Pigment composition comprising

surface modified calcium carbonate and ground natural calcium carbonate

The present invention relates to an aqueous pigment composition comprising a blend of ground natural calcium carbonate (GNCC) and surface modified calcium carbonate (MCC). The invention further relates to a process for producing the inventive pigment composition and its use in paints and coatings.

Commonly used pigments in the field of paints and coatings include, for example, clay, mica, silica, talc, titanium dioxide or different types of calcium carbonate such as ground natural calcium carbonate or synthetic calcium carbonate and surface modified variants of the aforementioned calcium carbonates.

In case of opaque paints or coats, pigments providing for high opacity and high contrast are generally preferred. Further desired properties may include, for example, a high whiteness degree, a low yellowness degree and good matting properties.

In order to achieve these goals, high performance pigments (in particular titanium dioxide or surface modified calcium carbonate) are often required and corresponding paints or coatings must therefore be produced at high costs. Thus, there is a general need for more efficient pigments in terms of opacity, contrast and the like or a general need for alternative pigments which may be used in the production of paints and coatings at less costs.

In this respect, EP 2 684 916 Al discloses a process for producing surface modified calcium carbonate from a calcium carbonate containing mineral slurry in the presence of at least one water-soluble acid and carbon dioxide under stirring conditions. The surface modified calcium carbonate may be used as matting agent in paints and coatings. Likewise, EP 2 264 108 Al and EP 2 264 109 Al disclose processes for preparing surface modified calcium carbonate using strong and medium-strong to strong acids, respectively, and carbon dioxide. To further reduce the amount of surface modified calcium carbonate in carbonate- based pigment compositions, which is also expensive compared to conventional ground natural calcium carbonate, EP 3 085 742 Al proposes a blend of surface modified calcium carbonate comprising particles (MCC) and precipitated calcium carbonate comprising particles (PCC). The blend being in the form of an aqueous slurry or the corresponding dried pigment slurry may be used in paper, paper coating, tissue paper, digital photo paper, paints, coatings, adhesives, plastics, waste water treating or waste water treating agents.

As a further alternative, US 2014/0158022 Al discloses the use of kaolin/calcium carbonate blends in mineral compositions for use in paints and coatings. Said blend comprises kaolin, wherein between 88 and 98% of the particles should be smaller than 2 microns and only between 10 and 30% should be smaller than 0.2 microns, and calcium carbonate, wherein between 88 and 96% of the particles should be smaller than 2 microns and between 4 and 14% should be smaller than 0.2 microns.

However, there is still a continuous need for alternative pigments and pigment compositions providing better performance (e.g. in terms of opacity or contrast ratio, whiteness, yellowness or matting properties) or which may be produced at less costs. Such alternative pigments and corresponding compositions may be used, for example, as an enhancer for established high performance pigments, such as titanium dioxide. Accordingly, it is one object of the present invention to provide a pigment or a pigment composition having improved optical properties. In particular, it is an object of the present invention to provide a pigment or pigment composition with improved optical properties when applied in paints or coatings.

One particular aim is the provision of pigments, pigment compositions and corresponding paints or coatings providing improved opacity or improved contrast properties. Still another object may be seen in the provision of pigments, pigment compositions and corresponding paints or coatings which have improved properties in terms of yellowness (preferably reduced yellowness) and whiteness (preferably increased whiteness). Still another object of the present invention may be seen in the provision of pigments, pigment compositions and corresponding paints or coatings which may be produced at lower costs or which may be used at lower costs compared to

conventional (high performance) pigments. Therefore, another object may be seen in the provision of a pigment or pigment composition which may be used as an enhancer for known (high performance) pigments without negatively affecting the optical properties of the final product, for example in terms of opacity, contrast ratio, yellowness or matting properties.

Another particular aim may be seen in the provision of a pigment or a corresponding composition which may be used as a first pigment together with a known second

(high performance) pigment, thereby enhancing the optical properties of that known second pigment. It is thus another object of the present invention to reduce the overall consumption of and the costs for conventional (high performance) pigments while maintaining or improving the optical properties of corresponding paints and coatings.

The preparation of known pigments or pigment compositions for use in paints or coatings typically comes along with a low productivity and high energy consumption for drying the materials and it is thus highly energy and cost consuming. As a result, conventional pigment compositions are typically obtained in the form of aqueous suspensions comprising relatively high amounts of water. In turn, existing pigment compositions having a high solids content typically have a high viscosity. Another object of the present invention may therefore be seen in the provision of pigments or pigment compositions with high solids content at acceptable or low viscosity.

The foregoing and other problems may be solved by the subject-matter as defined herein in the independent claims.

A first aspect of the present invention relates to an aqueous pigment composition comprising:

(i) ground natural calcium carbonate (GNCC) having a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter dm of 5 μιη or less; and

(ϋ) surface modified calcium carbonate (MCC) being a reaction product of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) treated with C0 ₂ and one or more H ₃ 0 ⁺ ion donors, wherein the CO2 is formed in situ by the H ₃ 0 ⁺ ion donors treatment and/or is supplied from an external source, said surface modified calcium carbonate (MCC) having a volume median particle diameter dso of 1.3 μιη or less and a volume-based particle diameter dm of 10 μι οΓ less; characterized in that the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition at a ratio of from 95 :5 to 5 :95, based on dry weights, wherein the aqueous pigment composition has a total solids content of from 50 to 85 wt%, based on the total weight of the aqueous pigment composition.

The inventors surprisingly found that an aqueous pigment composition comprising a blend of two calcium carbonate pigments, wherein the first pigment is a ground natural calcium carbonate (GNCC) and the second pigment is a surface modified calcium carbonate (MCC), provides improved optical properties, e.g. in terms of contrast ratio, yellowness and matting properties, compared to conventional ground calcium carbonate. Both calcium carbonate pigments contained in the blend have a specific particle size distribution: The ground natural calcium carbonate (GNCC) has a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter i¾ ₈ of 5 μιη or less and the surface modified calcium carbonate (MCC) has a volume median particle diameter dso of 1.3 μιη or less and a volume-based particle diameter dw of 10 μιη or less. According to the present invention, the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition at a ratio of from 95 :5 to 5 :95. The inventors further discovered that the aqueous compositions of the present invention provide good optical properties when used in paint and coating composition also at high solids content and good viscosity. The aqueous pigment composition has a total solids content of from 50 to 85 wt%, based on the total weight of the aqueous pigment composition. Surprisingly, the inventive pigment composition may be used as a titanium dioxide enhancer allowing for a reduction of the titanium dioxide consumption while, at the same time, satisfactory or even improved optical properties may be achieved (e.g. contrast ratio, yellowness and matting properties). Therefore, another aspect of the present invention relates to a process for preparing the inventive aqueous pigment composition, the process comprising the following steps:

(a) providing an aqueous suspension of ground natural calcium carbonate (GNCC) having a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter dw of 5 μιη or less;

(b) providing an aqueous suspension of surface modified calcium

carbonate (MCC) being a reaction product of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) treated with C0 ₂ and one or more H ₃ 0 ⁺ ion donors, wherein the CO2 is formed in situ by the H ₃ 0 ⁺ ion donors treatment and/or is supplied from an external source, said surface modified calcium carbonate (MCC) having a volume median particle diameter dso of 1.3 μιη or less and a volume-based particle diameter dw of 10 μιη or less;

(c) contacting the aqueous suspension provided in step (a) and the

aqueous suspension provided in step (b) to obtain an aqueous pigment composition comprising ground natural calcium carbonate (GNCC) and surface modified calcium carbonate (MCC); and

(d) optionally, adjusting the solids content of the aqueous pigment

composition of step (c);

characterized in that the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition at a ratio of from 95 :5 to 5 :95, based on dry weights, wherein the aqueous pigment composition has a total solids content of from 50 to 85 wt%, based on the total weight of the aqueous pigment composition.

Still another aspect of the present invention relates to the use of the inventive aqueous pigment composition in paints or coatings. Still another aspect of the present invention relates to the use of the inventive aqueous pigment as titanium dioxide enhancer. Still another aspect of the present invention relates to a paint or coating comprising the aqueous pigment composition.

