mild conditions. It is contemplated that mild conditions are necessary to reduce fines due to the low degree of abrasion, such that the surface treated filler material product produced by this process has substantially the same particle size distribution as the at least one filler material containing calcium carbonate, at stage a) with a low content of fine particles. In particular, this can be achieved if the total energy costs are lower than the energy costs typically required to carry out the methods known in the prior art. More specifically, the contacting in step c) is preferably carried out such that the total energy consumption resulting from the addition of at least one surface treatment agent from step b) to the at least one calcium carbonate containing filler material from step a) , is no more than 15 kWh/t. For example, the contacting in step c) is carried out such that the total energy consumption resulting from the addition of at least one surface treatment agent from step b) to the at least one calcium carbonate containing filler material from step a) is from 2 to 15 kWh/t, for example 2 to 10 kWh/t or 2 to 8 kWh/t.

In one embodiment of the present invention, the method according to the present invention, in particular the contacting step c) can be carried out in a continuous manner. In such a case, it can be ensured that the at least one filler material containing calcium carbonate is brought into contact with the at least one surface treatment agent in a continuous flow, whereby a constant concentration of the at least one surface treatment agent is achieved in step c). processing.

Alternatively, at least one calcium carbonate-containing filler material is contacted with at least one surface treatment agent in one step, wherein said at least one surface treatment agent is preferably added in one portion.

In another embodiment of the present invention, the method according to the present invention, in particular step c) can be carried out in a batch manner, i.e. at least one calcium carbonate containing filler material is contacted with at least one surface treatment agent in more than one step, said at least one surface treatment agent being preferably added in approximately equal portions. Alternatively, it is also possible to add at least one surface treatment agent to the at least one calcium carbonate containing filler material in unequal portions, i.e. in larger or smaller portions.

It is envisaged that the contacting step c) can be carried out such that at least one surface treatment agent from step b) is added to at least one calcium carbonate containing filler material from step a).

Alternatively, at least one calcium carbonate-containing filler material from step a) is added to at least one surface treatment agent from step b).

It is envisaged that an advantageous effect is achieved in particular if at least one surface treatment agent from step b) is added to at least one calcium carbonate-containing filler material from step a). For example, contacting step c) is carried out such that at least one surface treatment agent from step b) is sprayed onto at least one calcium carbonate containing filler material from step a).

To achieve low overall energy consumption, it is envisaged that process step c) should be carried out without additional temperature changes, i.e. heating or cooling. That is, the contacting step c) is preferably carried out at an appropriate ambient temperature. Thus, step c) of bringing into contact is preferably carried out at a temperature of from 18 to 45 °C.

In view of this, it is necessary that at least one surface treatment agent has a working viscosity within the specified temperature range, i.e. at least one surface treatment agent at temperatures between 18 and 45 °C must be in a molten or liquid state to achieve sufficient surface treatment.

Thus, it is preferable not to change the temperature before and/or during the contacting step c) so that the at least one surface treatment agent is in a molten or liquid state, i.e. The proposed method does not include the steps of adjusting the temperature before and/or during step c) bringing into contact.

The processing time for carrying out the contacting step c) is preferably 1000 seconds or less, preferably 500 seconds or less, more preferably 250 seconds or less, and most preferably 0.1 to 1000 seconds. For example, contacting step c) is carried out for 0.1 to 20 seconds, preferably 0.5 to 15 seconds, and most preferably 1 to 10 seconds.

It is further envisaged that the overall energy consumption can be reduced if the contacting step c) is carried out in an Archimedean screw, for example in a screw conveyor, a drum mixer, a pneumatic air conveyor system, a planetary mixer or a Guedu mixer.

Such equipment is generally known, and those skilled in the art can adapt the conditions used to suit the equipment used.

However, it is preferable that the drum mixer, planetary mixer or Guedu mixer has a diameter to height ratio of 1:1 to 1:5. It is further preferred that the drum mixer, planetary mixer or Guedu mixer is operated at a temperature of 18 to 45 °C.

With regard to the Archimedean screw, it is stipulated that the overall energy consumption is particularly low when the Archimedean screw is operated at a certain angle.

In one embodiment, the Archimedes screw is operated at an angle of from 0 to 80°, and more preferably from 0 to 70°. Preferably, the Archimedes screw is operated at an angle of from 30 to 80°, and more preferably from 35 to 70°.

When carrying out step c) of bringing into contact in one Archimedean screw, the Archimedes screw is preferably operated at an angle of from 30 to 80°, and more preferably from 35 to 70°.

In one embodiment, contacting step c) is carried out in two Archimedean screws. For example, the first Archimedes screw is operated at an angle from 0 to 30°, and more preferably from 0 to 20°, and the second Archimedes screw is operated at an angle from 30 to 80°, and more preferably from 35 to 70°. In such an embodiment, the first Archimedean screw is connected to the second Archimedes screw by an inclined groove. That is, the contents of the first Archimedean screw are preferably loaded through an inclined chute into the second Archimedes screw, i.e. the loading point of the second Archimedean screw is below the unloading point of the first Archimedean screw.

In addition, it is envisaged that the overall energy consumption can be particularly reduced if the contacting step c) is carried out such that at least one surface treatment agent from step b) is added to at least one filler material containing calcium carbonate , from stage a) in the lower 1/3 of the Archimedean screw.

For example, when performing step c) in one Archimedean screw, at least one surface treatment agent from step b) is preferably added to at least one calcium carbonate containing filler material from step a) in the lower 1/3 of the Archimedean screw , operated at an angle of from 30 to 80°, and more preferably from 35 to 70°.

