Anticaking agent

Abstract

The present invention relates to the use of a calcium carbonate-based composition as an anti-caking agent, the calcium carbonate-based composition comprising a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, the surface-reacted calcium carbonate being a mixture of natural ground calcium carbonate or precipitated calcium carbonate and carbon dioxide and at least one HO. + The carbon dioxide is a reaction product with an ion donor, and the reaction product is at least one H + They may be formed in situ by treatment with an ion donor and / or supplied from an external source.The present invention further relates to granular compositions comprising such anti-caking agents, and to methods for making such granular compositions.

Description

Technical Field

[0001] The present invention relates to the use of calcium carbonate-based compositions as anti-caking agents. Further, the present invention relates to granular compositions containing such anti-caking agents, and to methods for producing such granular compositions.

Background Art

[0002] Detergents, fertilizers, food or feed powders, pharmaceutical compositions, cosmetic powders, table salt, etc. may form agglomerates, especially when stored in a static state. This phenomenon is also called caking (solidification, coagulation). Caking can occur at almost all temperatures and almost all relative humidities, but in most cases, storage and / or handling of the composition at higher temperatures or higher relative humidities will result in more obvious caking problems.

[0003] Caking results in the hardening of such granular compositions, and aggregates or lumps are formed within the granular composition over a certain period of time. This aggregation can cause many problems and economic losses. For example, caked powder may not be suitable for further formulation or may not be discharged properly in an automatic device. Therefore, these products may have to be processed using a hammer mill, or remelted or simply discarded, which may result in huge additional costs and wasted resources. Further, when granular compositions such as table salt or sugar no longer have fluidity and form lumps in the package after a while, customers often regard it as a deterioration in quality.

[0004] Today, most manufacturers use anti-caking agents to control, reduce, or prevent the caking of particulate materials such as powders or granules. Examples of typical anti-caking additives are wheat flour, natural starch, natural ground calcium carbonate, phosphates, silicon dioxide, or calcium silicate. Depending on the application field, large amounts of these anti-caking agents may have to be used to control, reduce, or prevent caking in the desired composition.

[0005] In many application fields, especially in the food industry, additives such as anti-caking agents must be labeled in the ingredient list in the amounts typically contained in each composition or product. Therefore, it is desirable to use a small amount of anti-caking agent.

[0006] EP 2997833 A1 mentions the use of surface-reacted calcium carbonate as an anti-caking agent that can be used in relatively small amounts. Further anti-caking agents that have good anti-caking efficiency and can be used in reduced amounts are fumed silica or precipitated silica particles. Fumed silica or precipitated silica particles usually contain primary particles of nanosize. For example, silicon dioxide (E551), a food additive, is a substance composed of aggregated nanosize primary particles. These aggregates can further agglomerate to form larger structures. The size of the aggregates and agglomerates is usually larger than 100 nm. However, depending on the starting material and / or manufacturing method, it cannot be excluded that some aggregates of primary particles are smaller than 100 nm in size (see "Re-evaluation of silicon dioxide (E551) as a food additive", EFSA Journal, 2018, Volume 16). The safety of nanosize silica particles as food additives is still a matter of debate and has not yet been clearly established with certainty. This also applies to the application of nanosize silica in the fields of food, dietary supplements, or cosmetics. From that perspective, customers often reluctantly choose products containing silicon dioxide particles as additives.

Summary of the Invention

Problems to be Solved by the Invention

[0007] From the foregoing perspective, there is a continuing need for alternatives or improved agents for controlling, reducing, or preventing caking.

[0008] It is an object of the present invention to provide an alternative or improved agent for use as an anti-caking agent.

Means for Solving the Problems

[0009] The foregoing object is achieved by the uses, particulate compositions, and methods defined in the independent claims.

[0010] One aspect of the present invention is the use of a calcium carbonate-based composition as an anti-caking agent, wherein the calcium carbonate-based composition a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and a second component that is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H3O + ion donor and / or supplied from an external source, is the use.

[0011] Another aspect of the present invention is a particulate composition comprising a calcium carbonate-based anti-caking composition and a basic component, wherein the calcium carbonate-based anti-caking composition a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and It contains a second component which is surface-reacted calcium carbonate, where this surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with the at least one H3O + ion donor and / or supplied from an external source, This granular composition contains, in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition, an anti-caking composition based on the above calcium carbonate, is a granular composition.

[0012] Another aspect of the present invention is a method for producing a granular composition, which method includes a step of mixing an anti-caking composition based on calcium carbonate as a basic component, This anti-caking composition based on calcium carbonate is a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, where this surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with the at least one H3O + ion donor and / or supplied from an external source, and this anti-caking composition based on calcium carbonate is mixed with the above basic component in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition, is a method.

[0013] Preferred embodiments of the present invention are defined in the dependent claims.

[0014] According to one embodiment of the present invention, a calcium carbonate-based composition comprises a first component and a second component.

[0015] According to one embodiment of the present invention, the weight ratio of the first component to the second component (first component: second component) ranges from 99:1 to 1:99, preferably from 95:5 to 10:90, more preferably from 90:10 to 20:80, even more preferably from 85:15 to 30:70, and most preferably from 80:20 to 40:60.

[0016] According to one embodiment of the present invention, the first component is natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof, or the first component is precipitated calcium carbonate having a crystal form of aragonite, vaterite, or calcite, and is precipitated calcium carbonate selected from the group consisting of mixtures thereof.

[0017] According to one embodiment of the present invention, surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof, with carbon dioxide and at least one H3O + ion donor, wherein the carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, or surface-reacted calcium carbonate is a reaction product of precipitated calcium carbonate having a crystal form of aragonite, vaterite, or calcite, and mixtures thereof, with carbon dioxide and at least one H3O + ion donor, wherein the carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source.

[0018] According to one embodiment of the present invention, at least one H3O + ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acid salts, acetic acid, formic acid, and mixtures thereof, preferably, at least one H3O + ion donor is hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid; Li + , Na + and / or K + and at least partially neutralized by a cation selected from H2PO4 - ; Li + , Na + , K + , Mg 2+ and / or Ca 2+ and at least partially neutralized by a cation selected from HPO4 2- ; and is selected from the group consisting of mixtures thereof, more preferably, the at least one H3O + ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, and mixtures thereof, most preferably, the at least one H3O + ion donor is phosphoric acid.

[0019] According to one embodiment of the present invention, the first component has a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm, and / or 50 the first component has a specific surface area of 0.5 m / g to 30 m 2 / g, preferably 1 m 2 / g to 20 m 2 / g, more preferably 1 m 2 / g to 10 m 2 / g, measured using nitrogen and the BET method. 2 / g.

[0020] According to one embodiment of the present invention, the second component has a volume median particle size d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm. 50 and / or The second component has a specific surface area of 15 m 2 / g to 200 m 2 / g, preferably 20 m 2 / g to 180 m 2 / g, more preferably 25 m 2 / g to 160 m 2 / g, and most preferably 70 m 2 / g to 120 m 2 / g, as measured using nitrogen and the BET method.

[0021] According to one embodiment of the present invention, the calcium carbonate-based composition has less than 10.0% by weight, preferably less than 7.5% by weight, and more preferably less than 5.0% by weight of residual moisture, based on the total weight of the calcium carbonate-based composition.

[0022] According to one embodiment of the present invention, the calcium carbonate-based composition is added to a basic component selected from the group consisting of a food composition, a feed composition, a dietary supplement composition, a pharmaceutical composition, and a cosmetic composition, and preferably, the basic component is selected from a food composition or a feed composition.

[0023] According to one embodiment of the present invention, the anti-caking composition based on calcium carbonate consists of a first component and a second component, and / or The weight ratio of the first component to the second component (first component: second component) in the anti-caking composition based on calcium carbonate is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 20:80, more preferably in the range of 90:10 to 30:70, even more preferably in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:50.

[0024] According to one embodiment of the present invention, the basic component is selected from the group consisting of a food composition, a feed composition, a nutritional supplement composition, a pharmaceutical composition, and a cosmetic composition, and preferably, it is a food composition or a feed composition.

[0025] According to one embodiment of the present invention, the food composition is salt, curing salt, salt substitute, powdered milk, skimmed milk powder, cream powder, egg powder, whey fat powder, powdered protein, powder for vending machines, powdered cheese, sugar, powdered food flavor, spice, seasoning, packet soup mixture, baking mixture, pudding powder, mousse powder, or sauce powder, or the feed composition is pet food, animal milk replacer, or animal inorganic salt.

[0026] For the purposes of the present invention, the following terms should be understood to have the following meanings: In the context of the present invention, an "anticaking agent" is an agent added to a granular composition, which thereby reduces or prevents caking and / or maintains or improves the flow properties of the granular composition. In the context of the present invention, a "basic component" is a granular component to which an anticaking agent is added.

[0027] In the context of the present invention, the term "particles" represents a plurality of particles. This plurality of particles can be defined by a specific particle size distribution. A "granular" composition consists of, for example, powder particles, granules, agglomerates (crumbles), tablets, pellets, beads, and / or pellets.

[0028] In the context of the present invention, "ground calcium carbonate" (GCC) is calcium carbonate obtained from natural sources such as limestone, marble, or chalk, and is treated by wet and / or dry processes such as grinding, screening, and / or fractionation by a cyclone or classifier.

[0029] In the context of the present invention, "precipitated calcium carbonate" (PCC) is a synthetic material generally obtained by precipitation after the reaction of carbon dioxide and calcium hydroxide in an aqueous environment, or by precipitation of calcium ions and carbonate ions from a solution, for example, by precipitation of CaCl2 and Na2CO3. PCC can have a vaterite, calcite, or aragonite crystal form. PCC is described, for example, in European Patent Application Publication No. 2447213 A1, European Patent Application Publication No. 2524898 A1, European Patent Application Publication No. 2371766 A1, European Patent Application Publication No. 1712597 A1, European Patent Application Publication No. 1712523 A1, or International Publication No. 2013 / 142473 A1.

[0030] In the context of the present application, the term "surface reaction" refers to a process in which a substance is partially dissolved by treatment with an H3O + ion donor (for example, by use of a water-soluble free acid and / or acidic salt) in an aqueous environment, and then subjected to a crystallization process that can occur in the absence or presence of a further crystallization additive.

[0031] In the context of the present invention, "H3O + ion donor" is a Brønsted acid and / or acidic salt, that is, a salt containing acidic hydrogen.

[0032] As used herein, the term "acid" represents an acid in the sense of the definitions by Brønsted and Lowry (for example, H2SO4, HSO4 - ). The term "free acid" represents only such an acid in its fully protonated form (for example, H2SO4).

[0033] The "particle size" of a particulate material is described by its particle size distribution d x . Unless otherwise indicated, the value d x represents the diameter with respect to which x weight % of the particles have a diameter less than d x . This is, for example, d 20The value means that 20% by weight of all the particles have a particle size smaller than this particle size. Therefore, d 50 The value is the weight median particle size, that is, 50% by weight of all the particles are smaller than this particle size. For the purposes of the present invention, unless otherwise indicated, the particle size is the weight median particle size d 50 (wt.). The particle size was determined by using a Sedgraph® 5100 apparatus or a Sedgraph® 5120 apparatus of Micromeritics Instrument Corporation. This method and apparatus are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. The measurement was carried out in a 0.1% by weight aqueous solution of Na4P2O7. In particular, the particle size of natural ground calcium carbonate and precipitated calcium carbonate used for producing surface-reacted calcium carbonate is defined as the particle size on a weight basis.

[0034] For certain materials defined herein, the "particle size" is described as a volume-based particle size distribution. This is indicated, for example, as "volume-based median particle size", "volume median particle size" or "volume top cut particle size". The volume median particle size d 50 was evaluated using a Malvern Mastersizer 2000 or 3000 laser diffraction system. The d 50 or d 98 values measured using a Malvern Mastersizer 2000 or 3000 laser diffraction system, preferably a Malvern Mastersizer 3000 laser diffraction system, indicate diameter values such that 50% or 98% by volume of the particles have a diameter smaller than this value. The raw data obtained by the measurement was analyzed using Mie theory with a particle refractive index of 1.57 and an absorption coefficient of 0.005. The measurement was carried out in a 0.1% by weight aqueous solution of Na4P2O7. In particular, the particle size of natural ground calcium carbonate, precipitated calcium carbonate, and surface-reacted calcium carbonate used in the calcium carbonate-based compositions of the present invention, as well as the particle size of the basic components, is defined as the particle size on a volume basis.