The following terms used throughout the present application shall have the meanings set forth hereinafter:

The term "ground natural calcium carbonate" (GNCC) as used herein refers to a particulate material obtained from natural calcium carbonate-containing minerals (e.g. chalk, limestone, marble or dolomite) which has been processed in a wet and/or dry comminution step, such as crushing and/or grinding, and optionally has been subjected to further steps such as screening and/or fractionation, for example, by a cyclone or classifier.

A "precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment or by precipitation of a calcium- and a carbonate source in water. Additionally, precipitated calcium carbonate can also be the product of introducing calcium- and carbonate salts, for example calcium chloride and sodium carbonate, in an aqueous environment. PCC may have a vateritic, calcitic or aragonitic crystalline form. PCCs are described, for example, in EP 2 447 213 Al, EP 2 524 898 Al, EP 2 371 766 Al, EP 2 840 065 Al, or WO 2013/142473 Al. A "surface modified calcium carbonate" according to the present invention is a reaction product of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) treated with CO2 and one or more H ₃ 0 ⁺ ion donors, wherein the CO2 is formed in situ by the H ₃ 0 ⁺ ion donors treatment and/or is supplied from an external source. A H ₃ 0 ⁺ ion donor in the context of the present invention is a Bronsted acid and/or an acid salt.

The term "particulate" in the meaning of the present application refers to materials composed of a plurality of particles. Said plurality of particles may be defined, for example, by its particle size distribution (i¾8, dso etc.).

The "particle size" of surface modified calcium carbonate herein is described as volume-based particle size distribution d _x . Therein, the value d _x represents the diameter relative to which x % by volume of the particles have diameters less than d _x . This means that, for example, the 20 value is the particle size at which 20 vol% of all particles are smaller than that particle size. The 50 value is thus the volume median particle size, i.e. 50 vol% of all particles are smaller than that particle size and the 8 value, referred to as volume topcut, is the particle size at which 98 vol% of all particles are smaller than that particle size.

The "particle size" of particulate materials other than surface modified calcium carbonate (e.g. ground natural calcium carbonate) herein is described by a weight- based distribution of particle sizes d _x . Therein, the value d _x represents the diameter relative to which x % by weight of the particles have diameters less than d _x . This means that, for example, the 20 value is the particle size at which 20 wt% of all particles are smaller than that particle size. The 50 value is thus the weight median particle size, i.e. 50 wt% of all particles are smaller than that particle size and the 8 value, referred to as weight topcut, is the particle size at which 98 wt% of all particles are smaller than that particle size.

Throughout the present document, the "specific surface area" (in m ² /g) of surface modified calcium carbonate or other materials is determined using the BET method (using nitrogen as adsorbing gas).

For the purpose of the present invention, the "porosity" or "pore volume" refers to the intra-particle intruded specific pore volume.

In the context of the present invention, the term "pore" is to be understood as describing the space that is found between and/or within particles, i.e. that is formed by the particles as they pack together under nearest neighbour contact (interparticle pores), such as in a powder or a compact and/or the void space within porous particles (intraparticle pores), and that allows the passage of liquids under pressure when saturated by the liquid and/or supports absorption of surface wetting liquids.

A "suspension" or "slurry" in the meaning of the present invention refers to a mixture comprising at least one insoluble solid in a liquid medium, for example water, and optionally further additives, and usually contains large amounts of solids and, thus, is more viscous (higher viscosity) and can have a higher density than the liquid medium from which it is formed.

For the purpose of the present invention, the term "viscosity" refers to the Brookfield viscosity.

"Water-insoluble" materials are defined as materials which, when 100 g of said material is mixed with 100 g deionized water and filtered on a filter having a 0.2 μιη pore size at 20 °C under atmospheric pressure to recover the liquid filtrate, provide less than or equal to 1 g of recovered solid material following evaporation at 95 to 100 °C of 100 g of said liquid filtrate at ambient pressure. "Water-soluble" materials are thus defined as materials which, when 100 g of said material is mixed with 100 g deionized water and filtered on a filter having a 0.2 μιη pore size at 20 °C under atmospheric pressure to recover the liquid filtrate, provide more than 1 g of recovered solid material following evaporation at 95 to 100 °C of 100 g of said liquid filtrate at ambient pressure. The term "solid" according to the present invention refers to a material that is solid under standard ambient temperature and pressure (SATP) which refers to a temperature of 298.15 K (25 °C) and an absolute pressure of exactly 1 bar. The solid may be in the form of a powder, tablet, granules, flakes etc. Accordingly, the term "liquid medium" refers to a material that is liquid under standard ambient temperature and pressure (SATP) which refers to a temperature of 298.15 K (25 °C) and an absolute pressure of exactly 1 bar.

A "titanium dioxide enhancer" in the meaning of the present invention is a pigment which, when used together with a titanium dioxide pigment, is capable of improving the optical properties of titanium dioxide. Preferably, the aforementioned improved optical properties include opacity, contrast ratio, matting properties or any combinations thereof.

Where an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an" or "the", this includes a plural of that noun unless anything else is specifically stated. Where the term "comprising" is used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term "consisting of is considered to be a preferred embodiment of the term "comprising". If hereinafter a group is defined to comprise at least a certain number of

embodiments, this is also to be understood to disclose a group, which preferably consists only of these embodiments.

Terms like "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. This, for example, means that, unless the context clearly dictates otherwise, the term "obtained" does not mean to indicate that, for example, an embodiment must be obtained by, for example, the sequence of steps following the term "obtained" though such a limited understanding is always included by the terms "obtained" or "defined" as a preferred embodiment. Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined hereinabove.

In the following, preferred embodiments of the aqueous pigment composition according to the present invention will be described. It is to be understood that these details and embodiments also apply to the process for preparing the inventive composition and its use as titanium dioxide enhancer, and its use in paints and coatings.

In a first embodiment of the present invention, the ground natural calcium carbonate (GNCC) of the pigment composition has:

(i) a weight median particle diameter dso in the range of from 0.05 to 1.5 μιη, preferably from 0.1 to 1.3 μιη, more preferably from 0.2 to 1 μιη, and most preferably from 0.5 to 0.9 μιη; a weight-based particle diameter dm in the range of from 3 to 5 μιη, preferably from 3.2 to 4.8 μιη, more preferably from 3.5 to 4.5 μιη, and most preferably from 3.8 to 4.2 μιη; and/or

a weight-based particle diameter ratio dwldso of 3 or higher, preferably 4 or higher, and most preferably in the range of from 4.5 to 6.5.

In another embodiment of the present invention, the surface modified calcium carbonate (MCC) of the pigment composition has:

(i) a volume median particle diameter dso in the range of from 0.05 to 1.3 μιη, preferably from 0.1 to 1 μιη, more preferably from 0.2 to 0.9 μιη, and most preferably from 0.3 to 0.7 μιη;

(ii) a volume-based particle diameter dm in the range of from 3 to 10 μιη, preferably from 3.5 to 8 μιη, more preferably from 4 to 6 μιη, and most preferably from 4.5 to 5.5 μιη; and/or

(iii) a volume-based particle diameter ratio dwldso of 10 or less, preferably 6 or less, and most preferably in the range of from 3.5 to 5.5.

In still another embodiment of the present invention, the surface modified calcium carbonate (MCC) of the pigment composition has a specific surface area in the range of from 20 to 200 m ² /g, preferably from 25 to 100 m ² /g, and most preferably from 30 to 50 m ² /g, measured using nitrogen and the BET method according to

ISO 9277:2010.

In still another embodiment of the present invention, the surface modified calcium carbonate (MCC) of the pigment composition has an intra-particle intruded specific pore volume in the range of from 0.08 to 1.80 cm ³ /g, preferably from 0.10 to 1.50 cm ³ /g, and most preferably from 0.18 to 1.30 cm ³ /g, calculated from mercury porosimetry measurement. In another embodiment of the present invention, the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the inventive aqueous pigment composition at a ratio of from 90: 10 to 30:70, and preferably from 88: 12 to 60:40, for example at a ratio of 85 : 15, each based on dry weights.