When performing step c) in two Archimedean screws, at least one surface treatment agent from step b) is preferably added to at least one calcium carbonate containing filler material from step a) in the lower 1/3 of the first Archimedean screw, operated at an angle from 0 to 30°, and more preferably from 0 to 20°, and/or in the lower 1/3 of the second Archimedean screw, operated at an angle from 30 to 80°, and more preferably from 35 to 70°. For example, the at least one surface treatment agent from step b) is preferably added to the at least one calcium carbonate containing filler material from step a) in the lower 1/3 of the first Archimedean screw operated at an angle of from 0 to 30° , and more preferably from 0 to 20°, and/or in the lower 1/3 of the second Archimedean screw, operated at an angle from 30 to 80°, and more preferably from 35 to 70°. Alternatively, the at least one surface treatment agent from step b) is preferably added to the at least one calcium carbonate containing filler material from step a) in the lower 1/3 of the first Archimedean screw operated at an angle of from 0 to 30° , and more preferably from 0 to 20°, and in the lower 1/3 of the second Archimedean screw operated at an angle of from 30 to 80°, and more preferably from 35 to 70°. In such an embodiment, the at least one surface treatment agent from step b) is thus divided into multiple portions, for example two portions containing equal or unequal amounts of the at least one surface treatment agent from step b).

Additionally, it is preferable that the Archimedes screw be operated at a temperature of 18 to 45 °C.

In view of the above, it is preferable that at least one surface treatment agent from step b) is added to at least one calcium carbonate containing filler material from step a), which is loaded into an Archimedes screw, for example, a screw conveyor, a drum mixer, pneumatic air conveyor system, planetary mixer or Guedu mixer.

It is provided that at least one surface treatment agent is added at stage c) bringing into contact in a total amount of from 0.1 to 3 wt.%. relative to the total dry weight of the at least one calcium carbonate containing filler material from step a). For example, at least one surface treatment agent is added during contacting step d) in an amount of from 0.1 to 2% by weight. or from 0.1 to 1.5% wt. relative to the total dry weight of the at least one calcium carbonate containing filler material from step a).

The resulting surface treated filler material product has a 45 µm sieve residue, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the product based on the filler material with a treated surface. Preferably, the resulting surface treated filler material product has a 45 µm sieve residue, measured in accordance with ISO 787/7, of 0.5 to 30% by weight, and more preferably from 0.75 to 25% by weight. relative to the total mass of the product based on the filler material with a treated surface. For example, the resulting surface treated filler material product has a 45 µm sieve residue measured in accordance with ISO 787/7 of 0.75 to 15% by weight. or from 0.75 to 10% wt. relative to the total mass of the product based on the filler material with a treated surface.

As already indicated above, the proposed method is characterized by almost complete absence of abrasion due to low energy consumption and, therefore, the resulting surface treated filler material product has substantially the same particle size distribution as at least one filler material containing calcium carbonate, in step a).

Taking this into account, the amount of residue on the 45 μm sieve of at least one filler material containing calcium carbonate from step a), measured in accordance with ISO 787/7, and the residue on the 45 μm sieve of the product based on the treated filler material surface measured in accordance with ISO 787/7 preferably differs by less than 20 wt.%. Preferably, the amount of 45 µm sieve residue of at least one calcium carbonate containing filler material from step a) measured in accordance with ISO 787/7, and the 45 µm sieve residue of the surface treated filler material product, measured in accordance with ISO 787/7, differs by less than 15% by weight, more preferably by less than 10% by weight, even more preferably by less than 5% by weight.

It should be noted that the 45 µm sieve residue of a surface treated filler material product, measured in accordance with ISO 787/7, may be greater or less than the 45 µm sieve residue of at least one calcium carbonate containing filler material , from stage a), measured in accordance with ISO 787/7.

The treatment layer formed on the surface of at least one filler material containing calcium carbonate is provided to contain at least one surface treatment agent presented in step b) and/or reaction product(s) thereof formed as products interaction by bringing into contact the filler material containing calcium carbonate with at least one surface treatment agent from step b). In such a case, the treatment layer on the surface treated filler material product preferably further comprises a reaction product(s) of at least one surface treatment agent formed on the surface of the at least one calcium carbonate containing filler material in the step c). For example, the reaction product(s), such as one or more calcium salts and/or magnesium salts of at least one surface treatment agent.

The treatment layer is preferably characterized in that the total weight of at least one surface treatment agent and/or its reaction product(s) on the surface of the surface treated filler material product is from 0.1 to 35 mg/m ² or more preferably from 0.2 to 20 mg/m ² , and most preferably from 0.5 to 15 mg/m ² , from 0.1 to 5 mg/m ² of at least one filler material containing calcium carbonate.

The treatment layer is preferably characterized in that the total weight of at least one surface treatment agent and/or its reaction product(s) on the surface of the surface treated filler material product is from 0.1 to 2 mg/m ² or more preferably from 0.2 to 1 mg/m ² , and most preferably from 0.3 to 0.5 mg/m ² of at least one filler material containing calcium carbonate.

It is further provided that the resulting surface treated filler material product contains a treatment layer in an amount of 0.1 to 3% by weight, preferably in an amount of 0.1 to 2% by weight, more preferably in an amount of 0.2 up to 4% wt., and most preferably in an amount from 0.1 to 1.5% wt. relative to the total dry weight of at least one filler material containing calcium carbonate.

Thus, it is envisaged that at least one calcium carbonate-containing filler material product obtained in process step c) comprises, preferably consists of, at least one calcium carbonate-containing filler material and a treatment layer containing at least one surface treatment agent and/or reaction product(s) thereof. The treatment layer is formed on the surface of the at least one filler material containing calcium carbonate from step a).

Additionally or alternatively, the treatment layer of the surface treated filler material product contains at least one surface treatment agent and/or reaction product(s) thereof in a specified molar ratio. For example, the molar ratio of the at least one surface treatment agent to its reaction product(s) is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.

The expression "molar ratio of at least one surface treatment agent to its reaction product(s)" in the context of the present invention refers to the ratio of the sum of the molecular weights of at least one surface treatment agent to the sum of the molecular weights of the molecules of the surface treatment agent in its products reactions.