[0035] The "specific surface area" of the substances used throughout this specification (expressed in m 2 / g) can be determined by using the Brunauer-Emmett-Teller (BET) method with nitrogen as the adsorbed gas and by using a Micromeritics ASAP 2460 apparatus. This method is well-known to those skilled in the art and is defined in ISO 9277:2010. Before such measurements, the sample was filtered in a Büchner funnel, rinsed with deionized water, and dried in an oven at 110 °C for at least 12 hours. The total surface area (m 2 ) of this substance can be obtained by multiplying the specific surface area (m 2 / g) of this substance by the mass (g).

[0036] In the context of the present invention, the term "pore" refers to the spaces found between and / or within particles, i.e., the spaces formed by particles that are densely packed under the closest contact, such as in powders or compacts (interparticle pores) and / or the voids within porous particles (intraparticle pores), which are understood to describe spaces that allow the passage of a liquid under pressure when saturated with the liquid and / or support the absorption of a surface wetting liquid.

[0037] Unless otherwise specified, the term "drying" refers to a method of removing at least a portion of the water from the substance to be dried, such that the resulting "dried" substance reaches a constant weight at 200 °C. Further, a "dried" or "dry" substance can be defined, unless otherwise specified, as having a total water content of 1.0 wt% or less, preferably 0.5 wt% or less, more preferably 0.2 wt% or less, and most preferably 0.03 - 0.07 wt% relative to the total weight of the dried substance.

[0038] For the purposes of the present application, a "water-insoluble" substance is defined as a substance that, when mixed with 100 mL of deionized water at 20 °C and filtered to recover the filtrate, gives 0.1 g or less of recovered solid matter after evaporating 100 g of this filtrate at 95 to 100 °C. A "water-soluble" substance is defined as a substance that results in the recovery of more than 0.1 g of solid matter after evaporating 100 g of the above filtrate at 95 to 100 °C. To evaluate whether a substance is water-insoluble or water-soluble in the context of the present invention, the sample size is greater than 0.1 g, preferably 0.5 g or more.

[0039] In the context of the present invention, a "suspension" or "slurry" contains undissolved solids and water and, optionally, further additives, and usually contains a large amount of solids and thus can be more viscous and denser than the liquid forming it.

[0040] When using an indefinite or definite article, such as "a", "an" or "the", when referring to a singular noun, this includes the plural of that noun, unless otherwise specified.

[0041] When using the term "comprising" in this specification and the claims, this does not exclude other elements. For the purposes of the present invention, the term "consisting of" is considered a preferred embodiment of the term "comprising". In the following, when a group is defined as including at least a certain number of embodiments, it should be understood that this also preferably discloses a group consisting of only these embodiments.

[0042] Terms such as "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. For example, this means that, unless the context clearly indicates otherwise, the term "obtained" does not imply that, for example, a certain embodiment must be obtained by the order of steps following the term "obtained", but such a limited understanding means that, as a preferred embodiment, it is always included in the terms "obtained" or "defined".

[0043] Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

[0044] The present invention will be described in more detail below.

[0045] Use of a calcium carbonate-based composition as an anti-caking agent One aspect of the present invention is the use of a calcium carbonate-based composition as an anti-caking agent, wherein this calcium carbonate-based composition, comprises a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and a second component that is surface-reacted calcium carbonate, wherein this surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with the at least one H3O + ion donor and / or supplied from an external source, relating to use.

[0046] The inventors have surprisingly found that a calcium carbonate-based composition comprising a mixture of natural ground calcium carbonate or precipitated calcium carbonate (first component) and surface-reacted calcium carbonate as described herein (second component) can be advantageously used as an anti-caking agent for granular compositions, thereby reducing or preventing caking of the granular composition and / or maintaining or improving the flow properties of the granular composition. Furthermore, the inventors have found that this calcium carbonate-based composition has an improved anti-caking effect and / or is a better flow aid than comparable known anti-caking agents such as known calcium carbonate anti-caking agents.

[0047] The use of the calcium carbonate-based composition as an anti-caking agent found by the inventors provides the use of an anti-caking agent that is non-toxic, readily available, and can be used in relatively small amounts.

[0048] The anti-caking effect and / or improvement in fluidity brought about in the granular composition by the addition of the calcium carbonate-based composition of the present invention can be represented by the normalized basic flow energy (BFE norm ). The basic flow energy (BFE: basic flow energy) is evaluated by the rotation of a high-precision blade descending through a spiral passage through a fixed volume of the powder composition. During this downward traverse, the torque and axial pressure acting on the blade are measured, and the flow resistance in this dynamic state is calculated and expressed as the flow energy. The normalized basic flow energy (BFE norm ) is obtained by dividing the BFE by the mass of the powder at a fixed volume. BFE norm is directly correlated with the fluidity of the granular composition. This means that a granular composition having a lower BFE norm has better fluidity than a composition having a higher BFE norm . The method for determining the BFE and BFE norm of the composition is known to those skilled in the art.

[0049] According to one embodiment, the anti-caking composition according to the present invention has an anti-caking effect, and this effect is the normalized basic flow energy (BFE norm ) of the granular composition containing the basic component and the anti-caking agent of the present invention.

[0050] According to one embodiment of the present invention, the normalized basic flow energy (BFE norm ) of the granular composition containing the basic component and the anti-caking agent of the present invention is at least 2%, for example at least 5%, for example at least 10% lower than the normalized basic flow energy (BFE norm ) of the granular composition containing the same basic component but not containing the anti-caking agent of the present invention. According to one preferred embodiment of the present invention, the normalized basic flow energy (BFE norm ) of the granular composition containing the basic component and the anti-caking agent of the present invention is at least 10% lower than the normalized basic flow energy (BFE norm ) of the granular composition containing the same basic component but not containing the anti-caking agent of the present invention, preferably consisting of the same basic component.

[0051] It should be understood that the normalized basic flow energy (BFE norm ) of both compositions (i.e., the composition containing the anti-caking agent of the present invention and the composition not containing the anti-caking agent of the present invention) is measured under the same conditions.

[0052] The anti-caking effect and / or the improvement in fluidity brought about by the addition of the calcium carbonate-based composition of the present invention to the granular composition can be further represented by the aeration ratio (AR). The aeration ratio is the ratio of BFE (airflow velocity = n) to BFE (in the absence of air; airflow velocity = 0) at an airflow velocity of 18 mm / second in the powder composition.

[0053]

Number

[0054] The aeration rate is inversely proportional to the cohesivity of the powder composition. This means that a granular composition having a higher aeration rate has better flowability than a composition having a lower aeration rate.

[0055] The powder aeration test is performed by introducing air into the substrate of a powder column and quantifying how this changes the flow properties by measuring the reduction in flow energy. Those skilled in the art are familiar with the aeration test procedure.

[0056] According to one embodiment, the anti-caking composition according to the present invention has an anti-caking effect, and this effect is represented by the aeration rate of the granular composition containing the basic component and the anti-caking composition of the present invention.

[0057] According to one embodiment of the present invention, the aeration rate of the granular composition containing the basic component and the anti-caking composition of the present invention is at least 5%, for example at least 10%, for example at least 20%, for example at least 50% higher than the aeration rate of the granular composition containing the same basic component but not containing the anti-caking composition of the present invention.

[0058] According to one preferred embodiment of the present invention, the aeration rate of the granular composition containing the basic component and the anti-caking composition of the present invention is at least 25% higher than the aeration rate of the granular composition containing the same basic component but not containing the anti-caking agent of the present invention, preferably consisting of the same basic component.

[0059] It should be understood that the aeration rates of both compositions (i.e., the composition containing the anti-caking agent of the present invention and the composition not containing the anti-caking agent of the present invention) are measured under the same conditions.

[0060] Furthermore, the anti-caking effect and / or the improvement in fluidity brought about by the addition of the calcium carbonate-based composition of the present invention to the granular composition can be further measured based on the presence and / or the depth of the caking crust in the granular composition. The caking crust can form on the top of the powder composition by moisture entering the powder composition over time. The presence of moisture in the composition can lead to aggregates, agglomerates, and caking in the powder, which results in a deterioration of the powder quality. The depth of the caking crust in the powder bulk is inversely proportional to the anti-caking effect of the anti-caking agent. This means that a granular composition having no caking crust or having a not-so-deep caking crust exhibits less caking than a composition having a caking crust or having a deeper caking crust.

[0061] According to one embodiment, the anti-caking composition according to the present invention has an anti-caking effect, and this effect is represented by the depth of the caking crust present on the surface of the granular composition containing the basic component and the anti-caking composition of the present invention.

[0062] According to one preferred embodiment of the present invention, the depth of the caking crust present on the surface of the granular composition containing the basic component and the anti-caking composition of the present invention is at least 2%, for example 5%, for example 10% lower than the caking crust of a granular composition containing the same basic component but not containing the anti-caking composition of the present invention, preferably consisting of the same basic component.

[0063] It should be understood that the depth of the caking crust of both compositions (i.e., the composition containing the anti-caking agent of the present invention and the composition not containing the anti-caking agent of the present invention) is measured under the same conditions.

[0064] In addition to the aforementioned anti-caking effect, a granular composition containing a calcium carbonate-based composition of the present invention as an anti-caking agent shows less dust (powdering), i.e., only temporary dust formation, when storing and / or handling the granular composition, compared to granular compositions containing different anti-caking agents such as silica-based anti-caking agents.

[0065] The calcium carbonate-based composition contains a first component that is natural ground calcium carbonate or precipitated calcium carbonate.

[0066] According to one embodiment, the first component has a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm. 50 and / or the first component has a specific surface area of 0.5 m 2 / g to 30 m 2 / g, preferably 1 m 2 / g to 20 m 2 / g, more preferably 1 m 2 / g to 10 m 2 / g, measured using nitrogen and the BET method.

[0067] According to another embodiment, the first component has a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm. 50 and the first component has a specific surface area of 0.5 m 2 / g to 30 m 2 / g, preferably 1 m 2 / g to 20 m 2 / g, more preferably 1 m 2 / g to 10 m 2 / g, measured using nitrogen and the BET method.

[0068] The first component of the calcium carbonate-based composition can have a specific residual moisture content. According to one embodiment, the first component has a residual moisture content of less than 3.0% by weight, preferably less than 2.0% by weight, more preferably less than 1.0% by weight, based on the total weight of the first component. Those skilled in the art know how to measure the residual moisture content.

[0069] According to a preferred embodiment, the calcium carbonate-based composition comprises a first component that is natural ground calcium carbonate.

[0070] It is understood that the natural ground calcium carbonate can be one specific natural ground calcium carbonate or a mixture of different types of natural ground calcium carbonate.

[0071] In one embodiment of the present invention, the natural ground calcium carbonate comprises one type of natural ground calcium carbonate and preferably consists of one type of natural ground calcium carbonate. Alternatively, the natural ground calcium carbonate comprises two or more types of natural ground calcium carbonate and preferably consists of two or more types of natural ground calcium carbonate. For example, the natural ground calcium carbonate comprises two or three types of natural ground calcium carbonate and preferably consists of two or three types of natural ground calcium carbonate. Preferably, the natural ground calcium carbonate comprises one type of natural ground calcium carbonate, and more preferably consists of one type of natural ground calcium carbonate.

[0072] In one embodiment of the present invention, the natural ground calcium carbonate is a pulverized calcium carbonate-containing mineral, and preferably the calcium carbonate-containing mineral is selected from the group consisting of chalk, limestone, marble, dolomite, and mixtures thereof.

[0073] According to a preferred embodiment of the present invention, the natural ground calcium carbonate is selected from the group consisting of chalk, limestone, and marble. More specifically, the natural ground calcium carbonate is limestone or marble, and most preferably marble.

[0074] Natural ground calcium carbonate can be obtained, for example, from natural calcium carbonate-containing minerals (such as chalk, limestone, marble, or dolomite) through wet and / or dry grinding processes such as crushing and / or grinding. According to one embodiment, the natural ground calcium carbonate is wet natural ground calcium carbonate. In another embodiment, the natural ground calcium carbonate is dry natural ground calcium carbonate.

[0075] For example, under conditions such that purification is mainly obtained from the impact with secondary objects, the grinding process can be carried out with any conventional grinding device, that is, a ball mill, a rod mill, a vibration mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a micronizer, a shredder, a declumper, a knife cutter, or one or more of other such devices known to those skilled in the art. The grinding process may be carried out under conditions such that self-grinding occurs, and / or by horizontal ball mill grinding, and / or by other such methods known to those skilled in the art.