In another embodiment of the present invention, the inventive aqueous pigment composition has a total solids content of from 55 to 80 wt%, preferably from 60 to 78 wt%, and most preferably from 65 to 75 wt%, each based on the total weight of the aqueous pigment composition.

In one embodiment, the ground natural calcium carbonate (GNCC) of step (a) of the inventive process has:

(i) a weight median particle diameter dso in the range of from 0.05 to 1.5 μιη, preferably from 0.1 to 1.3 μιη, more preferably from 0.2 to 1 μιη, and most preferably from 0.5 to 0.9 μιη;

(ii) a weight-based particle diameter dw in the range of from 3 to 5 μιη, preferably from 3.2 to 4.8 μιη, more preferably from 3.5 to 4.5 μιη, and most preferably from 3.8 to 4.2 μιη; and/or

(iii) a weight-based particle diameter ratio d^ldso of 3 or higher, preferably 4 or higher, and most preferably in the range of from 4.5 to 6.5.

In another embodiment, the surface modified calcium carbonate (MCC) of step (b) of the inventive process has:

(i) a volume median particle diameter dso in the range of from 0.05 to 1.3 μιη, preferably from 0.1 to 1 μιη, more preferably from 0.2 to 0.9 μιη, and most preferably from 0.3 to 0.7 μιη; (ii) a volume-based particle diameter 98 in the range of from 3 to 10 μιη, preferably from 3.5 to 8 μιη, more preferably from 4 to 6 μιη, and most preferably from 4.5 to 5.5 μιη; and/or

(iii) a volume-based particle diameter ratio dwldso of 10 or less, preferably 6 or less, and most preferably in the range of from 3.5 to 5.5.

In still another embodiment, the surface modified calcium carbonate (MCC) of step (b) of the inventive process has a specific surface area in the range of from 20 to 200 m ² /g, preferably from 25 to 100 m ² /g, and most preferably from 30 to 50 m ² /g, measured using nitrogen and the BET method according to ISO 9277:2010.

In still another embodiment, the surface modified calcium carbonate (MCC) of step (b) of the inventive process has an intra-particle intruded specific pore volume in the range of from 0.08 to 1.80 cm ³ /g, preferably from 0.10 to 1.50 cm ³ /g, and most preferably from 0.18 to 1.30 cm ³ /g, calculated from mercury porosimetry

measurement.

In another embodiment, the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition of the inventive process at a ratio of from 90: 10 to 30:70, preferably from 88: 12 to 60:40, for example at a ratio of 85 : 15, each based on dry weights.

In still another embodiment, the aqueous pigment composition of the inventive process has a total solids content of from 55 to 80 wt%, preferably from 60 to 78 wt%, and most preferably from 65 to 75 wt%, each based on the total weight of the aqueous pigment composition. (A) Ground natural calcium carbonate (GNCC)

The aqueous pigment composition of the present invention comprises ground natural calcium carbonate (GNCC) which may be obtained, for example, in a wet and/or dry comminution step, such as crushing and/or grinding, from natural calcium carbonate- containing minerals (e.g. chalk, limestone, marble or dolomite).

In one embodiment of the present invention, the ground natural calcium carbonate (GNCC) is a ground calcium carbonate-containing mineral, preferably the calcium carbonate-containing mineral is selected from the group consisting of chalk, limestone, marble, dolomite and mixtures thereof. More preferably, the calcium carbonate-containing mineral is chalk, limestone or marble, even more preferably limestone or marble, and most preferably marble.

It is appreciated that the ground natural calcium carbonate (GNCC) can be one or a mixture of different kinds of ground natural calcium carbonate(s).

In one embodiment of the present invention, the ground natural calcium carbonate (GNCC) comprises, preferably consists of, one kind of ground natural calcium carbonate. Alternatively, the ground natural calcium carbonate (GNCC) comprises, preferably consists of, two or more kinds of ground natural calcium carbonates. For example, the ground natural calcium carbonate (GNCC) comprises, preferably consists of, two or three kinds of ground natural calcium carbonates. Preferably, the surface modified calcium carbonate comprises, more preferably consists of, one kind of ground natural calcium carbonate.

The ground natural calcium carbonate (GNCC) used in the pigment composition of the present invention has a specific particle size distribution, wherein the weight median particle diameter dso is 1.5 μιη or less and the weight-based particle diameter ύ? 8 is 5 μιη or less. The ground natural calcium carbonate (GNCC) used in the inventive pigment composition may also be referred to as ultrafme ground natural calcium carbonate (UF-GNCC).

In general, ground natural calcium carbonate (GNCC) having a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter dw of 5 μιη or less as used in the present invention may be obtained by any suitable grinding method known in the art, wherein dry grinding, wet grinding or both, a combination of wet grinding and dry grinding steps may be used.

According to one embodiment, the ground natural calcium carbonate (GNCC) is a wet-ground natural calcium carbonate. In another embodiment, the ground natural calcium carbonate (GNCC) is a dry-ground natural calcium carbonate.

The grinding step can be carried out with any conventional grinding device, for example, under conditions such that refinement predominantly results from impacts with a secondary body, i.e. in one or more of a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man. The grinding step may also be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled man. In one embodiment, grinding is carried out in a vertical or horizontal ball mill, preferably in a vertical ball mill. Such vertical and horizontal ball mills usually consist of a vertically or horizontally arranged, cylindrical grinding chamber comprising an axially fast rotating agitator shaft being equipped with a plurality of paddles and/or stirring discs, such as described for example in EP 0 607 840 Al .

It is to be noted that grinding of the calcium carbonate-containing mineral may be carried out by using at least one of the aforementioned grinding methods or devices. However, it is also possible to use a combination of any of the foregoing methods or a series of any of the aforementioned grinding devices.

Subsequent to the grinding step, the ground calcium carbonate-containing mineral may, optionally, be divided into two or more fractions, each having different particle distributions, by use of a classifying step. A classifying step in general serves to divide a feed fraction having a certain particle size distribution into a coarse fraction, which may be subjected to another grinding cycle, and a fine fraction, which may be used as the final product. For this purpose, screening devices as well as gravity-based devices, such as centrifuges or cyclones (e.g. hydrocyclones) and any combination of the aforementioned devices may be used.

As already indicated above, the ground natural calcium carbonate (GNCC) used in the pigment composition of the present invention is an ultrafme ground natural calcium carbonate (UF-GNCC) having a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter dw of 5 μιη or less.

The particle size distribution of the ground natural calcium carbonate (GNCC), defined in terms of a specific weight-based dso (median particle size) or dw (topcut), may have an influence on the desired optical properties of the inventive pigment composition and paints or coatings prepared thereof, for example in terms of opacity, contrast ratio, yellowness or matting properties. The particle size distribution may also have an influence one the viscosity of the inventive pigment composition, which is an aqueous composition.

In some embodiments of the present invention, the ground natural calcium carbonate (GNCC) may thus have a weight median particle diameter dso in the range of from 0.05 to 1.5 μιη, preferably from 0.1 to 1.3 μιη, more preferably from 0.2 to 1 μιη, and most preferably from 0.5 to 0.9 μιη.

Additionally or alternatively, the ground natural calcium carbonate (GNCC) may have a weight-based particle diameter i¾ ₈ in the range of from 3 to 5 μιη, preferably from 3.2 to 4.8 μιη, more preferably from 3.5 to 4.5 μιη, and most preferably from 3.8 to 4.2 μιη.

As indicated above, both dso and i¾8 may influence the desired optical properties of the inventive pigment composition, paints or coatings prepared thereof, or the viscosity of the inventive pigment composition. It may therefore be appropriate, additionally or alternatively, to define the particle size distribution of the ground natural calcium carbonate (GNCC) in terms of a weight-based particle diameter ratio d9s/d5o. Said ratio is indicative for the steepness of the particle size distribution meaning that, for example, a high value represents a broad distribution curve.

Therefore, in some embodiments, the ground natural calcium carbonate (GNCC) may have a weight-based particle diameter ratio dwldso of 3 or higher, preferably 4 or higher, and most preferably in the range of from 4.5 to 6.