It is contemplated that the at least one filler material containing calcium carbonate may contain water or an organic solvent. In one embodiment, the surface treated filler material product thus obtained may be dried. This optional step is preferably carried out to reduce the water or organic solvent content of the resulting surface treated filler material product. Thus, the resulting dried surface treated filler material product has a moisture content that is lower than the moisture content of the surface treated filler material product obtained before the drying step, i.e. after stage c).

Thus, in accordance with one embodiment of the present invention, the proposed method includes the additional step of d) drying the surface treated filler material product obtained in step c).

For example, the optional drying step d) is carried out at a temperature of from 60 to 180 °C, preferably from 50 to 150 °C, more preferably from 60 to 120 °C, and most preferably from 80 to 120 °C, at atmospheric or reduced pressure to reducing the water or organic solvent content in the resulting product based on a filler material with a treated surface.

In one embodiment, the optional drying step d) is carried out until the resulting surface treated filler material product reaches a water or organic solvent content of from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0. 01 to 10% wt., and most preferably from 0.05 to 5% wt. relative to the total weight of at least one filler material containing calcium carbonate.

It is contemplated that the optional drying step d) may be carried out at atmospheric pressure or under reduced pressure. Preferably, drying is carried out at atmospheric pressure.

Thus, the optional drying step d) is preferably carried out at a temperature of from 60 to 180 °C at atmospheric pressure. For example, the optional drying step d) is carried out at a temperature of from 50 to 150 °C, preferably from 60 to 120 °C, and more preferably from 80 to 120 °C at atmospheric pressure.

Preferably, steps a) to c) of the proposed method are carried out without water or an organic solvent and, therefore, the method according to the present invention does not include process step d).

The surface treated filler material product produced in accordance with the present invention is a coarse material.

In particular, the surface treated filler material product contains

a) at least one filler material product containing calcium carbonate, which has

i) volumetric median particle size d ₅₀ from 5 to 100 µm,

ii) upper size limit ( d ₉₈ ) from 30 to 500 µm,

b) a treatment layer on the surface of at least one filler material containing calcium carbonate, which contains at least one surface treatment agent and/or reaction products thereof, wherein the surface treated filler material product contains a treatment layer in an amount from 0.1 to 3% wt. relative to the total dry weight of at least one filler material containing calcium carbonate,

wherein said surface treated filler material product has a residue on a 45 μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the product based on the filler material with a treated surface.

With respect to the definition of at least one calcium carbonate containing filler material, at least one surface treatment agent, and preferred embodiments thereof, reference is made to the comments provided above in the description of process steps a), b) and c).

Preferably, the surface treated filler material product is in powder form.

In one embodiment of the present invention, a surface treated filler material product may be produced (or produced) by the method of the present invention.

Thus, a product based on a surface-treated filler material contains

a) at least one filler material containing calcium carbonate, which has

i) volumetric median particle size d ₅₀ from 5 to 100 µm,

ii) upper size limit ( d ₉₈ ) from 30 to 500 µm,

b) a treatment layer on the surface of at least one filler material containing calcium carbonate, which contains at least one surface treatment agent and/or reaction products thereof, wherein the resulting surface treated filler material product comprises a treatment layer in amount from 0.1 to 3% wt. relative to the total dry weight of at least one filler material containing calcium carbonate,

wherein said surface treated filler material product has a residue on a 45 μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the product based on the filler material with a treated surface,

wherein the surface treated filler material product may be produced (or produced) by a method for producing the surface treated filler material product, which method comprises at least the steps of:

a) providing at least one filler material containing calcium carbonate, which has

i) volumetric median particle size d ₅₀ from 5 to 100 µm,

ii) upper size limit ( d ₉₈ ) from 30 to 500 µm, and

iii) residue on a 45 µm sieve, measured in accordance with ISO 787/7, greater than 0.5% by weight. relative to the total mass of filler material containing calcium carbonate,

b) providing at least one surface treatment agent in a molten or liquid state at a temperature between 18 and 45 °C,

c) bringing into contact, by mixing in one or more stages, the surface of at least one calcium carbonate containing filler material from step a) with at least one surface treatment agent from step b), such that on the surface of said at least at least one filler material containing calcium carbonate, from step a) a treatment layer is formed containing at least one surface treatment agent and/or reaction product(s) thereof,

wherein the resulting product based on the surface treated filler material has a residue on a 45 μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the product based on the filler material with a treated surface.

The surface treated filler material product thus obtained is advantageously used to produce an article, preferably a polymer article, containing at least one polymer resin and from 1 to 95% by weight. product based on a filler material with a treated surface.

Thus, in a further aspect, the present invention relates to an article, preferably a polymer article, comprising a surface treated filler material product. In one embodiment, the product, preferably a polymer product, contains at least one polymer resin and from 1 to 95 wt.%. product based on a filler material with a treated surface relative to the total weight of the polymer composition. For example, the product, preferably a polymer product, contains a product based on a surface-treated filler material in an amount of from 5 to 95% by weight. and preferably from 10 to 85% wt. relative to the total weight of the product. For example, the product, preferably a polymer product, contains a product based on a surface-treated filler material in an amount of from 15 to 80% by weight. relative to the total weight of the product.

Accordingly, the polymer composition contains at least one polymer resin. The polymer resin forms the basis of the composition and provides strength, flexibility, rigidity and wear resistance to the finished product, preferably a polymer product.

Preferably, the at least one polymer resin according to the present invention is not limited to a particular resinous material, as long as such polymer composition is suitable for preparing an article, preferably a polymer article.

In one embodiment of the present invention, the at least one polymer resin is at least one thermoplastic polymer. Thus, it is preferred that the at least one polymer resin is a thermoplastic polymer selected from the group consisting of homopolymers and/or copolymers of polyolefins, polyamides, halogenated polymers, polyesters, polyurethanes and thermoset resins.

Additionally or alternatively, the at least one polymer resin is a polyolefin homopolymer and/or copolymer. For example, the at least one polymer resin is a homopolymer and a copolymer of a polyolefin. Alternatively, the at least one polymer resin is a polyolefin homopolymer or copolymer.