[0076] In one embodiment, grinding is carried out using a vertical or horizontal ball mill, preferably a vertical ball mill. Such vertical and horizontal ball mills generally consist of a vertically or horizontally arranged cylindrical grinding chamber equipped with an axially high-speed rotating stirring shaft equipped with a plurality of paddles and / or stirring disks, for example, those described in European Patent Application Publication No. 0607840 A1.

[0077] It should be noted that the grinding of calcium carbonate-containing minerals can be carried out by using at least one of the aforementioned grinding methods or equipment. However, any of the aforementioned methods, or any combination of a series of the aforementioned grinding equipment, can also be used.

[0078] After the grinding step, the ground calcium carbonate-containing mineral can be optionally divided, by use of a classification step, into two or more fractions each having a different particle distribution. The classification step generally serves to divide a feed fraction having a certain particle size distribution into a coarse fraction that can be subjected to another grinding cycle and a fine fraction that can be used as the final product. For this purpose, screening equipment can of course be used, as well as gravitational equipment such as centrifuges or cyclones (e.g., hydrocyclones), and any combination of the aforementioned equipment.

[0079] When the first component of the calcium carbonate-based composition is natural ground calcium carbonate, the natural ground calcium carbonate can have certain physical properties such as a specific particle size and / or specific surface area.

[0080] According to one embodiment, the natural ground calcium carbonate has a volume median diameter d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm 50 , and / or a volume top cut diameter d of 2 to 80 μm, preferably 2 to 60 μm, more preferably 2 to 40 μm, even more preferably 3 to 30 μm, and most preferably 4 to 20 μm 98 .

[0081] According to one embodiment, the natural ground calcium carbonate has a specific surface area of 0.5 m 2 / g to 30 m 2 / g, preferably 1 m 2 / g to 20 m 2 / g, more preferably 1 m 2 / g to 10 m 2 / g, measured using nitrogen and the BET method.

[0082] According to one embodiment, the first component has a volume median diameter d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm50 and a volume top cut particle size d of 2 to 80 μm, preferably 2 to 60 μm, more preferably 2 to 40 μm, even more preferably 3 to 30 μm, and most preferably 4 to 20 μm 98 and natural ground calcium carbonate having a specific surface area of 0.5 m 2 / g to 30 m 2 / g, preferably 1 m 2 / g to 20 m 2 / g, more preferably 1 m 2 / g to 10 m 2 / g, as measured using nitrogen and the BET method.

[0083] In one embodiment, the natural ground calcium carbonate has a volume median particle size d of 0.8 to 8 μm 50 and a volume top cut particle size d of 4 to 20 μm 98 and a specific surface area of 1 m 2 / g to 10 m 2 / g, as measured using nitrogen and the BET method. In one embodiment, the natural ground calcium carbonate has a volume median particle size d of 0.8 to 6 μm 50 and a volume top cut particle size d of 4 to 18 μm 98 and a specific surface area of 1 m 2 / g to 5 m 2 / g, as measured using nitrogen and the BET method.

[0084] According to another embodiment, the first component of the calcium carbonate-based composition is precipitated calcium carbonate.

[0085] It is understood that the precipitated calcium carbonate can be one type of precipitated calcium carbonate or a mixture of different types of precipitated calcium carbonate.

[0086] In one embodiment of the present invention, the precipitated calcium carbonate comprises one type of precipitated calcium carbonate and preferably consists of one type of precipitated calcium carbonate. Alternatively, the precipitated calcium carbonate comprises two or more types of precipitated calcium carbonate and preferably consists of two or more types of precipitated calcium carbonate. For example, the precipitated calcium carbonate comprises two or three types of precipitated calcium carbonate and preferably consists of two or three types of precipitated calcium carbonate. Preferably, the precipitated calcium carbonate comprises one type of precipitated calcium carbonate, and more preferably consists of one type of precipitated calcium carbonate.

[0087] According to one embodiment, the precipitated calcium carbonate is selected from the group consisting of precipitated calcium carbonate having a crystalline form of aragonite, vaterite, or calcite, and mixtures thereof.

[0088] It is understood that the precipitated calcium carbonate can have specific physical properties such as a specific particle size or specific surface area.

[0089] According to one embodiment, the precipitated calcium carbonate has a volume median diameter d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm 50 thereof.

[0090] According to another embodiment, the precipitated calcium carbonate has a volume median diameter d of 0.25 to 50 μm, more preferably 0.3 to 10 μm, and most preferably 0.4 to 7 μm 50 thereof. In one embodiment, the precipitated calcium carbonate has a volume top cut diameter d of 1 to 100 μm, preferably 1 to 50 μm, more preferably 1.5 to 30 μm, and most preferably 1.5 to 20 μm 98 thereof. According to another embodiment, the precipitated calcium carbonate has a volume median diameter d of 0.3 to 10 μm, most preferably 0.4 to 7 μm 50 and a volume top cut diameter d of 1.5 to 30 μm, most preferably 1.5 to 20 μm 98It has.

[0091] According to another embodiment, the precipitated calcium carbonate has a specific surface area of 3 m 2 / g to 50 m 2 / g, preferably 3 m 2 / g to 35 m 2 / g, most preferably 3 m 2 / g to 25 m 2 / g, measured using nitrogen and the BET method.

[0092] According to another embodiment, the precipitated calcium carbonate has a volume median particle size d of 0.3 to 10 μm, most preferably 0.4 to 7 μm 50、 and a volume top cut particle size d of 1.5 to 30 μm, most preferably 1.5 to 20 μm 98 , and a specific surface area of 3 m 2 / g to 50 m 2 / g, preferably 3 m 2 / g to 35 m 2 / g, most preferably 4 m 2 / g to 25 m 2 / g, measured using nitrogen and the BET method.

[0093] The calcium carbonate-based composition contains a second component. The second component is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with at least one H3O + ion donor, and this carbon dioxide is formed in situ and / or supplied from an external source by treatment with at least one H3O + ion donor.

[0094] According to one embodiment, the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed by treatment with at least one H3O +Formed in situ by treatment with an ion donor and / or supplied from an external source, or Surface-reacted calcium carbonate is a precipitated calcium carbonate selected from the group consisting of precipitated calcium carbonate having a crystalline form of aragonite, vaterite, or calcite, and mixtures thereof, and carbon dioxide and at least one H3O + Is a reaction product with an ion donor, and this carbon dioxide is at least one H3O + Formed in situ by treatment with an ion donor and / or supplied from an external source.

[0095] According to one preferred embodiment, the surface-reacted calcium carbonate is a natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof, and carbon dioxide and at least one H3O + Is a reaction product with an ion donor, and this carbon dioxide is at least one H3O + Formed in situ by treatment with an ion donor and / or supplied from an external source.

[0096] The second component of the calcium carbonate-based composition can have a specific residual moisture content. According to one embodiment, the second component has a residual moisture content of less than 10% by weight, preferably less than 5.0% by weight, based on the total weight of the second component. For example, the residual moisture may be approximately 3.0% by weight based on the total weight of the second component.

[0097] It is understood that the surface-reacted calcium carbonate can be one type of surface-reacted calcium carbonate or a mixture of different types.

[0098] In one embodiment of the present invention, the surface-reacted calcium carbonate contains one type of surface-reacted calcium carbonate and preferably consists of one type of surface-reacted calcium carbonate. Alternatively, the surface-reacted calcium carbonate contains two or more types of surface-reacted calcium carbonate and preferably consists of two or more types of surface-reacted calcium carbonate. For example, the surface-reacted calcium carbonate contains two or three types of surface-reacted calcium carbonate and preferably consists of two or three types of surface-reacted calcium carbonate. Preferably, the surface-reacted calcium carbonate contains one type of surface-reacted calcium carbonate, and more preferably consists of one type of surface-reacted calcium carbonate.

[0099] In a preferred embodiment of the present invention, the surface-reacted calcium carbonate is obtained by a method comprising the following steps: (a) Providing a suspension of natural or precipitated calcium carbonate; (b) Adding at least one acid having a pK a value of 0 or less at 20 °C, or having a pK a value of 0 to 2.5 at 20 °C to the suspension of step (a); and (c) Treating the suspension of step (a) with carbon dioxide before, during, or after step (b). According to another embodiment, the surface-reacted calcium carbonate is obtained by a method comprising the following steps: (A) Providing natural or precipitated calcium carbonate; (B) Providing at least one water-soluble acid; (C) Providing CO2 gas; (D) Contacting the natural or precipitated calcium carbonate of step (A) with at least one acid of step (B) and the CO2 of step (C), wherein the method is characterized in that: (i) at least one acid of step (B) has a pK ahaving and the corresponding anion being formed upon loss of this first available hydrogen which is capable of producing a water-soluble calcium salt, and (ii) after contact of at least one acid of step (B) with natural or precipitated calcium carbonate of step (A), in relation to ionization of the first available hydrogen, the hydrogen-containing salt has a pK exceeding 7 at 20 °C a having and when its salt anion is capable of forming a water-insoluble calcium salt, additionally providing at least one water-soluble salt.

[0100] Ground natural calcium carbonate (GCC) is preferably selected from calcium carbonate-containing minerals selected from the group consisting of marble, chalk, limestone, and mixtures thereof. Ground natural calcium carbonate may contain further naturally occurring components such as magnesium carbonate, aluminosilicates, etc.

[0101] Generally, the grinding of ground natural calcium carbonate may be a dry or wet grinding process, for example, it can be carried out with any conventional grinding equipment under conditions such that the grinding is mainly obtained from the impact with a secondary object, that is, in a ball mill, rod mill, vibration mill, roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, micronizer, shredder, declumper, knife cutter, or one or more of other such devices known to those skilled in the art. When the calcium carbonate-containing mineral substance contains a wet-ground calcium carbonate-containing mineral substance, the grinding process can be carried out under conditions such that autogenous grinding occurs, and / or by horizontal ball mill grinding, and / or by other such methods known to those skilled in the art. The wet-process ground calcium carbonate-containing mineral substance thus obtained can be washed and dehydrated by well-known methods, for example, by agglomeration, filtration, or forced evaporation before drying. The subsequent drying process (if necessary) can be carried out in a one-step process such as spray drying, or at least a two-step process. It is also common to carry out a beneficiation process (flotation, bleaching, or magnetic separation process) to remove impurities for such mineral substances.

[0102] In the context of the present invention, "precipitated calcium carbonate" (PCC) is generally a synthetic material obtained by precipitation after the reaction of carbon dioxide and calcium hydroxide in an aqueous environment, or by the precipitation of calcium ions and carbonate ions from a solution, for example, by the precipitation of CaCl2 and Na2CO3. Further possible methods for PCC production are the lime-soda process or the Solvay process where PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystal forms, namely, calcite, aragonite, and vaterite crystal forms, and there are many different polymorphs (crystal habits) for each of these crystal forms. Calcite has a trigonal crystal system structure with typical crystal habits such as scalenohedron (S-PCC), rhombohedron (R-PCC), hexagonal prism, trapezohedron, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite has an orthorhombic crystal system structure with typical crystal habits of twinned hexagonal prisms, as well as structures with various combinations of thin and elongated prisms, curved blades, steep-gradient cones, chisel-shaped crystals, branched tree forms, and coral or worm-like forms. Vaterite belongs to the hexagonal crystal system. The obtained PCC slurry can be mechanically dehydrated and dried.

[0103] According to one embodiment of the present invention, the precipitated calcium carbonate is preferably precipitated calcium carbonate containing a mineralogical crystal form of aragonite, vaterite, or calcite, or a mixture thereof.

[0104] Precipitated calcium carbonate can be ground by the same means as used for grinding the above-described natural calcium carbonate before treatment with carbon dioxide and at least one H3O + ion donor.

[0105] According to one embodiment of the present invention, the natural ground calcium carbonate or precipitated calcium carbonate has a weight median particle size d of 0.05 to 10.0 μm, preferably 0.2 to 5.0 μm, and most preferably 0.4 to 3.0 μm. 50It is in the form of particles having. According to a further embodiment of the present invention, natural ground calcium carbonate or precipitated calcium carbonate has a weight top cut particle size d of 0.15 to 30 μm, preferably 0.6 to 15 μm, more preferably 1.2 to 10 μm, most preferably 1.5 to 4 μm, particularly 1.6 μm. 98 It is in the form of particles having.