Additionally or alternatively, the ground natural calcium carbonate (GNCC) may be characterized by its specific surface area which may also have an influence on the desired optical properties. Therefore, in one embodiment, the ground natural calcium carbonate (GNCC) has a specific surface area of from 1 to 75 m ² /g, preferably from 2 to 50 m ² /g, more preferably from 5 to 25 m ² /g, even more preferably from 8 to 20 m ² /g, and most preferably from 9 to 15 m ² /g, measured using nitrogen and the BET method according to ISO 9277:2010.

Optionally, the ground natural calcium carbonate (GNCC) used in the inventive aqueous pigment composition may be surface-treated with any suitable

hydrophobizing agent known to the skilled person, for example fatty acids having from 6 to 24 chain carbon atoms such as stearic acid. However, in a preferred embodiment, the ground natural calcium carbonate (GNCC) is untreated.

Where the ground natural calcium carbonate (GNCC, more precisely UF-GNCC) is used in the form of an aqueous suspension or slurry, said suspension or slurry may optionally be stabilized by a dispersant. Conventional dispersants known to the skilled person can be used. A preferred dispersant is comprised of polyacrylic acids and/or carboxymethylcelluloses. In one embodiment, the dispersant is a polyacrylate- based dispersant, including partially or fully neutralized polyacrylates.

(B) Surface modified calcium carbonate

The aqueous pigment composition of the present invention further comprises surface modified calcium carbonate (MCC). Surface modified calcium carbonate may also be referred to as functionalized calcium carbonate (FCC) or surface-reacted calcium carbonate (SRCC).

It is appreciated that the surface modified calcium carbonate (MCC) can be one or a mixture of different kinds of surface modified calcium carbonate(s). In one embodiment of the present invention, the surface modified calcium carbonate (MCC) comprises, preferably consists of, one kind of surface modified calcium carbonate. Alternatively, the surface modified calcium carbonate (MCC) comprises, preferably consists of, two or more kinds of surface modified calcium carbonates. For example, the surface modified calcium carbonate (MCC) comprises, preferably consists of, two or three kinds of surface modified calcium carbonates. Preferably, the surface modified calcium carbonate (MCC) comprises, more preferably consists of, one kind of surface modified calcium carbonate.

The surface modified calcium carbonate (MCC) is a reaction product of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) treated with C0 ₂ and one or more H ₃ 0 ⁺ ion donors, wherein the CO2 is formed in situ by the H ₃ 0 ⁺ ion donors treatment and/or is supplied from an external source. Because of the reaction of ground natural calcium carbonate or precipitated calcium carbonate with CO2 and the one or more H ₃ 0 ⁺ ion donors, surface modified calcium carbonate may comprise GNCC or PCC and at least one water-insoluble calcium salt.

In a preferred embodiment of the present invention, said surface modified calcium carbonate (MCC) comprises ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) and at least one water-insoluble calcium salt which is present on at least part of the surface of said GNCC and/or PCC. More preferably, said surface modified calcium carbonate (MCC) comprises a total amount of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) in the range of from 1 to 50 wt%, based on the total dry weight of the surface modified calcium carbonate (MCC).

An H ₃ 0 ⁺ ion donor in the context of the present invention is a Bronsted acid and/or an acid salt. In a preferred embodiment of the invention, the surface modified calcium carbonate (MCC) is obtained by a process comprising the steps of:

(a) providing a suspension of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);

(b) adding at least one acid having a pKa value of 0 or less at 20 °C, or having a pKa value from 0 to 2.5 at 20 °C to the suspension provided in step (a); and

(c) treating the suspension provided in step (a) with C0 ₂ before, during or after step (b).

According to another embodiment, the surface modified calcium carbonate (MCC) is obtained by a process comprising the steps of:

(a) providing a ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);

(b) providing at least one water-soluble acid;

(c) providing gaseous C0 ₂ ; and

(d) contacting said GNCC or PCC provided in step (a), the at least one acid provided in step (b) and the gaseous CO2 provided in step (c); characterized in that

(i) the at least one acid provided in step (b) has a pKa of greater than 2.5 and less than or equal to 7 at 20 °C, associated with the ionisation of its first available hydrogen, and a

corresponding anion is formed on loss of this first available hydrogen capable of forming a water-soluble calcium salt; and (ii) following contacting the at least one water-soluble acid

provided in step (b) and the GNCC or PCC provided in step (a), at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pKa of greater than 7 at 20 °C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water- insoluble calcium salts, is additionally provided. The source of calcium carbonate, e.g. ground natural calcium carbonate (GNCC), preferably is selected from calcium carbonate-containing minerals selected from the group comprising marble, chalk, limestone and mixtures thereof. Natural calcium carbonate may comprise further naturally occurring components such as magnesium carbonate, alumino silicate etc. According to one embodiment, natural calcium carbonate, such as GNCC, comprises aragonitic, vateritic or calcitic mineralogical crystal forms of calcium carbonate or mixtures thereof.

In general, the grinding of ground natural calcium carbonate may be performed in a dry or wet grinding process and may be carried out with any conventional grinding device, for example, under conditions such that comminution predominantly results from impacts with a secondary body, i.e. in one or more of a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulverizer, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled person. In case the ground natural calcium carbonate comprises wet ground calcium carbonate, the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled person. The wet processed ground natural calcium carbonate thus obtained may be washed and dewatered by well-known processes, e.g. by flocculation, filtration or forced evaporation prior to drying. The subsequent step of drying (if necessary) may be carried out in a single step such as spray drying, or in at least two steps. It is also common that such a mineral material undergoes a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities. As already indicated hereinabove, a precipitated calcium carbonate (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following a reaction of CO2 and calcium hydroxide in an aqueous environment or by precipitation of calcium and carbonate ions, for example CaCl ₂ and Na ₂ C0 ₃ , out of solution. Further possible ways of producing PCC are the lime soda process, or the Solvay process in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms. Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite is an orthorhombic structure with typical crystal habits of twinned hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved bladed, steep pyramidal, chisel shaped crystals, branching tree, and coral or worm-like form. Vaterite belongs to the hexagonal crystal system. The obtained aqueous PCC slurry can be mechanically dewatered and dried.

According to one embodiment of the present invention, the precipitated calcium carbonate comprises aragonitic, vateritic or calcitic mineralogical crystal forms of calcium carbonate or mixtures thereof.

Precipitated calcium carbonate may be ground prior to the treatment with C0 ₂ and at least one H ₃ 0 ⁺ ion donor by the same means as used for grinding natural calcium carbonate and described above.

According to one embodiment of the present invention, the natural or precipitated calcium carbonate used for preparing the surface modified calcium carbonate (MCC) is in form of particles having a weight median particle size 50 of from 0.05 to 10.0 μιη, preferably from 0.2 to 5.0 μιη, more preferably from 0.4 to 3.0 μιη, most preferably from 0.6 to 1.2 μιη, and especially 0.7 μιη. According to a further embodiment of the present invention, the natural or precipitated calcium carbonate is in form of particles having a weight-based topcut particle size dm of from 0.15 to 55 μιη, preferably from 1 to 40 μιη, more preferably from 2 to 25 μιη, most preferably from 3 to 15 μιη, and especially 4 μιη.

The natural or precipitated calcium carbonate for preparing the surface modified calcium carbonate (MCC) may be used dry or suspended in water. Preferably, a corresponding aqueous slurry has a content of natural or precipitated calcium carbonate within the range of from 1 to 90 wt%, more preferably from 3 to 60 wt%, even more preferably from 5 to 40 wt%, and most preferably from 10 to 25 wt%, based on the total weight of said slurry.

The one or more H ₃ 0 ⁺ ion donor used for the preparation of surface modified calcium carbonate may be any strong acid, medium-strong acid, or weak acid, or mixtures thereof, generating H ₃ 0 ⁺ ions under the preparation conditions. According to the present invention, the at least one H ₃ 0 ⁺ ion donor can also be an acid salt, generating H ₃ 0 ⁺ ions under the preparation conditions.