It is provided that the at least one polymer resin is preferably a polyolefin homopolymer.

For example, the polyolefin may be polyethylene and/or polypropylene and/or polybutylene. Accordingly, if the polyolefin is polyethylene, then said polyolefin is selected from the group consisting of homopolymers and/or copolymers of polyethylene, such as high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), very low density polyethylene (LDPE), linear low density polyethylene (LLDPE).

For example, the polyolefin is a homopolymer and/or copolymer of polyethylene.

The expression "polyethylene homopolymer" in the context of the present invention refers to a polyethylene containing polyethylene, which consists essentially, i.e. more than 99.7% wt., even more preferably at least 99.8% wt. relative to the total weight of polyethylene, from ethylene units. For example, in a polyethylene homopolymer, only ethylene units are detectable.

If at least one polymer resin in the polymer composition contains a polyethylene copolymer, it is provided that the polyethylene contains units that can be obtained from ethylene as main components. Accordingly, the polyethylene copolymer contains at least 55% wt. units that can be derived from ethylene, more preferably at least 60% wt. units derived from ethylene, relative to the total weight of polyethylene. For example, the polyethylene copolymer contains from 60 to 99.5% wt., more preferably from 90 to 99% wt. units derived from ethylene, relative to the total weight of polyethylene. The comonomers present in such a polyethylene copolymer are C3 - C10 α-olefins, preferably 1-butene, 1-hexene and 1-octene, the latter being particularly preferred.

Additionally or alternatively, the polyolefin is a homopolymer and/or copolymer of polypropylene.

The expression "polypropylene homopolymer" in the context of the present invention refers to polypropylene, which consists essentially, i.e. more than 99% by weight, even more preferably at least 99.5% by weight, for example at least 99.8% by weight. relative to the total weight of polypropylene, made from propylene units. In a preferred embodiment, only propylene units are detectable in the polypropylene homopolymer.

In case at least one polymer resin in the polymer composition contains a polypropylene copolymer, the polypropylene preferably contains units that can be derived from propylene as main components. The polypropylene copolymer preferably contains, preferably consists of units derived from propylene and a C2 and/or at least one C4 - C10 α-olefin. In one embodiment of the present invention, the polypropylene copolymer comprises, preferably consists of, units derived from propylene and at least one α-olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene . For example, a polypropylene copolymer contains, preferably consists of units derived from propylene and ethylene. In one embodiment of the present invention, the units, which may be derived from propylene, form the bulk of the polypropylene, i.e. at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, even more preferably from 60 to 99% by weight, even more preferably from 70 to 99% by weight, and most preferably from 80 to 99% wt. relative to the total weight of polypropylene. The amount of units derived from C2 and/or at least one C4 - C10 α-olefin in said polypropylene copolymer is from 1 to 40% by weight, more preferably from 1 to 30% by weight, and most preferably from 1 to 20 % wt. relative to the total weight of the polypropylene copolymer.

If the polypropylene copolymer contains only units that can be obtained from propylene and ethylene, the amount of ethylene is preferably from 1 to 20% by weight, preferably from 1 to 15% by weight, and most preferably from 1 to 10% by weight. relative to the total weight of the polypropylene copolymer. Accordingly, the amount of propylene is preferably 80 to 99% by weight, preferably 85 to 99% by weight, and most preferably 90 to 99% by weight. relative to the total weight of the polypropylene copolymer.

Additionally or alternatively, the polyolefin is a homopolymer and/or copolymer of polybutylene.

The expression "polybutylene homopolymer" in the context of the present invention refers to polybutylene, which consists essentially, i.e. more than 99% by weight, even more preferably at least 99.5% by weight, for example at least 99.8% by weight. relative to the total weight of polybutylene, from butylene units. In a preferred embodiment, only butylene units are detectable in the polybutylene homopolymer.

In case at least one polymer resin in the polymer composition contains a polybutylene copolymer, the polybutylene preferably contains units that can be derived from butylene as main components. The polybutylene copolymer preferably contains, preferably consists of units derived from butylene and a C2 and/or C3 and/or at least one C5 to C10 α-olefin. In one embodiment of the present invention, the polybutylene copolymer comprises, preferably consists of, units derived from butylene and at least one a-olefin selected from the group consisting of ethylene, 1-propene, 1-pentene, 1-hexene and 1-octene . For example, a polybutylene copolymer contains, preferably consists of units derived from butylene and ethylene. In one embodiment of the present invention, the units that can be derived from butylene form the bulk of the polybutylene, i.e. at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, even more preferably from 60 to 99% by weight, even more preferably from 70 to 99% by weight, and most preferably from 80 to 99% wt. relative to the total weight of polybutylene. The amount of units derived from C2 and/or C3 and/or at least one C5 to C10 α-olefin in said polybutylene copolymer is from 1 to 40% by weight, more preferably from 1 to 30% by weight, and most preferably from 1 to 20% wt. relative to the total weight of the polybutylene copolymer.

If the at least one polymer resin is a homopolymer and/or copolymer of a halogen-containing polymer, the at least one polymer resin is preferably selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and PVC-PVC copolymers. polyvinyl acetate, and plasticized PVC and their copolymers.

If the at least one polymer resin is a polyester homopolymer and/or copolymer, the at least one polymer resin is preferably selected from polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), as well as degradable polyesters such as polylactic acid (polylactide, PLA).

In one embodiment of the present invention, the at least one polymer resin is a homopolymer of polyethylene and/or polypropylene and/or polybutylene. For example, the at least one polymer resin is a homopolymer of polyethylene and polypropylene. Alternatively, the at least one polymer resin is a homopolymer of polyethylene or polypropylene. In one embodiment of the present invention, the at least one polymer resin is a polypropylene homopolymer.

The expression “at least one” polymer resin means that one or more types of polymer resins may be present in the polymer composition of the present invention.