[0106] Natural ground calcium carbonate and / or precipitated calcium carbonate can be used in a dry state or suspended in water. Preferably, the corresponding slurry has a content of natural ground calcium carbonate or precipitated calcium carbonate of 1 wt% to 90 wt%, more preferably 3 wt% to 60 wt%, even more preferably 5 wt% to 40 wt%, most preferably 10 wt% to 25 wt% based on the weight of the slurry.

[0107] One or more H3O used in the production of surface-reacted calcium carbonate + ion donors may be any strong acid, medium-strength acid, or weak acid, or mixtures thereof that generate H3O ions under the production conditions. According to the present invention, at least one H3O + ion donor may also be an acidic salt that generates H3O ions under the production conditions. + ion donors may be any strong acid, medium-strength acid, or weak acid, or mixtures thereof that generate H3O ions under the production conditions. According to the present invention, at least one H3O + ion donor may also be an acidic salt that generates H3O ions under the production conditions.

[0108] According to one embodiment, at least one H3O + ion donor is a strong acid having a pK of 0 or less at 20 °C. a having.

[0109] According to another embodiment, at least one H3O + ion donor is a medium-strength acid having a pK value of 0 to 2.5 at 20 °C. The pK at 20 °C a When the value is 0 or less, the acid is preferably selected from sulfuric acid, hydrochloric acid, or mixtures thereof. When the pK at 20 °C a is 0 or less, the acid is preferably selected from sulfuric acid, hydrochloric acid, or mixtures thereof. When the pK at 20 °C a is 0 to 2.5, H3O +The ion donor is preferably selected from H2SO3, H3PO4, oxalic acid, or mixtures thereof. At least one H3O + The ion donor is an acidic salt, for example, Li + , Na + or K + and the like, and HSO4 - or H2PO4 - partially neutralized by the corresponding cation, or Li + , Na + , K + , Mg 2+ or Ca 2+ and the like, and HPO4 2- partially neutralized by the corresponding cation. It can be. At least one H3O + The ion donor can be a mixture of one or more acids and one or more acidic salts.

[0110] According to yet another embodiment, at least one H3O + The ion donor has a pK a value greater than 2.5 and less than or equal to 7 in relation to the ionization of the first available hydrogen when measured at 20 ° C., and is a weak acid having a corresponding anion, which can form a water-soluble calcium salt. Then, when measured at 20 ° C., the hydrogen-containing salt has a pK a greater than 7 in relation to the ionization of the first available hydrogen, and the salt anion can form a water-insoluble calcium salt, an additional at least one water-soluble salt is provided. According to a preferred embodiment, the weak acid has a pK aIt has a value, and more preferably, this weak acid is selected from the group consisting of acetic acid, formic acid, propanoic acid, and mixtures thereof. Preferred cations of the water-soluble salt are selected from the group consisting of potassium, sodium, lithium, and mixtures thereof. In a more preferred embodiment, the cation is sodium or potassium. Preferred anions of the water-soluble salt are selected from the group consisting of phosphate anions, dihydrogen phosphate anions, hydrogen phosphate anions, oxalate anions, silicate anions, mixtures thereof, and hydrates thereof. In a more preferred embodiment, the anion is selected from the group consisting of phosphate anions, dihydrogen phosphate anions, hydrogen phosphate anions, mixtures thereof, and hydrates thereof. In the most preferred embodiment, the anion is selected from the group consisting of dihydrogen phosphate anions, hydrogen phosphate anions, mixtures thereof, and hydrates thereof. The addition of the water-soluble salt can be carried out dropwise or in one step. In the case of dropwise addition, the addition is preferably carried out within 10 minutes. It is more preferable to add the above salt in one step.

[0111] According to one embodiment of the present invention, at least one H3O + ion donors are selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, and mixtures thereof. Preferably, at least one H3O + ion donors are selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid; Li + , Na + or K + such as H2PO4 at least partially neutralized by the corresponding cation - ; Li + , Na + , K + , Mg 2+ or Ca 2+ such as HPO4 at least partially neutralized by the corresponding cation 2- ; and are selected from the group consisting of mixtures thereof, and more preferably at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, and mixtures thereof, and most preferably at least one H3O +The ion donor is phosphoric acid.

[0112] One or more H3O + The ion donor can be added to the suspension as a high-concentration solution or a more diluted solution. Preferably, the molar ratio of H3O to 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.

[0113] Alternatively, before suspending the natural or precipitated calcium carbonate, it is also possible to add the H3O + ion donor to water.

[0114] In the next step, the natural ground calcium carbonate or precipitated calcium carbonate is treated with carbon dioxide. When using a strong acid such as sulfuric acid or hydrochloric acid for the treatment with the H3O + ion donor, carbon dioxide is automatically generated. Alternatively or in addition, carbon dioxide can be supplied from an external source.

[0115] H3O + The treatment with the ion donor and the treatment with carbon dioxide can be carried out simultaneously when using a strong acid or an acid of medium strength. For example, using an acid of medium strength having a pK a from 0 to 2.5 at 20 °C, it is also possible to first carry out the treatment with the H3O + ion donor, where carbon dioxide is formed in situ, and thus the treatment with carbon dioxide is automatically carried out simultaneously with the treatment with the H3O + ion donor, and then additional treatment is carried out with carbon dioxide supplied from an external source.

[0116] In a preferred embodiment, the H3O + ion donor treatment step and / or the carbon dioxide treatment step are repeated at least once, more preferably several times. According to one embodiment, at least one H3O +The ion donor is added over a period of at least about 5 minutes, usually about 5 to about 30 minutes. Alternatively, at least one H3O + The ion donor is added over a period of about 30 minutes, preferably about 45 minutes, and sometimes about 1 hour or more.

[0117] H3O + After treatment with the ion donor and treatment with carbon dioxide, the pH of the aqueous suspension measured at 20 °C reaches a value that naturally exceeds 6.0, preferably exceeds 6.5, more preferably exceeds 7.0, and even more preferably exceeds 7.5, thereby producing surface-reacted natural or precipitated calcium carbonate as an aqueous suspension having a pH exceeding 6.0, preferably exceeding 6.5, more preferably exceeding 7.0, and even more preferably exceeding 7.5.

[0118] H3O + The treatment with the ion donor and the treatment with carbon dioxide can be carried out over a wide temperature range. Preferably, H3O + The treatment with the ion donor and the treatment with carbon dioxide can be carried out at room temperature or at a high temperature. For example, H3O + When the treatment with the ion donor and the treatment with carbon dioxide are carried out at a high temperature, this treatment is preferably carried out in the range of 30 to 90 °C, more preferably 40 to 80 °C, most preferably 50 to 80 °C, for example 60 to 80 °C.

[0119] Further details regarding the production of surface-reacted natural calcium carbonate are disclosed in International Publication No. 00 / 39222 A1, International Publication No. 2004 / 083316 A1, International Publication No. 2005 / 121257 A2, International Publication No. 2009 / 074492 A1, European Patent Application Publication No. 2264108 A1, European Patent Application Publication No. 2264109 A1, and U.S. Patent Application Publication No. 2004 / 0020410 A1, the contents of these references being incorporated herein by reference.

[0120] Similarly, surface-reacted precipitated calcium carbonate is obtained. As can be understood in detail from WO 2009 / 074492 A1, surface-reacted precipitated calcium carbonate is obtained by contacting precipitated calcium carbonate in an aqueous medium with H3O + ions and an anion that can be dissolved in the aqueous medium and form a water-insoluble calcium salt to form a slurry of surface-reacted precipitated calcium carbonate, where this surface-reacted precipitated calcium carbonate contains a calcium salt of the above anion that is insoluble and at least partially crystalline formed on at least a part of the surface of the precipitated calcium carbonate.

[0121] The solubilized calcium ions described above correspond to excess solubilized calcium ions compared to solubilized calcium ions naturally formed by the dissolution of precipitated calcium carbonate by H3O + ions, and this H3O + ions are provided exclusively in the form of counterions to the anion, i.e., exclusively through the addition of an anion in the form of an acid or non-calcium acid salt and in the absence of any further calcium ions or calcium ion sources.

[0122] The excess solubilized calcium ions described above are preferably provided by the addition of a soluble neutral or acidic calcium salt, or by the addition of an acid or neutral or acidic non-calcium salt that generates a soluble neutral or acidic calcium salt in situ.

[0123] The above H3O + ions may be provided by the addition of an acid or an acidic salt of the above anion, or by the addition of an acid or acidic salt that acts simultaneously to provide all or part of the above excess solubilized calcium ions.

[0124] In a further preferred embodiment of the production of surface-reacted natural ground calcium carbonate or precipitated calcium carbonate, natural ground calcium carbonate or precipitated calcium carbonate is reacted with an acid and / or carbon dioxide in the presence of at least one compound selected from the group consisting of silicates, silica, aluminum hydroxide, alkaline earth aluminates such as sodium or potassium aluminate, magnesium oxide, or mixtures thereof. Preferably, at least one silicate is selected from aluminum silicate, calcium silicate, or silicates of alkaline earth metals. These components can be added to an aqueous suspension containing natural ground calcium carbonate or precipitated calcium carbonate prior to the addition of the acid and / or carbon dioxide.

[0125] Alternatively, silicate and / or silica and / or aluminum hydroxide and / or alkaline earth aluminate and / or magnesium oxide components can be added to an aqueous suspension of natural or precipitated calcium carbonate, while the reaction of natural or precipitated calcium carbonate with an acid and carbon dioxide has already started. Further details regarding the production of surface-reacted natural or precipitated calcium carbonate in the presence of at least one silicate and / or silica and / or aluminum hydroxide and / or alkaline earth aluminate component are disclosed in International Publication No. WO 2004 / 083316 A1, the content of which is incorporated herein by reference.

[0126] The surface-reacted calcium carbonate can be held in suspension and further stabilized, if necessary, with a dispersant. Conventional dispersants known to those skilled in the art can be used. Preferred dispersants consist of polyacrylic acid and / or carboxymethyl cellulose.

[0127] Alternatively, the above aqueous suspension can be dried, thereby obtaining surface-reacted natural ground calcium carbonate or precipitated calcium carbonate in solid form (i.e., substantially free of water that is either dried or not in fluid form) in granular or powder form.

[0128] Surface-reacted calcium carbonate can have various particle shapes, such as, for example, the shape of a rose, a golf ball, and / or a brain.

[0129] According to one embodiment, the surface-reacted calcium carbonate has a specific surface area of 15 m 2 / g to 200 m 2 / g, preferably 20 m 2 / g to 180 m 2 / g, more preferably 25 m 2 / g to 160 m 2 / g, most preferably 70 m 2 / g to 120 m 2 / g, measured using nitrogen and the BET method. In the context of the present invention, the BET specific surface area is defined as the surface area of the particles divided by the mass of the particles. As used herein, the specific surface area is measured by adsorption using the BET isotherm (ISO 9277:2010) and is specified in m 2 / g.

[0130] The inventors have surprisingly found that the use of surface-reacted calcium carbonate having a specific surface area of 70 m 2 / g to 120 m 2 / g as the second component of a calcium carbonate-based composition results in a further improved anti-caking effect and / or improved flow properties.

[0131] According to one embodiment, the surface-reacted calcium carbonate has a volume median particle size d 50 of 0.1 to 75 μm, preferably 0.5 to 50 μm, more preferably 1 to 40 μm, even more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm.

[0132] Furthermore, the surface-reacted calcium carbonate particles have a volume top cut particle size d 98 of 2 to 150 μm, preferably 4 to 100 μm, more preferably 6 to 80 μm, even more preferably 8 to 60 μm, even more preferably 8 to 30 μm, and most preferably 12 to 25 μm.

[0133] Value d x represents the diameter related to the fact that x% of the particles have a diameter less than d x . This means that the d 98 value is such that 98% of all the particles have a particle size smaller than this value. The d 98 value is also called the "top cut". The d x value can be expressed in volume % or weight %. Thus, the d 50 (wt) value is the weight median particle size, that is, 50 wt% of all the particles are smaller than this particle size, and the d 50 (vol) value is the volume median particle size, that is, 50 vol% of all the particles are smaller than this particle size.

[0134] The volume median particle size d 50 was evaluated using a Malvern Mastersizer 2000 laser diffraction system or a Malvern Mastersizer 3000 laser diffraction system. The d measured using a Malvern Mastersizer 2000 laser diffraction system or a Malvern Mastersizer 3000 laser diffraction system 50 or d 98 values respectively indicate diameter values such that 50 vol% or 98 vol% of the particles have a diameter smaller than this value. The raw data obtained by measurement was analyzed using Mie theory with a particle refractive index of 1.57 and an absorption coefficient of 0.005. The measurement was carried out in a 0.1 wt% aqueous solution of Na4P2O7.