According to one embodiment, the at least one H ₃ 0 ⁺ ion donor is a strong acid having a pKa of 0 or less at 20 °C. According to another embodiment, the at least one H ₃ 0 ⁺ ion donor is a medium- strong acid having a pKa value from 0 to 2.5 at 20 °C. If the pKa at 20 °C is 0 or less, the acid is preferably selected from sulphuric acid, hydrochloric acid, or mixtures thereof. If the pKa at 20 °C is from 0 to 2.5, the H ₃ 0 ⁺ ion donor is preferably selected from H2SO3, H3PO4, oxalic acid, or mixtures thereof. The at least one H ₃ 0 ⁺ ion donor can also be an acid salt, for example, HSC ^" or Η ₂ Ρ0 ₄ ^~ , being at least partially neutralized by a corresponding cation such as Li ⁺ , Na ⁺ or K ⁺ , or HPO4 ^2" , being at least partially neutralized by a corresponding cation such as Li ⁺ , Na ⁺ ' K ⁺ , Mg ²⁺ or Ca ²⁺ . The at least one H ₃ 0 ⁺ ion donor can also be a mixture of one or more acids and one or more acid salts.

According to still another embodiment, the at least one H ₃ 0 ⁺ ion donor is a weak acid having a pKa value of greater than 2.5 and less than or equal to 7, when measured at 20 °C, associated with the ionisation of the first available hydrogen, and having a corresponding anion, which is capable of forming water-soluble calcium salts. Subsequently, at least one water-soluble salt, which in the case of a hydrogen- containing salt has a pKa of greater than 7, when measured at 20 °C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided. According to a more preferred embodiment, the weak acid has a pKa value from greater than 2.5 to 5 at 20 °C, and more preferably the weak acid is selected from the group consisting of acetic acid, formic acid, propanoic acid and mixtures thereof. Exemplary cations of said water-soluble salt are selected from the group consisting of potassium, sodium, lithium and mixtures thereof. In a more preferred embodiment, said cation is sodium or potassium. Exemplary anions of said water-soluble salt are selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, oxalate, silicate, mixtures thereof and hydrates thereof. In a more preferred embodiment, said anion is selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. In a most preferred embodiment, said anion is selected from the group consisting of dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. Water-soluble salt addition may be performed dropwise or in one step. In the case of dropwise addition, this addition preferably takes place within a time period of 10 min. It is more preferred to add said salt in one step.

According to one embodiment of the present invention, the at least one H ₃ 0 ⁺ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid and mixtures thereof. Preferably the at least one H ₃ 0 ⁺ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, H2PO4 ^" , being at least partially neutralized by a corresponding cation such as Li ⁺ , Na ⁺ or K ⁺ , HPC ^2- , being at least partially neutralized by a corresponding cation such as Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ or Ca ²⁺ and mixtures thereof, more preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, or mixtures thereof. A particularly preferred H ₃ 0 ⁺ ion donor is phosphoric acid.

The one or more H ₃ 0 ⁺ ion donor can be added to the suspension as a concentrated solution or a more diluted solution. Preferably, the molar ratio of the H ₃ 0 ⁺ ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1 and most preferably from 0.1 to 0.58.

In another preferred embodiment, the at least one H ₃ 0 ⁺ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid and mixtures thereof, wherein the molar ratio of the H ₃ 0 ⁺ ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1 and most preferably from 0.1 to 0.58. In a particularly preferred embodiment, the at least one H ₃ 0 ⁺ ion donor is a mixture of phosphoric acid and citric acid, more preferably the molar ratio of the H ₃ 0 ⁺ ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1 and most preferably from 0.1 to 0.58.

As already indicated hereinabove, the treatment of GNCC or PCC with the at least one H ₃ 0 ⁺ ion donor and C0 ₂ may lead to the formation of at least one water- insoluble calcium salt. Therefore, surface modified calcium carbonate (MCC) may comprise GNCC and/or PCC and at least one water-insoluble calcium salt other than calcium carbonate. In one embodiment, said at least one water-insoluble calcium salt is present on at least part of the surface of said GNCC or PCC.

The use of phosphoric acid, H2PO4 ^" or HPO4 ^2" as the H ₃ 0 ⁺ ion donor may lead to the formation of hydroxylapatite. Therefore, in a preferred embodiment, the at least one water-insoluble calcium salt is hydroxylapatite.

In a similar manner, the use of other H ₃ 0 ⁺ ion donors may lead to the formation of corresponding water-insoluble calcium salts other than calcium carbonate on at least part of the surface of the surface modified calcium carbonate. In one embodiment, the at least one water-insoluble calcium salt is thus selected from the group consisting of octacalcium phosphate, hydroxylapatite, chlorapatite, fluorapatite, carbonate apatite and mixtures thereof. It is also possible to add the H ₃ 0 ⁺ ion donor to the water before the natural or precipitated calcium carbonate is suspended. In a next step, the natural or precipitated calcium carbonate is treated with C0 ₂ . If a strong acid such as sulphuric acid or hydrochloric acid is used for the H ₃ 0 ⁺ ion donor treatment of the natural or precipitated calcium carbonate, the CO2 is automatically formed. Alternatively or additionally, the CO2 can be supplied from an external source.

H ₃ 0 ⁺ ion donor treatment and treatment with CO2 can be carried out simultaneously which is the case when a strong or medium-strong acid is used. It is also possible to carry out H ₃ 0 ⁺ ion donor treatment first, e.g. with a medium strong acid having a pKa in the range of 0 to 2.5 at 20 °C, wherein CO2 is formed in situ, and thus, the CO2 treatment will automatically be carried out simultaneously with the H ₃ 0 ⁺ ion donor treatment, followed by the additional treatment with CO2 supplied from an external source. Preferably, the concentration of gaseous CO2 in the suspension is, in terms of volume, such that the ratio (volume of suspension): (volume of gaseous CO2) is from 1 :0.05 to 1 :20, even more preferably 1 :0.05 to 1 :5.

In a preferred embodiment, the H ₃ 0 ⁺ ion donor treatment step and/or the CO2 treatment step are repeated at least once, more preferably several times. According to one embodiment, the at least one H ₃ 0 ⁺ ion donor is added over a time period of at least about 5 min, preferably at least about 10 min, typically from about 10 to about 20 min, more preferably about 30 min, even more preferably about 45 min, and sometimes about 1 h or more.

Subsequent to the H ₃ 0 ⁺ ion donor treatment and CO2 treatment, the pH of the aqueous suspension, measured at 20 °C, naturally reaches a value of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5, thereby preparing the surface modified natural or precipitated calcium carbonate as an aqueous suspension having a pH of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5.

Further details on the preparation of surface modified natural calcium carbonate are disclosed in WO 00/39222 Al, WO 2004/083316 Al, WO 2005/121257 A2, WO 2009/074492 Al, EP 2 264 108 Al, EP 2 264 109 Al and

US 2004/0020410 Al, the content of these references herewith being included in the present application.

Similarly, surface reacted precipitated calcium carbonate may be obtained. As can be taken in detail from WO 2009/074492 Al, surface reacted precipitated calcium carbonate is obtained by contacting precipitated calcium carbonate with H ₃ 0 ⁺ ions and with anions being solubilized in an aqueous medium and being capable of forming water-insoluble calcium salts, in an aqueous medium to form a slurry of surface reacted precipitated calcium carbonate, wherein said surface reacted precipitated calcium carbonate comprises an insoluble, at least partially crystalline calcium salt of said anion formed on the surface of at least part of the precipitated calcium carbonate.

Said solubilized calcium ions correspond to an excess of solubilized calcium ions relative to the solubilized calcium ions naturally generated on dissolution of precipitated calcium carbonate by H ₃ 0 ⁺ ions, where said H ₃ 0 ⁺ ions are provided solely in the form of a counter ion to the anion, i.e. via the addition of the anion in the form of an acid or non-calcium acid salt, and in absence of any further calcium ion or calcium ion generating source. Said excess solubilized calcium ions are preferably provided by the addition of a soluble neutral or acid calcium salt, or by the addition of an acid or a neutral or acid non-calcium salt which generates a soluble neutral or acid calcium salt in situ. Said H ₃ 0 ⁺ ions may be provided by the addition of an acid or an acid salt of said anion, or the addition of an acid or an acid salt which simultaneously serves to provide all or part of said excess solubilized calcium ions.