Accordingly, it is contemplated that the at least one polymer resin may be a mixture of two or more types of polymer resins. For example, if at least one polymer resin is a mixture of two or more polymer resins, then one polymer resin is a homopolymer or copolymer of polypropylene, and the second or additional polymer resins are selected from the group consisting of homopolymers and/or copolymers of polyethylene, polybutylene, polyamides , polyesters, halogen-containing polymers, and mixtures thereof.

In one embodiment of the present invention, the at least one polymer resin is one type of polymer resin. Preferably, the at least one polymer resin is a homopolymer of polyethylene or polypropylene.

In one embodiment of the present invention, the at least one polymer resin has a melting point Tm. above 100 °C, more preferably above 150 °C, for example above 200 °C. For example, the melting point of the at least one polymer resin is from 100 to 350°C, more preferably from 150 to 325°C, even more preferably from 180 to 260°C, and most preferably from 200 to 300°C.

It is further contemplated that the at least one polymer resin may be selected from polyolefins having a wide range of melt flow properties. In general, it is preferable that the polyolefin has a melt flow index MFR (190 °C) from 0.1 to 3000 g/10 min, more preferably from 0.2 to 2500 g/10 min. For example, polyolefin has a melt flow index MFR (190 °C) from 0.3 to 2000 g/10 min. or from 0.3 to 1600 g/10 min. Additionally or alternatively, the at least one polymer resin has a melt flow index MFR (230°C) from 0.1 to 3000 g/10 min, more preferably from 0.2 to 2500 g/10 min. For example, polyolefin has a melt flow index MFR (230 °C) from 0.3 to 2000 g/10 min. or from 0.3 to 1600 g/10 min.

For example, if the at least one polymer resin is a polyolefin that is a homopolymer and/or copolymer of polypropylene, then preferably the at least one polymer resin has a melt flow index MFR (190 °C, 2.16 kg) from 1 to 3000 g/10 min., more preferably 3 to 2500 g/10 min. For example, at least one polymer resin that is a homopolymer and/or copolymer of polypropylene has a melt flow index MFR (190 °C) from 5 to 2000 g/10 min. or from 10 to 1600 g/10 min. Preferably, the at least one polymer resin, which is a homopolymer and/or copolymer of polypropylene, has a melt flow index MFR (230 °C) from 1 to 3000 g/10 min, more preferably from 3 to 2500 g/10 min . For example, at least one polymer resin that is a homopolymer and/or copolymer of polypropylene has a melt flow index MFR (230 °C) from 5 to 2000 g/10 min. or from 10 to 1600 g/10 min.

If the at least one polymer resin is a polyolefin, which is a homopolymer and/or copolymer of polyethylene, it is provided that the at least one polymer resin has a sufficiently low melt flow rate. Accordingly, it is preferable that at least one polymer resin, which is a homopolymer and/or copolymer of polyethylene, has a melt flow index MFR (190 °C) from 0.5 to 20 g/10 min, more preferably from 0.7 up to 15 g/10 min. For example, at least one polymer resin has a melt flow index MFR (190 °C) from 0.9 to 10 g/10 min. or from 0.9 to 5 g/10 min. Additionally or alternatively, at least one polymer resin, which is a homopolymer and/or copolymer of polyethylene, has a melt flow index MFR (230 °C) from 0.1 to 3000 g/10 min, more preferably from 0.2 to 2500 g/10 min. For example, at least one polymer resin that is a homopolymer and/or copolymer of polyethylene has a melt flow index MFR (230 °C) from 0.3 to 2000 g/10 min. or from 0.3 to 1600 g/10 min.

In one embodiment of the present invention, the polymer composition contains a surface treated filler material product in an amount of from 5 to 95% by weight. and preferably from 10 to 85% wt. relative to the total weight of the polymer composition. For example, the polymer composition contains a product based on a surface-treated filler material in an amount of from 15 to 80 wt.%. relative to the total weight of the polymer composition.

Brief description of graphic materials

In fig. Figure 1 shows a comparison of the viscosity of ASA-treated CaCO ₃ in a PVC plastisol floor covering.

The following examples may further illustrate the present invention, but should not be construed as limiting the present invention to the exemplified embodiments.

EXAMPLES

A) Measurement methods

The following measurement methods were used to determine the parameters specified in the examples and claims.

Particle size distribution (% wt. particles with diameter < X) and mass median diameter ( d ₅₀ ) dispersed material

Volumetric median particle size d ₅₀ (vol) and volumetric upper limit particle size d ₉₈ (vol) were measured using a Malvern Mastersizer 2000 laser diffraction system (Malvern Instruments Pic., UK). The value d ₅₀ (vol.) or d ₉₈ (vol.) means a diameter value such that 50% or 98% by volume, respectively, of the particles have a diameter less than the specified value. The raw data obtained from the measurement was analyzed using Mie theory, with a particle refractive index of 1.57 and an absorption index of 0.005. These methods and instruments are known to those skilled in the art and are commonly used to determine the particle size distribution of fillers and pigments.

Specific surface area of the material according to BET

In the present invention, the specific surface area (in m ² /g) of the mineral filler was determined by the BET method (using nitrogen as adsorbing gas), well known to those skilled in the art (ISO 9277:2010). The total surface area (in m ² ) of the mineral filler was then determined by multiplying the specific surface area by the mass (in g) of the mineral filler before treatment.

Weight of surface treatment layer

The weight of the treatment layer on the calcium carbonate-containing filler material was calculated theoretically based on the BET values of the untreated calcium carbonate-containing filler material and the amount of monosuccinic anhydride and a mixture of aliphatic linear or branched carboxylic acids containing stearic acid that was used for the surface treatment . It was considered that the surface treatment layer on the surface of the filler material containing calcium carbonate was 100% monosubstituted succinic anhydride and a mixture of aliphatic linear or branched acids containing stearic acid added to the filler material containing calcium carbonate.

Tensile tests

Type IB specimens were used in accordance with ISO 3167, and tests were carried out in accordance with ISO 527 on a 15 cm "dumbbell shaped specimen". E-modulus and tensile strength, elongation at break tests were carried out on a Zwick Roell type Z020 in accordance with ISO 527-3.