[0135] The weight median particle size is measured by the sedimentation method, which is an analysis of the sedimentation behavior in a weight measurement field. The measurement is carried out using a Sedigraph® 5100 or 5120 of Micromeritics Instrument Corporation. This method and apparatus are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. The measurement is carried out in a 0.1 wt% aqueous solution of Na4P2O7. The sample was dispersed using a high-speed stirrer and subjected to ultrasonic treatment.

[0136] These methods and apparatuses are known to those skilled in the art and are commonly used to determine the particle sizes of fillers and pigments.

[0137] The specific pore volume is measured using mercury intrusion porosimetry with a Micromeritics Autopore IV 9620 mercury porosimeter having a maximum applied pressure of mercury of 414 MPa (60,000 psi), which is equivalent to a Laplace throat diameter of 0.004 μm (~nm). The equilibration time used in each pressurization step is 20 seconds. The sample material is sealed in a 5 cm 3 chamber powder penetrometer for analysis. The data is corrected for mercury compression, penetrometer expansion, and sample material 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, 35(5), 1996, pp. 1753-1764).

[0138] The total pore volume found in the cumulative intrusion data can be separated into two regions having intrusion data from 214 μm down to about 1 - 4 μm, indicating that the coarse packing of the sample between any aggregate structures contributes strongly. Below these diameters, there is fine interparticle packing of the particles themselves. If the particles also have intraparticle pores, this region is bimodal, and the intraparticle specific pore volume is defined with the specific pore volume of mercury intruded into pores finer than, i.e., finer than the inflection point of the bimodality, the mode conversion point. The sum of these three regions gives the total pore volume of the powder, but is strongly influenced by the precipitation of the powder at the coarse pore ends of the original sample's compression / distribution.

[0139] By taking the first derivative of the cumulative intrusion curve, the pore size distribution based on the equivalent Laplace diameter including pore blockage is inevitably revealed. Its differential curve clearly shows the pore structure region of coarse aggregates, the inter-particle pore region, and, if present, the intra-particle pore region. If the intra-particle pore size range is known, by subtracting the remaining inter-particle pore volume and the inter-aggregate pore volume from the total pore volume, it is possible to obtain only the desired pore volume of the internal pores as the pore volume per unit mass (as the specific pore volume). Naturally, the same subtraction principle also applies when separating any other pore size region of interest.

[0140] Preferably, the surface-reacted calcium carbonate has an intra-particle intrusion specific pore volume in the range of 0.1 to 2.3 cm 3 / g, more preferably 0.2 to 2.0 cm 3 / g, particularly preferably 0.4 to 1.8 cm 3 / g, most preferably 0.6 to 1.6 cm 3 / g.

[0141] The intra-particle pore size of the surface-reacted calcium carbonate is determined by mercury porosimetry measurement and is preferably in the range of 0.004 to 1.6 μm, more preferably 0.005 to 1.3 μm, particularly preferably 0.006 to 1.15 μm, most preferably 0.007 to 1.0 μm, for example, in the range of 0.004 to 0.16 μm.

[0142] According to an exemplary embodiment, the surface-reacted calcium carbonate has a volume median particle size d of 1.5 to 15 μm, preferably 4 to 8 μm 50 ; a specific surface area of 30 to 140 m 2 / g, preferably 30 to 90 m 2 / g measured using nitrogen and the BET method; and an intra-particle intrusion specific pore volume of 0.2 to 2.0 cm 3 , preferably 0.6 to 1.6 cm 3 .

[0143] According to another exemplary embodiment, the surface reactive calcium carbonate has a volume median particle size d of 5 to 9 μm 50 ; a specific surface area of 45 to 85 m 2 / g measured using nitrogen and the BET method; and a volume top cut particle size d of 13 to 20 μm 98 .

[0144] Due to the pore and interpore structure of the surface reactive calcium carbonate, the surface reactive calcium carbonate can be an excellent agent (acting agent) for delivering previously adsorbed and / or absorbed substances over time compared to normal substances having a similar specific surface area. Thus, generally, any agent that fits within the intra- and / or inter-particle pores of the surface reactive calcium carbonate is suitable for being transported by the surface reactive calcium carbonate according to the present invention. For example, active agents selected from the group including pharmaceutically active agents, biologically active agents, bactericides, preservatives, fragrances, surfactants, oils, flavoring agents, essential oils, and mixtures thereof can be used. According to one embodiment, at least one active agent is used in the surface reactive calcium carbonate.

[0145] According to one embodiment of the present invention, the surface reactive calcium carbonate comprises at least one water-insoluble and at least partially crystalline calcium salt of an anion of an acid formed on the surface of natural ground calcium carbonate or precipitated calcium carbonate. According to one embodiment, the water-insoluble and at least partially crystalline salt of the anion of at least one acid at least partially, preferably completely covers the surface of the natural ground calcium carbonate or precipitated calcium carbonate. Depending on the at least one acid used, the anion may be a sulfate anion, a sulfite anion, a phosphate anion, a citrate anion, an oxalate anion, an acetate anion, a formate anion, and / or a chloride anion.

[0146] According to one embodiment, the surface reactive calcium carbonate has the following: (i) a specific surface area of 15 to 200 m 2 / g measured using nitrogen and the BET method according to ISO9277:2010, and (ii) The pore volume of intrusion ratio within particles calculated from mercury porosimetry measurement is 0.1 to 2.3 cm 3 / g.

[0147] According to one embodiment, the second component has a volume median particle size d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm, 50 and / or the second component has a specific surface area of 15 m 2 / g to 200 m 2 / g, preferably 20 m 2 / g to 180 m 2 / g, more preferably 25 m 2 / g to 160 m 2 / g, and most preferably 70 m 2 / g to 120 m 2 / g, as measured using nitrogen and the BET method.

[0148] According to one embodiment, the second component has a volume median particle size d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm, 50 and the second component has a specific surface area of 15 m 2 / g to 200 m 2 / g, preferably 20 m 2 / g to 180 m 2 / g, more preferably 25 m 2 / g to 160 m 2 / g, and most preferably 70 m 2 / g to 120 m 2 / g, as measured using nitrogen and the BET method.

[0149] According to one preferred embodiment, the second component, which is surface-reactive calcium carbonate, has a specific surface area of 20 m 2 / g to 180 m 2 / g, preferably 25 m 2 / g to 160 m 2 / g, and most preferably 70 m 2 / g~120 m 2 The specific surface area of / g, the volume median particle size d of 1.2 to 30 μm, preferably 1.5 to 15 μm, most preferably 3 to 10 μm 50 , and / or the volume top cut particle size d of 8 to 60 μm, even more preferably 8 to 30 μm, most preferably 12 to 25 μm 98 has.

[0150] According to one preferred embodiment, the second component, which is surface-reacted calcium carbonate, has a specific surface area of 20 m 2 / g to 180 m 2 / g, preferably 25 m 2 / g to 160 m 2 / g, most preferably 90 m 2 / g to 120 m 2 The specific surface area of / g, the volume median particle size d of 1.2 to 30 μm, preferably 1.5 to 15 μm, most preferably 3 to 10 μm 50 , and the volume top cut particle size d of 8 to 60 μm, even more preferably 8 to 30 μm, most preferably 12 to 25 μm 98 has.

[0151] According to a preferred embodiment, the calcium carbonate-based composition comprises: a first component that is natural ground calcium carbonate, and a second component that is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O + ion donor, and the carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source.

[0152] According to a preferred embodiment, the calcium carbonate-based composition comprises: a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, most preferably 0.8 to 8 μm 50A first component that is natural ground calcium carbonate having, and A second component that is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, The surface-reacted calcium carbonate has a volume median particle size d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm. 50 Having.

[0153] According to a preferred embodiment, the calcium carbonate-based composition comprises: A first component that is natural ground calcium carbonate having a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm, and 50 A second component that is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O ion donor, and this carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, + The surface-reacted calcium carbonate has a volume median particle size d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm and has, and 50 At least one H3O ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acid salts, acetic acid, formic acid, and mixtures thereof, + Preferably, at least one H3O ​+ The ion donor is hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid; Li + , Na + or K + and is at least partially neutralized by a cation selected from H2PO4 - ; Li + , Na + , K + , Mg 2+ and / or Ca 2+ and is at least partially neutralized by a cation selected from HPO4 2- ; and is selected from the group consisting of these mixtures, more preferably, at least one H3O + The ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, or mixtures thereof, most preferably, at least one H3O + The ion donor is phosphoric acid.

[0154] According to a preferred embodiment, the calcium carbonate-based composition comprises: A first component which is natural ground calcium carbonate having a volume median particle size d of 0.5 to 10 μm, preferably 0.8 to 8 μm 50 , and A second component which is surface-reacted calcium carbonate wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, The surface-reacted calcium carbonate has a volume median particle size d of 1.5 to 15 μm, preferably 3 to 10 μm 50 , and at least one H3O + The ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, and mixtures thereof, preferably, at least one H3O +The ion donor is phosphoric acid.

[0155] The first component and the second component can be present in a calcium carbonate-based composition in a specific total amount.

[0156] According to one preferred embodiment, the first component and the second component can be present in a calcium carbonate-based composition in an amount in the range of 80 to 100% by weight, more preferably 90 to 100% by weight, even more preferably 95 to 100% by weight, and most preferably 98 to 100% by weight, based on the total amount of the calcium carbonate-based composition.

[0157] According to one preferred embodiment, the calcium carbonate-based composition consists of the first component and the second component.

[0158] Furthermore, the first component and the second component can be present in a calcium carbonate-based composition in a specific weight ratio.

[0159] According to one preferred embodiment, the weight ratio of the first component to the second component (first component: second component) is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 10:90, even more preferably in the range of 90:10 to 20:80, even more preferably in the range of 85:15 to 30:70, and most preferably in the range of 80:20 to 40:60.

[0160] According to one preferred embodiment, the weight ratio of the first component to the second component is in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:50.

[0161] According to another preferred embodiment, the weight ratio of the first component to the second component is in the range of 98:2 to 2:98, preferably in the range of 95:5 to 5:95, even more preferably in the range of 90:10 to 10:90, even more preferably in the range of 85:15 to 15:85, and most preferably in the range of 80:20 to 20:80.

[0162] According to one preferred embodiment, the weight ratio of the first component to the second component ranges from 85:15 to 30:70. According to a more preferred embodiment, the weight ratio of the first component to the second component ranges from 80:20 to 40:60.

[0163] The inventors have surprisingly found that the anti-caking effect brought about by the calcium carbonate-based composition is particularly remarkable when the first and second components are used in a specific weight ratio as shown above.

[0164] According to a preferred embodiment, the calcium carbonate-based composition comprises, preferably consists of: a first component that is natural ground calcium carbonate, and a second component that is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O + ion donor, and the carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, The weight ratio of the first component to the second component ranges from 98:2 to 2:98, preferably from 95:5 to 5:95, more preferably from 90:10 to 10:90, even more preferably from 85:15 to 15:85, and most preferably from 80:20 to 20:80.

[0165] According to a preferred embodiment, the calcium carbonate-based composition comprises, preferably consists of: a first component that is natural ground calcium carbonate having a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm, and 50 a second component that is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O ion donor,+ It is a reaction product with an ion donor, and this carbon dioxide is at least one H3O + It is formed in situ by treatment with an ion donor and / or supplied from an external source. This surface-reacted calcium carbonate has a volume median particle size d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm 50 and The weight ratio of the first component to the second component ranges from 98:2 to 2:98, preferably from 95:5 to 5:95, even more preferably from 90:10 to 10:90, even more preferably from 85:15 to 15:85, and most preferably from 80:20 to 20:80.

[0166] The calcium carbonate-based composition can have a particle size distribution on a specific volume basis.

[0167] According to one embodiment, the particle size distribution on a volume basis is multimodal, preferably bimodal.

[0168] The inventors have found that using a calcium carbonate-based composition having a multimodal particle size distribution is more advantageous, for example, than using a calcium carbonate-based composition having a unimodal particle size distribution.

[0169] According to one embodiment, the calcium carbonate-based composition has a volume-based median particle size d in the range of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm 50 and has.

[0170] In one embodiment, the calcium carbonate-based composition has a volume top cut particle size d of 2 to 80 μm, preferably 4 to 60 μm, even more preferably 8 to 30 μm, and most preferably 12 to 25 μm 98 and has.