In a further preferred embodiment of the preparation of the surface reacted natural or precipitated calcium carbonate, the natural or precipitated calcium carbonate is reacted with the acid and/or the C0 ₂ in the presence of at least one compound selected from the group consisting of silicate, silica, aluminium hydroxide, earth alkali aluminate such as sodium or potassium aluminate, magnesium oxide, aluminium sulphate or mixtures thereof. Preferably, the at least one silicate is selected from an aluminium silicate, a calcium silicate, or an earth alkali metal silicate.

In another preferred embodiment, said at least one compound is aluminium sulphate hexadecahydrate. In a particularly preferred embodiment, said at least one compound is aluminium sulphate hexadecahydrate, wherein the at least one H ₃ 0 ⁺ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid and mixtures thereof, more preferably the molar ratio of said H ₃ 0 ⁺ ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1 and most preferably from 0.1 to 0.58.

The foregoing components can be added to an aqueous suspension comprising the natural or precipitated calcium carbonate before adding the acid and/or CO2. Alternatively, the foregoing components can be added to the aqueous suspension of natural or precipitated calcium carbonate while the reaction of natural or precipitated calcium carbonate with an acid and CO2 has already started. Further details about the preparation of the surface reacted natural or precipitated calcium carbonate in the presence of at least one silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate component(s) are disclosed in WO 2004/083316 Al, the content of this reference herewith being included in the present application. The surface modified calcium carbonate can be kept in suspension, optionally further stabilized by a dispersant. Conventional dispersants known to the skilled person can be used. A preferred dispersant is comprised of polyacrylic acids and/or

carboxymethylcelluloses. In one embodiment, the dispersant is a polyacrylate-based dispersant, including partially or fully neutralized polyacrylates.

Alternatively, the aqueous suspension described above can be dried, thereby obtaining the solid (i.e. dry or containing as little water that it is not in a fluid form) surface reacted natural or precipitated calcium carbonate in the form of granules or a powder.

In a preferred embodiment, the surface modified calcium carbonate (MCC) has a specific surface area of from 20 to 200 m ² /g, preferably from 25 to 100 m ² /g, and most preferably from 30 to 50 m ² /g, measured using nitrogen and the BET method according to ISO 9277:2010. In a further embodiment, the surface modified calcium carbonate (MCC) has a specific surface area of 120 m ² /g or less, more preferably from 60 to 120 m ² /g, and most preferably from 70 to 105 m ² /g, measured using nitrogen and the BET method according to ISO 9277:2010. For example, the surface modified calcium carbonate (MCC) may have a specific surface area of from 75 to 100 m ² /g, measured using nitrogen and the BET method according to

ISO 9277:2010.

As in case of the ground natural calcium carbonate (GNCC), also the particle size distribution of the surface modified calcium carbonate (MCC), defined in terms of a specific volume-based dso (median particle size) or dw (topcut), may have an influence on the desired optical properties of the inventive pigment composition and paints or coatings prepared thereof, for example in terms of opacity, contrast ratio, yellowness or matting properties. The particle size distribution may also have an influence one the viscosity of the inventive pigment composition, which is an aqueous composition.

The surface modified calcium carbonate (MCC) is defined by a volume median particle diameter dso of 1.3 μιη or less. In some embodiments of the present invention, the surface modified calcium carbonate (MCC) may have a volume median particle diameter dso in the range of from 0.05 to 1.3 μιη, preferably from 0.1 to 1 μιη, more preferably from 0.2 to 0.9 μιη, and most preferably from 0.3 to 0.7 μιη. Furthermore, the surface modified calcium carbonate (MCC) is defined by a volume- based particle diameter dw of 10 μιη or less. In some embodiments of the present invention, the surface modified calcium carbonate (MCC) may have a volume-based particle diameter i¾ ₈ in the range of from 3 to 10 μιη, preferably from 3.5 to 8 μιη, more preferably from 4 to 6 μιη, and most preferably from 4.5 to 5.5 μιη.

As indicated above, both dso and i¾8 may influence the desired optical properties of the inventive pigment composition, paints or coatings prepared thereof, or the viscosity of the inventive pigment composition. It may therefore be appropriate, additionally or alternatively, to define the particle size distribution of the surface modified calcium carbonate (MCC) in terms of a volume-based particle diameter ratio dwldso. Said ratio is indicative for the steepness of the particle size distribution meaning that, for example, a low value represents a narrow distribution curve.

Therefore, in some embodiments, the surface modified calcium carbonate (MCC) may have a volume-based particle diameter ratio dwldso of 10 or less, preferably 6 or less, and most preferably in the range of from 3.5 to 5.5. According to another embodiment, the surface modified calcium carbonate (MCC) used in the present invention has an intra-particle intruded specific pore volume in the range of from 0.08 to 1.80 cm ³ /g, preferably from 0.10 to 1.50 cm ³ /g, and most preferably from 0.18 to 1.30 cm ³ /g, calculated from mercury porosimetry

measurement.

The intra-particle pore size of the surface modified calcium carbonate (MCC) preferably is in a range of from 0.03 to 1.3 μιη, more preferably from 0.04 to 1.1 μιη, and most preferably from 0.05 to 1.05 μιη, determined by mercury porosimetry measurement.

(C) Aqueous pigment composition

The aqueous pigment composition according to the present invention comprises:

(i) ground natural calcium carbonate (GNCC) having a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter dw of 5 μιη or less as disclosed hereinabove; and (ii) surface modified calcium carbonate (MCC) being a reaction product of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) treated with CO2 and one or more H ₃ 0 ⁺ ion donors, wherein the CO2 is formed in situ by the H ₃ 0 ⁺ ion donors treatment and/or is supplied from an external source, said surface modified calcium carbonate (MCC) having a volume median particle diameter dso of 1.3 μιη or less and a volume-based particle diameter ύ? 8 of 10 μιη or less as disclosed hereinabove.

The ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition at a ratio of from 95 :5 to 5 :95, based on dry weights. The aforementioned ratio may have an influence on the desired optical properties of the inventive pigment composition and paints or coatings prepared thereof, for example in terms of opacity, contrast ratio, yellowness or matting properties. The inventors surprisingly found that the aforementioned optical properties may be improved by using the inventive pigment composition, for example in comparison to conventional calcium carbonate pigments. The inventive pigment composition may also be used to enhance the optical properties of other high performance pigments, thereby reducing overall costs for the preparation of paints and coating at equal or improved performance.

In a particularly useful embodiment, the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition at a ratio of from 90: 10 to 30:70, preferably from 88: 12 to 60:40, for example at a ratio of 85 : 15, each based on dry weights. The ratio of ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) may be varied within the ranges disclosed herein, thereby ensuring good optical performance and adequate handleability (e.g. in terms of viscosity). The total solids content of the inventive pigment composition is relatively high and ranges from 50 to 85 wt%, based on the total weight of the composition. The ratio of the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) described herein above ensures good handleability (e.g. in terms of viscosity) within the specified solids content range.

In further embodiments, the aqueous pigment composition has a total solids content of from 55 to 80 wt%, preferably from 60 to 78 wt%, and most preferably from 65 to 75 wt%, each based on the total weight of the aqueous pigment composition.

In view of its good optical properties in combination with its good handleability (e.g. viscosity), the pigment composition of the present invention is particularly suitable for use in paints and coatings.

Therefore, one aspect of the present invention relates to the use of the inventive aqueous pigment composition in paints or coatings and to these paints or coatings as such comprising the inventive aqueous pigment composition. Due to its good optical properties at less costs, another aspect relates to the use of the inventive aqueous pigment composition as titanium dioxide enhancer.

Another aspect of the present invention relates to the use of the inventive aqueous pigment composition obtainable by the process described hereinafter in paints or coatings and to these paints or coatings as such comprising the inventive aqueous pigment composition obtainable by the process described hereinafter. Due to its good optical properties at less costs, another aspect relates to the use of the inventive aqueous pigment composition obtainable by the process described hereinafter as titanium dioxide enhancer. Still another aspect of the present invention relates to a pigment composition obtainable by drying the inventive aqueous pigment composition or the inventive aqueous pigment composition obtainable by the process described hereinafter.