Melt flow rate

The melt flow rate was determined in accordance with ISO 1133 (ASTM D1238) at 190 °C and under a load of 5 kg or 10 kg, respectively, on a Ceast (IT) type “Modular Melt Flow Line” instrument.

B) Examples

a) Example 1

This example relates to the preparation of a surface treated filler material product in accordance with the present invention.

To obtain a product based on a filler material with a treated surface, Urgon limestone was dry ground in a horizontal ball mill. The resulting filler material containing calcium carbonate had a d ₅₀ of approximately 6.6 μm, an upper limit of d ₉₈ size of 49.3 μm, a residue on a 45 μm sieve of 1.4 wt.%. and a BET specific surface area of 1.1 m ² /g, and a residual moisture content of 0.2% wt.

The resulting spray-dried calcium carbonate filler material was then processed as described in the following tests.

Test 1 (reference treatment)

A filler material containing spray-dried calcium carbonate was continuously fed at a speed of 200 kg/h into a pin mill and treated with liquid alkenyl succinic anhydride ("ASA", Hydrores AS 1000, CAS number 68784-12-3, commercially available from Kemira Oyj, Vasa, Finland), which was fed at a speed of 6 kg/h into a Contraplex 250 CW pin mill (with a 250 mm diameter disc, with a door rotation speed of 3000 rpm and with a horizontal body rotation speed of 6000 rpm, and containing 120 pins in the door and 120 pins in the body in three rows) manufactured by HOSOKAWA ALPINE™ (Ausburg, Delaware) and at 100°C to achieve a surface finish of 0.3% wt.

Test 2 (treatment according to the present invention)

The filler material containing spray-dried calcium carbonate was continuously fed at a speed of 750 kg/h into a 4 m long, 30° incline screw conveyor along a 2.8 m long horizontal screw conveyor. Liquid alkenyl succinic anhydride ( "ASA", Hydrores AS 1000, CAS number 68784-12-3, available from Kemira Oyj, Vasa, Finland) was fed at a rate of 22.5 kg/h onto a horizontal screw conveyor at an ambient temperature of approximately 25 °C. At the end of the inclined screw conveyor, the filler material product containing calcium carbonate, surface treated with a surface treatment degree of 0.3% by weight, was poured into a hopper.

The particle size distribution of the raw material for tests 1 and 2 was analyzed on a Mastersizer 2000 from Malvern Instruments (UK) to determine the average particle size distribution d ₅₀ and the upper limit of the size d ₉₈ , and the residue was measured on a 45 μm sieve in accordance with ISO 787/7, before and after processing in accordance with the reference pin mill processing and in accordance with the present invention, and the results are presented in Table 1.

Table 1

Raw materials
(original filler mineral containing spray dried calcium carbonate) Raw materials
(Challenge 1) Raw materials
(Challenge 2) Treatment with 0.3% ASA No Yes Yes Processing method - Pin mill Conveyor auger d ₉₈ 49.3 µm 28.0 µm 52.9 µm d ₅₀ 6.6 µm 7.8 µm 6.97 µm Residue on 45 µm sieve, mg/100 g 1387 3 1474

As shown in Table 1, during pin mill surface treatment (Test 1), the particle size distribution of the raw calcium carbonate-containing filler mineral changed significantly. The upper limit size d ₉₈ value is almost half of the original value, and the median particle size d ₅₀ has increased by about 20%, and there is almost no residue on the 45 µm sieve. Compared with the surface treated material of the present invention (Test 2), for which the median particle size d ₅₀ increased by only about 5% and the upper size limit value increased slightly, which may be due to the low aggregate content, the screen residue is also close to the value of raw raw material.

The results obtained demonstrate that the surface treatment method according to the present invention not only reduces the energy consumption for obtaining the said product, but also does not cause significant changes in the physical properties of the raw material and, therefore, the mineral product based on the filler material containing calcium carbonate with such surface treatment is almost equivalent to the raw material, except for the presence of surface treatment.

b) Example 2

A filler material product containing calcium carbonate was used with the surface treatment of Test 1 of Example 1, i.e. sample 1 was obtained in accordance with the reference treatment, as well as from test 2 of example 1, i.e. sample 2 was prepared in accordance with the method according to the present invention.

Sample 1 and Sample 2 were introduced into a PVC plastisol flooring composition and viscosity measurements were taken. In addition, a filler material containing calcium carbonate without surface treatment (raw material) without surface treatment agent (sample 3) and a filler material containing calcium carbonate without surface treatment (raw material) with separately added surface treatment agent (sample 4). Viscosity was measured on an Anton Paar (CH) rheometer type MCR 300 in accordance with method CC27, using a cylindrical system and a spindle with a diameter of 27 mm, a gap between the spindle and the cylinder of 1 mm, at 23 ° C with a preliminary soaking of the paste for 5 minutes at a shear rate 10 s ^-1 and 1.) increasing from 0 to 30 s ^-1 for 120 s, 2.) maintaining at a constant value for 60 s at 30 s ^-1 and 3.) decreasing from 30 to 0 s ^-1 ' for 120 s. Data analysis is based on values obtained by reducing the shift in 3 parts of the measurement. The composition of the PVC plastisol floor covering is presented in Table 2.

table 2

CaCO ₃ +0.3% wt. ASA (sample 1 - reference)
150 wt. h. CaCO ₃ +0.3% wt. ASA (sample 2 - according to the invention)
150 wt. h. CaCO ₃ (raw) without processing (sample 3)
150 wt. h. CaCO ₃ (raw material) without treatment (sample 4) 150 wt. h. E-PVC (LacovyI PB 1301) 100 wt. h. 100 wt. h. 100 wt. h. 100 wt. h. DINP* 75 wt. h. 75 wt. h. 75 wt. h. 75 wt. h. A.S.A. - - - 0.3% wt. in composition

* Diisononyl phthalate, CAS 68515-48-0, added as plasticizer

In fig. 1 shows the effect of particle size and surface treatment agent on the viscosity of a PVC plastisol flooring composition. The surface treated filler product produced by pin mill coating (reference) exhibits an increase in viscosity compared to untreated CaCO ₃ . Viscosity is improved by adding alkenyl succinic anhydride directly to the PVC plastisol flooring composition. The best viscosity results are obtained when the surface treated filler material product obtained in accordance with the present invention is added to the PVC plastisol flooring composition.

c) Example 3

The filler material product containing calcium carbonate with surface treatment was obtained in accordance with Test 2 of Example 1 according to the present invention, and the surface treatment degree of ASA was 0.5% by weight. The preparation of C-PVC samples is presented below in Table 3.