[0171] In one embodiment, the calcium carbonate-based composition has a volume-based median particle size d in the range of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm 50 , and a volume top cut particle size d of 2 to 80 μm, preferably 4 to 60 μm, even more preferably 8 to 30 μm, and most preferably 12 to 25 μm 98 .

[0172] According to one embodiment, the calcium carbonate-based composition is a solid composition.

[0173] It is more preferable that the calcium carbonate-based composition has a specific residual moisture content.

[0174] According to one preferred embodiment, the calcium carbonate-based composition has a residual moisture of less than 10.0% by weight, preferably less than 7.5% by weight, and more preferably less than 5.0% by weight based on the total weight of the calcium carbonate-based composition.

[0175] The use of the calcium carbonate-based composition as an anti-caking agent is not basically limited to specific basic components, namely, specific granular compositions to which an anti-caking agent is added.

[0176] According to one embodiment, the calcium carbonate-based composition is added as an anti-caking agent to the basic components.

[0177] Suitable basic components are, for example, food compositions, feed compositions, dietary supplement compositions, pharmaceutical compositions, and cosmetic compositions. According to one embodiment, the calcium carbonate-based composition is added as an anti-caking agent to a basic component selected from the group consisting of food compositions, feed compositions, dietary supplement compositions, pharmaceutical compositions, and cosmetic compositions, and preferably, the basic component is selected from food compositions or feed compositions.

[0178] Preferably, the food composition is salt, curing salt, salt substitute, milk powder, non-fat milk powder, cream powder, egg powder, whey fat powder, powdered protein, vending machine powder, powdered cheese, sugar, powdered food flavor, spice, seasoning, packet soup mixture, baking mixture, pudding powder, mousse powder, or sauce powder.

[0179] Preferably, the feed composition is pet food, animal milk replacer, or animal inorganic salt.

[0180] Preferably, the pharmaceutical composition is a pharmaceutical composition provided in the dosage form of powder or granule.

[0181] Preferably, the cosmetic composition is eye shadow, powder makeup, lip powder, face powder, body powder, or blusher.

[0182] Preferably, the dietary supplement composition is a food additive or food supplement such as vitamins, herbs, minerals, enzyme powder, amino acid powder, protein powder, or salts.

[0183] The basic component can have a specific particle size distribution. According to one embodiment, the basic component has a volume median particle diameter d in the range of 1 μm to 10 mm, preferably 5 μm to 5 mm, more preferably 10 μm to 1 mm, still more preferably 20 μm to 500 μm, and most preferably 20 μm to 100 μm. 50 to have.

[0184] According to one preferred embodiment, the basic component is a food composition or a feed composition, preferably a food composition, and has a volume median particle diameter d in the range of 1 μm to 10 mm, preferably 5 μm to 5 mm, more preferably 10 μm to 1 mm, still more preferably 20 μm to 500 μm, and most preferably 20 μm to 100 μm. 50 to have.

[0185] According to one preferred embodiment, the base component is a milk powder having a volume median particle diameter d in the range of 10 μm to 1 mm, preferably 20 μm to 500 μm, and most preferably 20 μm to 100 μm. 50 It is milk powder having 50 .

[0186] Furthermore, a calcium carbonate-based composition can be added to the base component as an anti-caking agent in a specific amount.

[0187] According to one embodiment, the calcium carbonate-based composition is added to the base component in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the base component and the calcium carbonate-based composition.

[0188] According to one preferred embodiment, the calcium carbonate-based composition is added to the base component in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the base component and the calcium carbonate-based composition. Most preferably, the calcium carbonate-based composition is added to the base component in an amount of 0.3 to 2.5% by weight (for example, 1.0% by weight) based on the total weight of the base component and the calcium carbonate-based composition.

[0189] According to one preferred embodiment, the calcium carbonate-based composition is added to the base component in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the base component and the calcium carbonate-based composition, wherein the base component is a food composition or a feed composition. Most preferably, the calcium carbonate-based composition is added to the base component in an amount of 0.3 to 2.5% by weight (for example, 1.0% by weight) based on the total weight of the base component and the calcium carbonate-based composition, wherein the base component is a food composition or a feed composition.

[0190] Another embodiment of the present invention relates to a method for reducing or preventing caking of a granular composition, the method comprising the step of adding a calcium carbonate-based composition as a basic component, the calcium carbonate-based composition comprising a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, the carbon dioxide being formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source.

[0191] Preferred embodiments of the method for reducing or preventing caking of a granular composition (e.g., calcium carbonate-based composition, its first component, its second component, basic component, etc.) are described above.

[0192] Granular composition Another aspect of the present invention relates to a granular composition comprising a calcium carbonate-based anti-caking composition and a basic component, wherein the calcium carbonate-based anti-caking composition comprises a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, the surface-reacted calcium carbonate being a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, the carbon dioxide being formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, the granular composition comprising the calcium carbonate-based anti-caking composition in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition.

[0193] According to one preferred embodiment, the granular composition is a solid composition. According to one preferred embodiment, the granular composition is a dry solid composition. According to one preferred embodiment, the granular composition is a dry solid composition, and this dry solid composition contains less than 20.0% by weight, preferably less than 10% by weight, more preferably less than 7.5% by weight of residual moisture based on the total weight of the granular composition.

[0194] The granular composition according to the present invention includes a calcium carbonate-based anti-caking composition and a basic component. Preferably, the granular composition consists of a calcium carbonate-based anti-caking composition and a basic component.

[0195] The calcium carbonate-based anti-caking composition should be understood to correspond to the calcium carbonate-based composition for use as the above-mentioned anti-caking agent. Preferred embodiments, the first component and the second component of the calcium carbonate-based anti-caking composition are described in the foregoing section.

[0196] The granular composition according to the present invention includes a basic component.

[0197] Suitable basic components are, for example, food compositions, feed compositions, dietary supplement compositions, pharmaceutical compositions, and cosmetic compositions. According to one preferred embodiment, the basic component is selected from the group consisting of food compositions, feed compositions, dietary supplement compositions, pharmaceutical compositions, and cosmetic compositions, and preferably is a food composition or a feed composition.

[0198] Preferably, the food composition is salt, curing salt, salt substitute, powdered milk, skimmed milk powder, cream powder, egg powder, whey fat powder, powdered protein, vending machine powder, powdered cheese, sugar, powdered food flavor, spice, seasoning, packet soup mixture, baking mixture, pudding powder, mousse powder, or sauce powder.

[0199] Preferably, the feed composition is pet food, animal milk replacer, or animal inorganic salts.

[0200] Preferably, the pharmaceutical composition is a pharmaceutical composition provided in the dosage form of powder or granules.

[0201] Preferably, the cosmetic composition is eyeshadow, powder makeup, lip powder, face powder, body powder, or a blusher.

[0202] Preferably, the dietary supplement composition is a food additive or food supplement such as vitamins, herbs, minerals, enzyme powder, amino acid powder, protein powder, or salts.

[0203] The basic component can have a specific particle size distribution. According to one embodiment, the basic component has a volume median particle diameter d in the range of 1 μm to 10 mm, preferably 5 μm to 5 mm, more preferably 10 μm to 1 mm, still more preferably 20 μm to 500 μm, and most preferably 20 μm to 100 μm. 50 having.

[0204] According to one preferred embodiment, the basic component is a food composition or a feed composition, preferably a food composition, and has a volume median particle diameter d in the range of 1 μm to 10 mm, preferably 5 μm to 5 mm, more preferably 10 μm to 1 mm, still more preferably 20 μm to 500 μm, and most preferably 20 μm to 100 μm. 50 having.

[0205] According to one preferred embodiment, the basic component is powdered milk having a volume median particle diameter d in the range of 10 μm to 1 mm, preferably 20 μm to 500 μm, and most preferably 20 μm to 100 μm. 50 having.

[0206] The granular composition according to the present invention contains an anti-caking composition based on calcium carbonate in an amount of 0.1 to 50% by weight.

[0207] According to a preferred embodiment, the granular composition comprises an anti-caking composition based on calcium carbonate in an amount of 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition.

[0208] According to one embodiment, the granular composition comprises an anti-caking composition based on calcium carbonate in an amount of 0.2 to 5% by weight, based on the total weight of the granular composition.

[0209] According to one embodiment, the granular composition comprises an anti-caking composition based on calcium carbonate in an amount of 0.3 to 2.5% by weight (e.g., 1.0% by weight), based on the total weight of the granular composition.

[0210] According to one preferred embodiment, the granular composition comprises an anti-caking composition based on calcium carbonate and a basic component, The anti-caking composition based on calcium carbonate comprises a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and a second component that is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and the carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, The granular composition comprises an anti-caking composition based on calcium carbonate in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition. The first component and the second component are present in the calcium carbonate-based anti-caking composition in an amount in the range of 80 to 100% by weight, more preferably 90 to 100% by weight, even more preferably 95 to 100% by weight, and most preferably 98 to 100% by weight, based on the total amount of the calcium carbonate-based anti-caking composition, and / or The weight ratio of the first component to the second component in the calcium carbonate-based anti-caking composition is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 20:80, even more preferably in the range of 90:10 to 30:70, even more preferably in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:50.

[0211] According to one preferred embodiment, the granular composition comprises a calcium carbonate-based anti-caking composition and a basic component, The calcium carbonate-based anti-caking composition consists of a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, The granular composition contains the calcium carbonate-based anti-caking composition in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition, and The weight ratio of the first component to the second component in the calcium carbonate-based anti-caking composition is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 20:80, even more preferably in the range of 90:10 to 30:70, even more preferably in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:50.

[0212] According to one preferred embodiment, the granular composition comprises an anti-caking composition based on calcium carbonate and a basic component, The anti-caking composition based on calcium carbonate consists of a first component which is natural ground calcium carbonate and a second component which is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with at least one H3O + ion donor and / or supplied from an external source, The granular composition contains an anti-caking composition based on calcium carbonate in an amount of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition, The weight ratio of the first component to the second component in the anti-caking composition based on calcium carbonate is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 20:80, more preferably in the range of 90:10 to 30:70, still more preferably in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:50.

[0213] According to one preferred embodiment, the granular composition comprises an anti-caking composition based on calcium carbonate and a basic component, preferably consists of an anti-caking composition based on calcium carbonate and a basic component, where the basic component is a food composition or a feed composition, The anti-caking composition based on calcium carbonate consists of a first component which is natural ground calcium carbonate and a second component which is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate with carbon dioxide and at least one H3O + ion donor, and this carbon dioxide is formed in situ by treatment with at least one H3O +formed in situ by treatment with an ion donor and / or supplied from an external source, The granular composition contains an anti-caking composition based on calcium carbonate in an amount of 0.2 to 5 wt%, most preferably 0.3 to 2.5 wt%, based on the total weight of the granular composition, and The weight ratio of the first component to the second component in the anti-caking composition based on calcium carbonate is in the range of 90:10 to 30:70, even more preferably in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:50.

[0214] Method for producing a granular composition Another aspect of the present invention relates to a method for producing a granular composition, The method includes a step of mixing an anti-caking composition based on calcium carbonate as a basic component, The anti-caking composition based on calcium carbonate includes a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and a second component that is surface-reacted calcium carbonate, where the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H3O + ion donor, and the carbon dioxide is at least one H3O + formed in situ by treatment with an ion donor and / or supplied from an external source, and The anti-caking composition based on calcium carbonate is mixed with the basic component in an amount of 0.1 to 50 wt%, preferably 0.1 to 20 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.2 to 5 wt%, and most preferably 0.3 to 2.5 wt%, based on the total weight of the granular composition.

[0215] According to one embodiment, the anti-caking composition based on calcium carbonate and / or the basic component is provided in solid form.

[0216] According to a preferred embodiment, a calcium carbonate-based anti-caking composition and a basic component are provided in solid form.

[0217] Preferably, the calcium carbonate-based anti-caking composition and / or the basic component are provided in a dry state. According to one embodiment, the calcium carbonate-based anti-caking composition and / or the basic component are provided in a dry state, wherein the calcium carbonate-based anti-caking composition and / or the basic component have a residual moisture content of less than 10% by weight, preferably less than 8% by weight.

[0218] According to one embodiment, the calcium carbonate-based anti-caking composition and the basic component are provided in a dry state, wherein the calcium carbonate-based anti-caking composition and / or the basic component have a residual moisture content of less than 10% by weight, preferably less than 8% by weight.