(D) Process for preparing the aqueous pigment composition

The present invention further relates to a process for preparing the aqueous pigment composition disclosed hereinabove. The process comprises the steps of:

(a) providing an aqueous suspension of ground natural calcium carbonate (GNCC) having a weight median particle diameter dso of 1.5 μιη or less and a weight-based particle diameter dw of 5 μιη or less;

(b) providing an aqueous suspension of surface modified calcium

carbonate (MCC) being a reaction product of ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) treated with C0 ₂ and one or more H ₃ 0 ⁺ ion donors, wherein the CO2 is formed in situ by the H ₃ 0 ⁺ ion donors treatment and/or is supplied from an external source, said surface modified calcium carbonate (MCC) having a volume median particle diameter dso of 1.3 μιη or less and a volume-based particle diameter dw of 10 μιη or less;

(c) contacting the aqueous suspension provided in step (a) and the

aqueous suspension provided in step (b) to obtain an aqueous pigment composition comprising ground natural calcium carbonate (GNCC) and surface modified calcium carbonate (MCC); and

(d) optionally, adjusting the solids content of the aqueous pigment

composition of step (c);

characterized in that the ground natural calcium carbonate (GNCC) and the surface modified calcium carbonate (MCC) are present in the aqueous pigment composition at a ratio of from 95:5 to 5:95, based on dry weights, wherein the aqueous pigment composition has a total solids content of from 50 to 85 wt%, based on the total weight of the aqueous pigment composition. The skilled person will appreciate that the details and embodiments discussed hereinabove with respect to the ground natural calcium carbonate (GNCC), the surface modified calcium carbonate (MCC) and the details and embodiments concerning the aqueous pigment composition as such will apply accordingly to the instant process for preparing the inventive pigment composition.

In a further embodiment, the aqueous suspension of ground natural calcium carbonate (GNCC) provided in step (a) and/or the aqueous suspension of surface modified calcium carbonate (MCC) provided in step (b) of the inventive process has a solids content of at least 5 wt%, preferably from 5 to 85 wt%, more preferably from 10 to 50 wt%, and most preferably from 15 to 35 wt%, based on the total weight of the aqueous suspension.

In still another embodiment of the inventive process, step (d) is a dewatering step. The term "dewatering" in the meaning of the present invention means a reduction of the water content and an increase of the solids content which is obtained by using a thermal and/or mechanical method.

Dewatering step (d) can be carried out by any thermal and/or mechanical method known to the skilled person for reducing the water content of calcium carbonate comprising aqueous slurries. For example, dewatering step (d) can be preferably carried out mechanically or thermally such as by filtration, centrifugation, sedimentation in a settling tank, evaporation etc., preferably by jet or spray drying. According to another aspect, the present invention is directed to an aqueous pigment composition obtainable by the inventive process comprising steps (a) - (c), or steps (a) - (d). The process according to the present invention may further comprise an optional drying step (e). In said drying step, the aqueous pigment composition obtained in contacting step (c) or dewatering step (d) is dried to obtain a dried blend of ground natural calcium carbonate (GNCC) and surface modified calcium carbonate (MCC). According to still another aspect, the present invention is thus directed to an aqueous pigment composition obtainable by the inventive process comprising steps (a) - (c) and (e), or steps (a) - (e).

The drying method applied to obtain said dried blend of ground natural calcium carbonate (GNCC) and surface modified calcium carbonate (MCC) can be any kind of drying method well known to the skilled person.

Examples

The scope and interest of the invention may be better understood on basis of the following examples which are intended to illustrate embodiments of the present invention.

(A) Analytical methods

All parameters defined throughout the present application and mentioned in the following examples are based on the following measuring methods:

Particle size distributions

The particle size of surface modified calcium carbonate (MCC) herein is described as volume-based particle size distribution d _x . The volume-based median particle size dso and the volume-based topcut i&8 were measured using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Pic, Great Britain). The raw data obtained by the measurement was analyzed using the Mie theory, with a particle refractive index of 1.57 and an absorption index of 0.005. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.

The particle size of particulate materials other than surface modified calcium carbonate (e.g. ground natural calcium carbonate, GNCC) is described herein as weight-based particle size distribution d _x . The weight determined median particle size dso and topcut dw were measured by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field. The measurement was made with a Sedigraph™ 5120 of Micromeritics Instrument Corporation, USA. The method and the instrument are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments. The measurement was carried out in an aqueous solution of 0.1 wt% Na ₄ P207. The samples were dispersed using a high speed stirrer and sonicated.

BET specific surface area (SSA)

Throughout the present document, the specific surface area (in m ² /g) was determined using the BET method (using nitrogen as adsorbing gas), which is well known to the skilled man (ISO 9277:2010). The total surface area (in m ² ) of the filler material was then obtained by multiplication of the specific surface area and the mass (in g) of the corresponding sample.

Porosimetry

The specific pore volume is measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 μιη. The equilibration time used at each pressure step is 20 s. The sample material is sealed in a 3 cm ³ chamber powder penetrometer for analysis. The data are corrected for mercury compression, penetrometer expansion and sample material elastic compression using the software Pore-Comp (Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., "Void Space

Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate

Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 1996, 35(5), 1753 - 1764).

The total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 214 μιη down to about 1 to 4 μιη showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then this region appears bimodal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bimodal point of inflection, we thus define the specific intraparticle pore volume. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.

By taking the first derivative of the cumulative intrusion curve, the pore size distributions based on equivalent Laplace diameter, inevitably including pore- shielding, are revealed. The differential curves clearly show the coarse agglomerate pore structure region, the interparticle pore region and the intraparticle pore region, if present. Knowing the intraparticle pore diameter range it is possible to subtract the remainder interparticle and interagglomerate pore volume from the total pore volume to deliver the desired pore volume of the internal pores alone in terms of the pore volume per unit mass (specific pore volume). The same principle of subtraction, of course, applies for isolating any of the other pore size regions of interest.

Brookfield viscosity

The Brookfield viscosity was measured by a Brookfield DV-III Ultra viscometer at 24 °C ± 3 °C at 100 rpm using an appropriate spindle of the Brookfield RV-spindle set and is specified in mPa-s. Once the spindle has been inserted into the sample, the measurement was started with a constant rotating speed of 100 rpm. The reported Brookfield viscosity values were the values displayed 60 seconds after the start of the measurement. Based on his technical knowledge, the skilled person will select a spindle from the Brookfield RV-spindle set which is suitable for the viscosity range to be measured. For example, for a viscosity range between 200 and 800 mPa-s the spindle number 3 may be used, for a viscosity range between 400 and 1 600 mPa-s the spindle number 4 may be used, for a viscosity range between 800 and

3 200 mPa-s the spindle number 5 may be used, for a viscosity range between 1 000 and 2 000 000 mPa-s the spindle number 6 may be used, and for a viscosity range between 4 000 and 8 000 000 mPa-s the spindle number 7 may be used.

Solids content

The suspension solids content (also known as "dry weight") was determined using a Moisture Analyser MJ33 (Mettler-Toledo, Switzerland), with the following settings: drying temperature of 150 °C, automatic switch off if the mass does not change more than 1 mg over a period of 30 s, standard drying of 5 g of suspension.

Rx, Rx and Rz

The colour values Rx, Ry, Rz indicated in the present application are determined over white and black fields of the Leneta contrast card and are measured with using a Spectraflash SF 450 X spectrophotomer of the company Datacolor, Montreuil, France according to DIN 53 140.

Contrast ratio

Contrast ratio values are determined according to ISO 2814 at a spreading rate of 10 ± 0.5 m ² /l. The contrast ratio is calculated as described by the following equation: Ry(black)

Contrast ratio [%] = 100 %

RyVhite) with Ry(biack) and R yhite) being obtained by the measurement of the color values as indicated above. Yellowness index

The yellowness index is measured according to DIN 6167.