Table 3

Samples E1
(reference) E2 (according to the invention) E3 (according to the invention) E4 (according to the invention) C-PVC (k value 66, Inovyn) 100 wt. h. 100 wt. h. 100 wt. h. 100 wt. h. DINP* 30 wt. h. 30 wt. h. 30 wt. h. 30 wt. h. Ca/Zn stabilizer (CZ 2913) 2.5 wt. h. 2.5 wt. h. 2.5 wt. h. 2.5 wt. h. CaCO ₃ (untreated) 170 wt. h. CaCO ₃ (surface treated with 0.5 wt.% ASA) 170 wt. h. 180 wt. h. 190 wt. h.

* Diisononyl phthalate, CAS 68515-48-0, added as plasticizer

E1 is a reference material produced with calcium carbonate filler material without coating. E2 to E4 are materials of the present invention prepared with a surface-coated calcium carbonate-containing filler material product prepared in accordance with the present invention, wherein the calcium carbonate-containing filler material product is coated on the surface surfaces were added in different quantities.

The samples were mixed dry in a Thermomix mixer (manufactured by Fa. Vorwerk, Germany) for 120 seconds at 120°C and 6000-7000 rpm, then processed in a two-roller mill at 170°C. Samples were cut from pressed sheets preformed on a Collin hydraulic press, type P300P, for tensile testing. Hydraulic pressing was carried out on a metal frame 2 mm thick, 17 cm x 17 cm, using 200 g of material after rolling. Pressing was carried out at 170 °C at 200 bar for 2 minutes. The press was then allowed to cool to 15°C (water cooling), maintaining the pressure at 200 bar. The test results of the obtained S-PVC samples are presented below in Table 4.

Table 4

Samples E1
(reference) E2
(according to the invention) E3
(according to the invention) E4
(according to the invention) Module E [N/mm ² ] 766 615 781 626 Tensile strength [N/ ^mm2 ] 9.4 8.6 9.0 7.6 Elongation at break [%] 93 104 100 106

The cut specimens for tensile testing were obtained using a cutting device manufactured by Fa. Hans Naef AG (Switzerland). Type 1B specimens were used in accordance with ISO 3167, and tests were carried out in accordance with ISO 527 on a 15 cm "dumbbell shaped specimen". E-modulus and tensile strength, elongation at break tests were carried out on a Zwick Roell type Z020 in accordance with ISO 527-3.

Examples E2 to E4 of the present invention show an overall increase in elongation at break compared to the reference sample, and E modulus and tensile strength are greatest in Example E3 of the present invention.

d) Example 4

The filler material product containing calcium carbonate with surface treatment was obtained in accordance with Test 2 of Example 1 according to the present invention, and the surface treatment degree of ASA was 0.5% by weight. The preparation of polyolefin samples is presented below in Table 5.

Table 5

Samples E5
(reference) E6
(according to the invention) E7
(reference) E8
(according to the invention) E9
(according to the invention) (1) (1) (2) (2) (2) LLDPE* 15% wt. 15% wt. 7% wt. 7% wt. 6% wt. CaCO3
(without processing) 85% wt. 75% wt. CaCO3 (0.5 wt.% ASA) 85% wt. 75% wt. 80% wt. Elastomer** 14% wt. 14% wt. 11% wt. Mineral oil * 4% wt. 4% wt. 3% wt.

*LLDPE (ExxonMobile, LLDPE LL 6101, MFR =20), **Elastomer (Dow, Engage 7270, MFR=0.8), # mineral oil (paraffin oil, VWR Chemicals, viscosity: 69 cSt); (1) application for compounding PE, (2) application for thick layers of PE

The sample materials were compounded and the melt flow index was determined using a Ceast (IT) Modular Melt Flow Line instrument in accordance with ISO 1133 (ASTM D1238) at 190°C and under a load of 5 kg or 10 kg, respectively. The test results for polyolefin samples are presented below in Table 6.

Table 6

E5
(reference) E6
(according to the invention) E7
(reference) E8
(according to the invention) E9
(according to the invention) MFI (190°C/10 kg) [g/10 min.] 1.2 2.8 MFI (190°C/5 kg) [g/10 min.] 4.3 6.6 3.1

The melt flow rate of a surface treated material containing a mineral filler product that contains calcium carbonate exhibits improved or nearly the same melt flow rate at the same or increased filler content.

e) Example 5

The filler material product containing calcium carbonate with surface treatment was obtained in accordance with Test 2 of Example 1 according to the present invention, and the surface treatment degree of ASA was 0.5% by weight. The preparation of C-PVC samples is presented below in Table 7.

Table 7

Samples E10
(reference) E11
(according to the invention) C-PVC (k value 66, Inovyn) 100 wt. h. 100 wt. h. Ca/Zn stabilizer (CZ 2913) 3.5 wt. h. 3.5 wt. h. CaCO ₃ (untreated) 60 wt. h. 0 CaCO ₃ (surface treated with 0.5 wt.% ASA) 0 60 wt. h.