[0219] The mixing step is preferably a dry blending step. Preferably, the dry blending step is carried out using a plowshare mixer, a ribbon mixer, or a cone single shaft mixer. Those skilled in the art are familiar with such types of mixers and mixing methods.

[0220] According to a preferred embodiment, the method includes the following steps: Providing a calcium carbonate-based anti-caking composition in solid form, preferably in a dry state, and a basic component in solid form, preferably in a dry state, Mixing the calcium carbonate-based anti-caking composition with the basic component, wherein this mixing is a dry blending step.

[0221] The method can include further steps such as packaging the resulting granular composition. Thus, according to one embodiment, the method includes the following steps: Providing an anti-caking composition based on calcium carbonate in solid form, preferably in dry state, and a basic component in solid form, preferably in dry state. Mixing an anti-caking composition based on calcium carbonate with a basic component, wherein this mixing is a dry blending step, and Packaging the obtained granular composition.

[0222] Mix the calcium carbonate-based anti-caking composition with the basic component in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition.

[0223] In a preferred embodiment, the calcium carbonate-based anti-caking composition is mixed with the basic component in an amount of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition.

[0224] In a preferred embodiment, the calcium carbonate-based anti-caking composition is mixed with the basic component in an amount of 0.3 to 2.5% by weight (for example, 1.0% by weight) based on the total weight of the granular composition.

Brief Description of the Drawings

[0225] [FIG. 1] Figure 1 shows the normalized basic flow energy (BFEnorm) measured for milk protein without additives, milk protein containing ground calcium carbonate or surface-reacted calcium carbonate, and milk protein containing the anti-caking agent of the present invention. [FIG. 2] Figure 2 shows the normalized basic flow energy (BFEnorm) measured for powdered milk without additives, powdered milk containing ground calcium carbonate or surface-reacted calcium carbonate, and powdered milk containing the anti-caking agent of the present invention. [FIG. 3]Figure 3 shows the aeration rates measured for milk protein without additives, milk protein containing ground calcium carbonate or surface-reacted calcium carbonate, and milk protein containing the anti-caking agent of the present invention. [FIG. 4] Figure 4 shows the aeration rates measured for powdered milk without additives, powdered milk containing ground calcium carbonate or surface-reacted calcium carbonate, and powdered milk containing the anti-caking agent of the present invention. [FIG. 5] Figure 5 shows the caking crust analysis for spice mix without additives, spice mix containing ground calcium carbonate or surface-reacted calcium carbonate, and spice mix containing the anti-caking agent of the present invention. The values on the y-axis correspond to the peak width in the total energy plot recorded by the rheometer and are related to the caking crust of the spice mix. [FIG. 6] Figure 6 shows the caking crust analysis measured for powdered milk without additives, powdered milk containing ground calcium carbonate or surface-reacted calcium carbonate, and powdered milk containing the anti-caking agent of the present invention. The values on the y-axis correspond to the peak width in the total energy plot recorded by the rheometer and are related to the caking crust of the powdered milk.

Examples

[0226] 1. Materials Calcium carbonate material : GCC1: Natural ground calcium carbonate; marble from Kemalpasa, Turkey; volume-based particle size distribution d 50 = 2.2 μm, d 98 = 10 μm; specific surface area = 1.4 m 2 / g GCC2: Natural ground calcium carbonate; marble from Arizona, USA; volume-based particle size distribution d 50 = 2.2 μm, d 98 = 9 μm; specific surface area = 1.3 m 2 / g SRCC: Surface-reacted calcium carbonate (SRCC) (d 50 (vol) = 5.1 μm, d 98(vol)=9.2 μm, specific surface area = 96.1 m 2 / g, internal particle intrusion ratio pore volume 1.588 cm 3 / g (pore diameter range of 0.004 - 0.4 μm)

[0227] Production of SRCC : In a mixing container, a solid of ground calcium carbonate having a particle size distribution with less than 2 μm being 90% by weight with respect to the total weight of the ground calcium carbonate was prepared so as to obtain a solid content of 15% by weight with respect to the total weight of the aqueous suspension, thereby producing a 10 - liter aqueous suspension of ground calcium carbonate. While mixing the slurry, 2.8 kg of phosphoric acid was added to the above suspension over a period of 10 minutes in the form of an aqueous solution containing 30% by weight phosphoric acid. Throughout the entire experiment, the temperature of the suspension was maintained at 70°C. After the addition of the acid, the suspension was stirred for an additional 5 minutes and then taken out of the container and dried.

[0228] The calcium carbonate-based composition (CCC) of the present invention : The ground calcium carbonate is a mixture of ground calcium carbonate and surface - reacted calcium carbonate in a ratio of 70:30.

[0229] The ground calcium carbonate used for the calcium - carbonate - based composition of the present invention has a volume - based particle size distribution d 50 = 2.2 μm, d 98 = 9 μm; specific surface area = 1.3 m 2 / g and is GCC2.

[0230] The surface - reacted calcium carbonate used for the calcium - carbonate - based composition of the present invention has a volume - based particle size distribution d 50 = 5.1 μm, d 98 = 9.2 μm; specific surface area = 96.1 m 2 / g and is SRCC.

[0231] Basic component : Milk powder: Obtained from Hofdorf, Switzerland, volume - based particle size distribution d 50 = 61 μm Milk protein: obtained from Horwoldt, Switzerland, volume-based particle size distribution d 50 = 46 μm

[0232] 2. Method Basic fluid energy (BFE) and normalized basic fluid energy (BFE norm ) : The basic flow energy (BFE) is calculated from the work done in moving a blade through a test powder composition from the top to the bottom of a container, i.e., the work done during a downward traverse. To minimize the effect of bulk density, the BFE is normalized by the mass of powder in a given volume. The apparatus used to determine the BFE and BFE norm was an FT4 Powder Rheometer® (Freeman Technology Ltd). Accessories of the apparatus such as blades can be rotated while measuring axial and rotational pressures and simultaneously moved axially into a powder sample. Several control modes are available on both axes, including speed, force, and torque. In a standard dynamic test, the aeration test is automated without operator involvement apart from sample preparation. In the dynamic test, a 48 mm diameter blade was used and a 160 mL powder sample was contained in a 50 mm borosilicate test container. All samples for the dynamic test were pre-conditioned using the "conditioning" method of the apparatus. The "conditioning" blade operation gently stirs the powder bed to create a uniform, slightly compacted test sample that can be easily and consistently reproduced. The basic flow energy of the powder is obtained from the force and torque measured during the downward movement of the blade. The BFE was measured using the standard program of the FT4 powder rheometer in the next conditioning cycle and test cycle. Downward traverse conditioning: 5° (helix angle), -60 mm / sec (tip speed); upward traverse conditioning: -5° (helix angle), 60 mm / sec (tip speed) Test: -5° (helix angle), -100 mm / sec (tip speed)

[0233] Aeration test and aeration rate : For the aeration test, the aeration program of the Freeman FT4 Powder Rheometer (registered trademark) was used. For the aeration test, air is introduced at the bottom of the powder column. Then, by measuring the decrease in the basic flow energy, it is measured how the introduction of air changes the flow characteristics. The aeration test is carried out at an air flow rate of 18 mm / second. The aeration rate is the ratio of BFE (in the absence of air) to BFE at an air flow rate of 18 mm / second in the powder composition. The aeration rate is inversely proportional to the cohesivity of the powder composition. The aeration rate was calculated using the method of the FT4 powder rheometer in the following conditioning cycle and test cycle. Downward cross-conditioning: 5° (helix angle), -60 mm / second (tip speed); upward cross-conditioning: 20° (helix angle), 60 mm / second (tip speed) Test: -5° (helix angle), -100 mm / second (tip speed)

[0234] Caking test : The rheological behavior of the powder compositions was evaluated by measuring the flow energy of the samples before and after caking using an FT4 Powder Rheometer (registered trademark) (Freeman Technology) to quantify the flow resistance. All samples were conditioned before being subjected to a relative humidity of 75% RH. The samples were conditioned by placing them in a 25 mm x 25 mL cylindrical container and passing a specially shaped blade through the powder in a defined pattern using a powder rheometer. This creates a stable, uniform, and reproducible stress state within the sample. Excess material was removed to create a 25 mL test sample, which was then stored in a constant 75% RH environment for 48 hours (for milk powder) or 144 hours (for spice mix) to induce powder caking. The use of a saturated sodium chloride solution maintained the inside of the desiccator at a fixed relative humidity of 75%. Caking creates a crust on top of the sample, resulting in a peak appearing in the total energy plot recorded by the rheometer. Powder caking was quantified by analyzing the peak width corresponding to the depth of the caking crust. The more caking occurs in the powder, the wider the peak becomes. Thus, a larger value of the peak width indicates more caking, and a smaller value of the peak width indicates less caking.

[0235] The caking test was performed using the method of the FT4 powder rheometer in the following conditioning cycle and test cycle. Downward traverse conditioning: 5° (helix angle), -40 mm / sec (tip speed); upward traverse conditioning: 5° (helix angle), 40 mm / sec (tip speed) Test: -5° (helix angle), -100 mm / sec (tip speed)

[0236] 3. Results Figure 1 shows the BFE measured using milk protein as the basic component normis shown. For milk proteins containing 1) milk protein without an anti-caking agent, 2) milk protein containing 1.0% by weight of GCC2 based on the total weight of the granular composition, 3) milk protein containing 1.0% by weight of SRCC based on the total weight of the granular composition, and 4) milk protein containing 1.0% by weight of the calcium carbonate-based composition of the present invention based on the total weight of the granular composition, BFE norm was measured.

[0237] Figure 2 shows the BFE measured using skim milk powder as the basic component. norm is shown. In this series of experiments, 1.0% by weight of GCC1 based on the total weight of the granular composition was used as a comparative example instead of GCC2.

[0238] When added to the basic component, it can be understood from Figures 1 and 2 that the calcium carbonate-based composition of the present invention significantly reduces the BFE norm value of the basic component, i.e., skim milk powder or milk protein. Therefore, the composition of the present invention has an excellent anti-caking effect and / or fluidity improvement effect on the basic component. Furthermore, as shown by the lower BFE norm value of the composition containing the anti-caking agent and the basic component of the present invention, Figures 1 and 2 show that the calcium carbonate-based composition of the present invention has an excellent anti-caking effect and / or fluidity improvement effect compared to ground calcium carbonate or surface-reacted calcium carbonate alone. Therefore, there is a synergistic effect in the mixture of GCC / SRCC compared to GCC or SRCC alone, which is particularly surprisingly remarkable.

[0239] Figure 3 shows the aeration rate measured using milk protein as the basic component. The aeration rate was measured for 1) milk protein without an anti-caking agent, 2) milk protein containing 1.0% by weight of GCC1 based on the total weight of the granular composition, 3) milk protein containing 1.0% by weight of SRCC based on the total weight of the granular composition, and 4) milk protein containing 1.0% by weight of the calcium carbonate-based composition of the present invention based on the total weight of the granular composition.

[0240] Figure 4 shows the values of the aeration rate measured using milk powder as the basic component in the same way. In this series of experiments, 1.0 wt% of GCC2 was used as a comparative example instead of GCC1 based on the total weight of the granular composition.

[0241] It can be understood from FIGS. 3 and 4 that when added to the basic component, the calcium carbonate-based composition of the present invention significantly increases the aeration rate of the basic component, i.e., milk powder or milk protein. Therefore, the composition of the present invention has an excellent anti-caking effect and / or fluidity improvement effect on the basic component. Furthermore, as shown by the higher aeration rate of the composition containing the anti-caking agent and the basic component of the present invention, FIGS. 3 and 4 show that the calcium carbonate-based composition of the present invention has an excellent anti-caking effect and / or fluidity improvement effect compared to ground calcium carbonate or surface-reacted calcium carbonate alone. Therefore, there is a synergistic effect in the mixture of GCC / SRCC compared to GCC or SRCC alone, which is particularly surprisingly remarkable.

[0242] Figure 5 shows the values of the peak width measured as described above using spice mix as the basic component. The peak width was measured for 1) a spice mix without an anti-caking agent, 2) a spice mix containing 1 wt% of GCC1 based on the total weight of the granular composition, 3) a spice mix containing 1 wt% of SRCC based on the total weight of the granular composition, and 4) a spice mix containing 1 wt% of the calcium carbonate-based composition of the present invention based on the total weight of the granular composition. As described above, the peak width measured for the samples correlates with the caking crust depth.

[0243] Figure 6 shows the values of the peak width measured in the same way using milk powder as the basic component.