Gloss values

The Gloss values are measured at the listed angles according to DIN 67 530 on painted surfaces prepared with a coater gap of 150 μιη on contrast cards. The contrast cards used are Leneta contrast cards, form 3-B-H, size 7-5/8 x 11-3/8 (194 x 289 mm), sold by the company Leneta, and distributed by Novamart, Stafa, Switzerland. The gloss is measured with a gloss measurement device from the company Byk Gardner, Geretsried, Germany. The gloss is obtained by measuring 5 Leneta cards (one measurement each) with the gloss measurement device, and the average value is calculated by the device and can be derived from the display of the device.

(B) Examples

The following examples are not to be construed to limit the scope of the claims in any manner whatsoever.

Materials

Colourless base paint

A colorless base paint (Table 1) was used for preparing different paints with different pigments. The base paint was composed as follows: Table 1 - Colorless base paint:

The components used for the colorless base test paint and their function are known to the skilled person and listed in Table 2 hereto below.

Table 2 - Materials for coloriess base paint:

Ultrafine ground natural calcium carbonate (UF-GNCC)

An aqueous suspension of ground marble having a weight median particle diameter dso of 0.7 μιη and a weight-based particle diameter dw of 4 μιη, and particles < 2 μιη of 90%, was used. The solids content of the aqueous suspension was 78 wt%. Ground natural calcium carbonate (GNCC-1)

An aqueous suspension of ground marble having a weight median particle diameter dso of 1.6 μιη and a weight-based particle diameter dw of 10 μιη, residue on a 45 μιη sieve (ISO 787/7) 20 ppm, was used as comparative material. The solids content of the aqueous suspension was 78.4 wt%. Ground natural calcium carbonate (GNCC-2)

As a further comparative material, an aqueous suspension of ground marble was used having a weight median particle diameter dso of 5.7 μιη and a weight-based particle diameter dw of 30 μιη. The solids content of the aqueous suspension was 78 wt%.

Surface modified calcium carbonate (MCC)

Surface modified calcium carbonate (MCC) was obtained from 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel obtained by adjusting the solids content of a ground marble calcium carbonate from

Hustadmarmor Norway having a weight-based particle size distribution of 90 % less than 2 μιη (Sedigraph), such that a solids content of 22 wt%, based on the total weight of the aqueous suspension, is obtained. In addition, a solution was prepared containing 30 wt% phosphoric acid. Whilst mixing the slurry, 0.83 kg of the phosphoric acid solution were added to said suspension over a period of 10 min at a temperature of 55 °C. Finally, after the addition of the phosphoric acid, the slurry was stirred for additional 5 min prior to adjusting the solids content. The surface modified calcium carbonate (MCC) showed a volume median particle size dso of 1.06 μιη, a volume-based i¾8 of 4.95 μιη and a specific surface area of 38.5 m ² /g (BET, nitrogen). The solids contents were adjusted to a range of from 47 to 67 wt% (see the details provided in the trials section hereinbelow).

Trials

Preparation of the pigment composition

1. Provide suspension of GNCC in a container

2. Place container under dissolver

3. Add suspension of MCC under agitation at 1 000 to 1 100 rpm

4. Stir for approx. 10 min.

The prepared inventive pigment compositions using UF-GNCC and MCC are summarized in the following:

73% solid (90:10)

UF-GNCC; 78% solids 1 15.00 MCC; 47% solids 21.00

136.00

73% solid (85:15)

UF-GNCC; 78% solids 80.00 MCC ; 55% solids 20.00

100.00

73% solid (80:20)

UF-GNCC; 78% solids 74,87 MCC; 55% solids 26,54

101.41

73% solid (70:30)

UF-GNCC; 78% solids 90.00 MCC; 63.5% solids 47.00

137.00

73% solid (60:40)

UF-GNCC; 78% solids 77.00 MCC; 67% solids 60.00

137.00

Preparation of the paint

Different paints, each having a final pigment volume concentration (PVC) of 70 %, were prepared by mixing the colorless base paint and the different aqueous pigment compositions described above under stirring conditions using a dissolver

(approx. 10 min, 1 000 to 1 100 rpm). Where necessary, water was added to adjust the pigment volume concentration. The corresponding mixing ratio is indicated in Table 3 hereinbelow.

The comparative paints were prepared in an analogous manner using the materials indicated above (UF-GNCC, GNCC- 1 , GNCC-2).

Results

The optical properties and the viscosity of a paint prepared by using the inventive pigment composition and comparative pigments are summarized in Table 3. The methods used to determine the indicated parameters are described hereinabove.

As may be gathered from the optical properties indicated in Table 3, the paints prepared from the inventive pigment composition show satisfactory, good or even improved optical properties, in particular in terms of contrast ratio and matting properties.

Table 3:

SC % 73% 73% 73% 73% 73% 73% 73% GNCC- GNCC-

PAINT

(pigm. solid solid solid solid solid solid solid 1 2

FORMULATIONS

comp.) (100:0) (90:10) (85:15) (80:20) (70:30) (60:40) (0:100) (100:0) (100:0)

Basis paint, colorless 32.10 32.10 32.10 32.10 32.10 32.10 32.10 32.10 32.10

UF-GNCC(78%) 78 58.40

UF-GNCC(78%) : MCC (55%) 73 62.32

UF-GNCC(78%) : MCC (55%) 73 62.32

UF-GNCC(78%) : MCC (63.5%) 73 62.32

UF-GNCC(78%) : MCC (67%) 73 62.32

MCC(67%) 67 67.90

UF-GNCC(78%) : MCC(47%) 73 62.32

GNCC-1(78.4%) 78.4 58.10

GNCC-2(78%) 78 58.40

Water 9.50 5.58 5.58 5.58 5.58 5.58 9.80 9.50

Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

PVC % 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0

Density (solid) g/cm ³ 2.17 2.17 2.17 2.17 2.17 2.17 2.17 2.17 2.17

Density (liquid) g/cm ³ 1.294 1.325 1.427 1.325 1.417 1.417 1.520 1.413 1.415

Volume solids per litre ml 311.48 319.06 343.32 318.89 341.08 341.08 318.43 340.31 340.85

Volume solids per kg ml 240.78 240.76 240.66 240.76 240.66 240.66 209.53 240.87 240.88

Solids content by weight % 54.43 54.42 54.39 54.42 54.39 54.39 47.36 54.45 54.45

Pigment/binder (100%) solids) 5.84: 1 5.84: 1 5.84: 1 5.84: 1 5.84: 1 5.84: 1 5.84: 1 5.84: 1 5.84: 1

Table 3 (continued):

OPTICAL 73% 73% 73% 73% 73% 73% 73% GNCC- GNCC- PROPERTIES solid solid solid solid solid solid solid 1 2 (GAP 150 MU) (100:0) (90:10) (85:15) (80:20) (70:30) (60:40) (0:100) (100:0) (100:0)

Ry at C2° DIN 53 140 % 90.4 n/d 90.7 90.7 90.8 90.7 91.5 88.0 86.7

Ry over black at C2° DIN 53 140 % 77.4 n/d 78.5 78.6 80.1 80.1 82.6 70.7 17.9

Yellowness Index 2.4 n/d 2.3 2.1 2.3 2.5 1.7 4.7 6.4

Contrast ratio ISO 2814 % 85.5 n/d 86.6 86.7 88.2 88.2 90.3 80.3 20.7

Gloss 60° 150 μηι gap DIN 67 530 2.9 n/d 2.8 2.8 2.9 2.8 2.7 2.5 1.0

Gloss 85° 150 μηι gap DIN 67 530 46.0 n/d 38.9 37.0 26.1 24.1 19.2 12.0 1.3

VISCOSITY

ICI Viscosity mPa-s 1 10 n/d 210 200 180 200 220 100 70

Viscosity, D=l s-1 mPa-s 10700 n/d 32400 29000 30400 32400 33600 12666 5030

Viscosity, D=5 s-1 mPa-s 3850 n/d 12000 11000 1 1300 12100 14520 4873 2560

Viscosity, D=10 s-1 mPa-s 2530 n/d 7940 7340 7500 7890 8010 3451 1990

Viscosity, D=40 s-1 mPa-s 1080 n/d 3230 3010 3050 3200 3340 1915 1100