The samples were mixed dry in a Thermomix mixer (manufactured by Fa. Vorwerk, Germany) for 120 seconds at 120 °C and 6000-7000 rpm, then processed in a two-roller mill at 170 °C. The dry mixture was further processed on a Haake™ Rheomix OS twin-screw kneader (Thermo Fisher) to evaluate the gelation characteristics of the dry mixture. Plasticization was carried out at 170 °C at 30 rpm. using two Delta rotors rotating in opposite directions. The amount of dry mix in the plasticizer chamber was 85 g. Gelation, sometimes also called plasticization, is generally understood as a process in which a binder, typically used with stabilizers, diffuses into the PVC resin particles during processing.

Sample Gel Time E10 (reference) 96 s E11 (according to the invention) 66 s

ASA treatment provides an obvious reduction in gelation time. This means that by using CaCO ₃ treated with ASA, the throughput of the extrusion line can be increased.

Claims (29)

1. A method for producing a filler material with a treated surface, comprising at least the stages of: a) providing at least one filler material containing calcium carbonate, which has i) volumetric median particle size d ₅₀ from 5 to 100 µm, ii) upper size limit (d ₉₈ ) from 30 to 500 µm and iii) 45 µm sieve residue, measured in accordance with ISO 787/7, greater than 0.5% by weight. relative to the total mass of filler material containing calcium carbonate, b) providing at least one surface treatment agent in a molten or liquid state at a temperature of from 18 to 45°C, c) bringing into contact the surface of at least one filler material containing calcium carbonate from step a) while mixing in one or more stages with at least one surface treatment agent from step b), so that on the surface of said at least At least one filler material containing calcium carbonate, step a) forms a treated layer containing at least one surface treatment agent and/or reaction product(s) thereof, where step c) bringing into contact is carried out in an Archimedean screw, for example in a screw conveyor or in a pneumatic air conveyor system, and where the Archimedes screw is operated at an angle of 30 to 80° and/or at a temperature of 18 to 45°C, wherein the resulting surface-treated filler material has a residue on a 45-μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the filler material with the treated surface. 2. The method according to claim 1, characterized in that the filler material containing calcium carbonate from step a) is selected from the group consisting of ground calcium carbonate, preferably marble, limestone, dolomite and/or chalk, precipitated calcium carbonate (PCC ), preferably vaterite, calcite and/or aragonite, surface reacted calcium carbonate (MCC) and mixtures thereof, more preferably the calcium carbonate containing filler material is ground calcium carbonate. 3. Method according to claim 1 or 2, characterized in that at least one filler material containing calcium carbonate, in step a) has a) the value of the volumetric median particle size d ₅₀ is from 6 to 80 μm, preferably from 7 to 60 μm and most preferably from 7.5 to 50 μm, b) an upper size limit (d ₉₈ ) of 40 to 400 µm, preferably 50 to 300 µm, more preferably 50 to 250 µm, and c) residue on a 45 µm sieve, measured in accordance with ISO 787/7, in the range from more than 0.5 to 30% by weight, preferably from 0.75 to 25% by weight. relative to the total mass of filler material containing calcium carbonate. 4. Method according to claim 1 or 2, characterized in that the amount of residue on the 45 μm sieve of at least one filler material containing calcium carbonate from step a), measured in accordance with ISO 787/7, and the residue on A 45-μm sieve of surface-treated filler material, measured in accordance with ISO 787/7, preferably differs by less than 20% by weight. 5. Method according to claim 1 or 2, characterized in that at least one surface treatment agent from step b) has a Brookfield viscosity≤1000 mPa⋅s at 25°C. 6. Method according to claim 1 or 2, characterized in that at least one surface treatment agent in step b) is a mixture of phosphoric acid esters of one or more phosphoric acid monoesters and/or one or more phosphoric acid diesters acid, and/or at least one monosubstituted succinic anhydride, consisting of succinic anhydride monosubstituted by a group selected from a linear, branched and aliphatic group having a total number of carbon atoms from at least C ₂ to C ₂₀ in the substituent, or a cyclic group having a total number of carbon atoms from at least C ₃ to C ₂₀ in the substituent; and/or added at stage c) bringing into contact in an amount of from 0.1 to 3% wt., preferably from 0.1 to 2% wt. and most preferably from 0.1 to 1.5% wt. relative to the total dry weight of the at least one calcium carbonate containing filler material from step a). 7. Method according to claim 1 or 2, characterized in that step c) of bringing into contact is carried out such that the total energy consumption when adding at least one surface treatment agent from step b) to at least one filler material, containing calcium carbonate, from stage a), is not more than 15 kWh/t, preferably from 2 to 15 kWh/t. 8. Method according to claim 1 or 2, characterized in that at least one surface treatment agent from step b) is added to at least one filler material containing calcium carbonate from step a), which is loaded into the Archimedean screw , for example in a screw conveyor. 9. The method according to claim 8, characterized in that the Archimedes screw is operated at an angle from 35 to 70°. 10. Method according to claim 8 or 9, characterized in that at least one surface treatment agent from step b) is added to at least one filler material containing calcium carbonate from step a) in the lower 1/3 of the Archimedes screw 11. Method according to claim 1 or 2, characterized in that stage c) of bringing into contact is carried out in a continuous or periodic mode. 12. Surface treated filler material containing a) at least one filler material containing calcium carbonate, which has i) volumetric median particle size d ₅₀ from 5 to 100 µm, ii) upper limit of size (d ₉₈ ) from 30 to 500 µm, b) a treated layer on the surface of at least one filler material containing calcium carbonate, which contains at least one surface treatment agent and/or reaction products thereof, wherein the surface treated filler material contains a treatment layer in an amount of from 0. 1 to 3% wt. relative to the total dry weight of at least one filler material containing calcium carbonate, wherein said surface-treated filler material has a residue on a 45-μm sieve, measured in accordance with ISO 787/7, of more than 0.5% by weight. relative to the total mass of the filler material with the treated surface. 13. A filler material with a treated surface according to claim 12, obtained by the method of producing a filler material with a treated surface according to any one of claims. 1-11. 14. A polymer product containing a filler material with a treated surface according to claim 12 or 13.