[0244] When added to the base composition, the calcium carbonate-based composition of the present invention can significantly reduce the peak width value of the base composition, i.e., the milk powder or the spice mix, as can be understood from FIGS. 5 and 6. Therefore, the composition of the present invention has an excellent anti-caking effect and / or fluidity improvement effect on the base composition. Furthermore, FIGS. 5 and 6 show that, as indicated by the lower peak depth value of the composition containing the anti-caking agent and the base composition of the present invention, the calcium carbonate-based composition of the present invention has an excellent anti-caking effect and / or fluidity improvement effect compared to ground calcium carbonate or surface-reacted calcium carbonate alone. Therefore, there is a synergistic effect in the GCC / SRCC mixture compared to GCC or SRCC alone, which is particularly surprisingly remarkable. The invention disclosed herein includes the following aspects: [1] Use of a calcium carbonate-based composition as an anti-caking agent, wherein the calcium carbonate-based composition a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and a second component that is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H 3 O + ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H 3 O + ion donor and / or supplied from an external source, Use [2] The use according to [1] above, wherein the calcium carbonate-based composition consists of the first component and the second component [3] The weight ratio of the first component to the second component is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 10:90, more preferably in the range of 90:10 to 20:80, still more preferably in the range of 85:15 to 30:70, and most preferably in the range of 80:20 to 40:60, the use according to [1] or [2] above [4] The first component is natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof, or the first component is precipitated calcium carbonate having a crystal form of aragonite, vaterite, or calcite, and precipitated calcium carbonate selected from the group consisting of mixtures thereof, The use according to any one of [1] to [3] above [5] The surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof with carbon dioxide and at least one H 3 O + ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H 3 O + ion donor and / or supplied from an external source, or The surface-reacted calcium carbonate is a precipitated calcium carbonate selected from the group consisting of precipitated calcium carbonate having a crystal form of aragonite, vaterite, or calcite, and mixtures thereof, and a reaction product of carbon dioxide and at least one H 3 O + ion donor, wherein the carbon dioxide is formed in situ by treatment with the at least one H 3 O + ion donor and / or supplied from an external source, Use according to any one of [1] to [4] above. [6] The at least one H 3O + ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acidic salts, acetic acid, formic acid, and mixtures thereof, Preferably, the at least one H 3 O + ion donor is at least partially neutralized by a cation selected from Li + , Na + and / or K + in H 2 PO 4 - ; at least partially neutralized by a cation selected from Li + , Na + 、K + , Mg 2+ and / or Ca 2+ in HPO 4 2- ; and selected from the group consisting of mixtures thereof, More preferably, the at least one H 3 O + ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, and mixtures thereof, Most preferably, the at least one H 3 O + ion donor is phosphoric acid, Use according to any one of [1] to [5] above. [7] The first component has a volume median particle size d 50 of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, still more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm, and / or The first component has a specific surface area of 0.5 m 2 / g to 30 m 2 / g, preferably 1 m 2 / g to 20 m 2 / g, more preferably 1 m 2 / g to 10 m 2 / g, measured using nitrogen and the BET method, Use according to any one of [1] to [6] above. [8] The second component has a volume median particle size d 50 of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, still more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm, and / or The second component has a specific surface area of 15 m 2 / g to 200 m 2 / g, preferably 20 m 2 / g to 180 m 2 / g, more preferably 25 m 2 / g to 160 m 2 / g, and most preferably 70 m 2 / g to 120 m 2 / g, measured using nitrogen and the BET method, Use according to any one of [1] to [7] above. [9] The calcium carbonate-based composition has a residual moisture of less than 10.0% by weight, preferably less than 7.5% by weight, more preferably less than 5.0% by weight, based on the total weight of the calcium carbonate-based composition, for use according to any one of [1] to [8] above. 。

[10] The calcium carbonate-based composition is added to a basic component selected from the group consisting of a food composition, a feed composition, a dietary supplement composition, a pharmaceutical composition, and a cosmetic composition, and preferably, the basic component is selected from a food composition or a feed composition, for use according to any one of [1] to [9] above.

[11] A granular composition comprising an anti-caking composition based on calcium carbonate and a basic component, wherein the anti-caking composition based on calcium carbonate, a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H 3 O + ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H 3 O + ion donor and / or supplied from an external source, and the granular composition contains the anti-caking composition based on calcium carbonate in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 5% by weight, most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition. Granular composition.

[12] The anti-caking composition based on calcium carbonate consists of the first component and the second component, and / or the weight ratio of the first component to the second component in the anti-caking composition based on calcium carbonate is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 20:80, more preferably in the range of 90:10 to 30:70, still more preferably in the range of 85:15 to 40:60, most preferably in the range of 80:20 to 50:50. The granular composition according to

[11] above.

[13] The granular composition according to

[11] or

[12] above, wherein the basic component is selected from the group consisting of a food composition, a feed composition, a nutritional supplement composition, a pharmaceutical composition, and a cosmetic composition, preferably a food composition or a feed composition.

[14] The food composition is salt, curing salt, salt substitute, powdered milk, skimmed milk powder, cream powder, egg powder, whey fat powder, powdered protein, powder for vending machines, powdered cheese, sugar, powdered food flavor, spice, seasoning, packet soup mixture, baking mixture, pudding powder, mousse powder, or sauce powder, or The feed composition is pet food, animal milk replacer, or animal inorganic salt. The granular composition according to

[13] above.

[15] A method for producing a granular composition, The method includes a step of mixing a calcium carbonate-based anti-caking composition as a basic component, The calcium carbonate-based anti-caking composition is a first component which is natural ground calcium carbonate or precipitated calcium carbonate, and a second component which is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H 3 O + ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H 3 O + ion donor and / or supplied from an external source, and The calcium carbonate-based anti-caking composition is mixed with the basic component in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition. Method.

Claims

1. Use of a calcium carbonate-based composition as an anti-caking agent, wherein the calcium carbonate-based composition is a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and It contains a second component which is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H ３ O ＋ ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H ３ O ＋ ion donor and / or supplied from an external source Use.

2. The use according to claim 1, wherein the calcium carbonate-based composition consists of the first component and a second component.

3. The weight ratio of the first component to the second component is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 10:90, more preferably in the range of 90:10 to 20:80, even more preferably in the range of 85:15 to 30:70, and most preferably in the range of 80:20 to 40:60, the use according to claim 1 or 2.

4. The first component is natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof, or the first component is precipitated calcium carbonate selected from the group consisting of precipitated calcium carbonate having the crystal form of aragonite, vaterite, or calcite, and mixtures thereof, the use according to any one of claims 1 to 3.

5. The surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate selected from the group consisting of marble, chalk, limestone, and mixtures thereof, carbon dioxide, and at least one H ３ O ＋ ion donor, wherein the carbon dioxide is formed in situ by treatment with the at least one H ３ O ＋ ion donor and / or supplied from an external source, or The surface-reacted calcium carbonate is a precipitated calcium carbonate selected from the group consisting of precipitated calcium carbonate having a crystal form of aragonite, vaterite, or calcite, and mixtures thereof, and a reaction product with carbon dioxide and at least one H ３ O ＋ ion donor, wherein the carbon dioxide is formed in situ by treatment with the at least one H ３ O ＋ ion donor and / or supplied from an external source The use according to any one of claims 1 to 4.

6. The at least one H ３ O ＋ ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acid salts, acetic acid, formic acid, and mixtures thereof, Preferably, the at least one H ３ O ＋ ion donor is hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid; H ＋ partially neutralized by a cation selected from Li ＋ , Na ＋ and / or K ２ PO ４ － ; HPO ＋ partially neutralized by a cation selected from Li ＋ , Na ＋ , K ２＋ , Mg ２＋ and / or Ca ４ ２－ ; and is selected from the group consisting of these mixtures, More preferably, the at least one H ３ O ＋ ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, and mixtures thereof, Most preferably, the at least one H ３ O ＋ ion donor is phosphoric acid, The use according to any one of claims 1 to 5.

7. The first component has a volume median particle size d of 0.1 to 50 μm, preferably 0.5 to 40 μm, more preferably 0.5 to 20 μm, even more preferably 0.5 to 10 μm, and most preferably 0.8 to 8 μm ５０ and / or The first component has a specific surface area of 0.5 m ２ / g to 30 m ２ / g, preferably 1 m ２ / g to 20 m ２ / g, more preferably 1 m ２ / g to 10 m ２ / g, measured using the nitrogen and BET methods, The use according to any one of claims 1 to 6.

8. The second component has a volume median particle diameter d of 0.5 to 50 μm, preferably 1 to 40 μm, more preferably 1.2 to 30 μm, even more preferably 1.5 to 15 μm, and most preferably 3 to 10 μm ５０ and / or The second component has a specific surface area measured using nitrogen and the BET method, of 15 m ２ / g to 200 m ２ / g, preferably 20 m ２ / g to 180 m ２ / g, more preferably 25 m ２ / g to 160 m ２ / g, most preferably 70 m ２ / g to 120 m ２ / g, and has a specific surface area of The use according to any one of claims 1 to 7.

9. The calcium carbonate-based composition has a residual moisture content of less than 10.0% by weight, preferably less than 7.5% by weight, more preferably less than 5.0% by weight, based on the total weight of the calcium carbonate-based composition, the use according to any one of claims 1 to 8.

10. The calcium carbonate-based composition is added to a basic component selected from the group consisting of food compositions, feed compositions, dietary supplement compositions, pharmaceutical compositions, and cosmetic compositions, and preferably, the basic component is selected from food compositions or feed compositions, the use according to any one of claims 1 to 9.

11. A granular composition comprising a calcium carbonate-based anti-caking composition and a basic component, wherein the calcium carbonate-based anti-caking composition is a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and a second component that is surface-reacted calcium carbonate, wherein, The surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate, carbon dioxide, and at least one H ３ O ＋ ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H ３ O ＋ ion donor and / or supplied from an external source, The surface-reacted calcium carbonate is the reaction product in which at least one water-insoluble and at least partially crystalline calcium salt of an acid at least partially covers the surface of the natural ground calcium carbonate or precipitated calcium carbonate. The at least one H₃O⁺ ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, and mixtures thereof. The at least one acid anion is selected from the group consisting of chloride anion, sulfate anion, sulfite anion, phosphate anion, dihydrogen phosphate anion, hydrogen phosphate anion, citrate anion, oxalate anion, acetate anion, formate anion, silicate anion, mixtures thereof, and hydrates thereof, and the carbon dioxide formed in situ by treatment with the at least one H₃O⁺ ion donor is carbon dioxide automatically generated by using an acid having a pKa value of 0 or less at 20 °C or an acid having a pKa value of 0 to 2.5 at 20 °C for the treatment with the at least one H₃O⁺ ion donor. The granular composition contains the calcium carbonate-based anti-caking composition in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight, based on the total weight of the granular composition. Granular composition.

12. The calcium carbonate-based anti-caking composition consists of the first component and the second component, and / or the weight ratio of the first component to the second component in the calcium carbonate-based anti-caking composition is in the range of 99:1 to 1:99, preferably in the range of 95:5 to 20:80, more preferably in the range of 90:10 to 30:70, still more preferably in the range of 85:15 to 40:60, and most preferably in the range of 80:20 to 50:

50. The granular composition according to claim 11.

13. The base component is selected from the group consisting of food compositions, feed compositions, dietary supplement compositions, pharmaceutical compositions, and cosmetic compositions, preferably a food composition or a feed composition. The granular composition according to claim 11 or 12.

14. The food composition is salt, curing salt, salt substitute, powdered milk, skimmed milk powder, cream powder, egg powder, whey fat powder, powdered protein, powder for vending machines, powdered cheese, sugar, powdered food flavor, spice, seasoning, packet soup mixture, baking mixture, pudding powder, mousse powder, or sauce powder, or The feed composition is pet food, animal milk replacer, or animal inorganic salt. The granular composition according to claim 13.

15. A method for producing a granular composition, The method includes a step of mixing an anti-caking composition based on calcium carbonate as a basic component, The anti-caking composition based on calcium carbonate is a first component that is natural ground calcium carbonate or precipitated calcium carbonate, and It contains a second component which is surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and at least one H ３ O ＋ ion donor, and the carbon dioxide is formed in situ by treatment with the at least one H ３ O ＋ ion donor and / or supplied from an external source, and mixing the anti-caking composition based on calcium carbonate into the basic component in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 5% by weight, and most preferably 0.3 to 2.5% by weight based on the total weight of the granular composition. Method.

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