KR20070032075A - Method for grinding mineral materials in the presence of thickening agents, resulting aqueous suspensions and use thereof - Google Patents

Abstract

The present invention relates to a process for grinding mineral materials in water in the presence of thickening agents, stable suspensions of mineral materials ground in water, obtained by the process, and aqueous formulations, in particular coating formulations such as aqueous paints, priming coatings. , Ink, surface coatings, sealants, adhesives, glues and other aqueous formulations incorporating mineral substances. The invention also relates to the aqueous formulations of the invention obtained.

Description

METHOD FOR GRINDING MINERAL MATERIALS IN THE PRESENCE OF THICKENING AGENTS, RESULTING AQUEOUS SUSPENSIONS AND USE THEREOF}

The present invention relates to the field of aqueous suspensions of ground mineral materials and their use in aqueous formulations.

Firstly, the present invention relates to a process for grinding mineral material in water in the presence of a thickening agent.

The present invention furthermore relates to a stable suspension of milled mineral material in water, obtained by the process according to the invention.

The invention also relates to aqueous formulations, in particular lining formulations such as, among others, aqueous paints, primers, inks, coatings, sealants, adhesives, glues, and other incorporating mineral materials. It relates to the use of such suspensions in aqueous formulations.

Finally, the present invention relates to an aqueous formulation obtained according to the present invention.

In order to adapt the rheology of the product to the application conditions by varying the properties of the surface to be covered, the means of application, and the amount of product to be applied, and independently, to impart satisfactory stability to these products, Has additives which can be used very widely, generally called "thickeners". These thickeners develop complex interactions with other constituents present in paint formulations, which have been the subject of much research for more than half a century: the goal of this study is to develop the desired rheology and paint formulation. It is intended to further understand the mechanism of action of these rheological additives in order to give those skilled in the art appropriate tools and rules for selecting a suitable thickener according to the other components present.

During this study, something very special was applied to the interactions in which thickeners could appear with an aqueous suspension of stabilized mineral fillers with the aid of dispersants. This interest is justified by the fact that mineral fillers which previously contributed in the form of dry powders, such as titanium dioxide or calcium carbonate, now contribute in the form of aqueous suspensions: in fact the latter is simpler to use and relates to the use of powdered materials. This eliminates the problem and facilitates filler handling operations by simple pumping of the suspension.

The interaction between dispersants and thickeners contained in aqueous suspensions of mineral substances is described in "Rheology of associative thickener pigment and pigmented commercial latex dispersions", Progress in Organic Coatings, 17, (1989), pp. 155-173, which tests the case of an aqueous suspension of titanium dioxide dispersed by polymethacrylic acid and in the presence of different thickening agents. According to this, when the concentration of dispersant is increased, the use of certain thickening agents of the HEUR (Hydrophobic Ethoxylated Urethane) type leads to destabilization of titanium dioxide, while in the presence of cellulose thickeners The stability of is believed to be maintained.

This study also demonstrated that the interaction between the dispersant and the thickener can affect the final properties of the paint film, such as brightness. In this regard, the article "Pigment stabilization through mixed associative thickener interactions" (Journal of Coatings Technology, 64, 807, (1992), pp. 53-61) describes the HEUR type (dispersant and copolymer of maleic acid and diisobutylene). It is taught that the use of a combination of thickeners of hydrophobe-modified Ethoxylated Urethanes increases the brightness in the case of latex paints. Conversely, the document "Interactions between rheology-modifying and pigment-dispersing agents" (Farbe + Lack, 100, 9, (1994), pp. 759-764) is a dispersant with high ionicity and HEUR type (hydrophobically modified ethoxylation). Paint formulations comprising thickeners of urethane) can reduce the brightness of the final product. The authors of these studies discuss possible combinations between different dispersants and thickeners of HEUR type (Hydrophobe-modified Ethoxylated Urethane) and HASE type (Hydrophobically modified Alkali-swellable Emulsions).

In summary, the general teaching of this document to those skilled in the art is that the interaction between dispersant and thickener is complex and determines both the stability of the formulated paint and the properties of the final paint film. The situation is summarized in "Adsorption studies of associative interactions between thickener and pigment particles", Progress in Organic Coatings, 30 (1997), pp.161-171, and the stability of the paints produced and the finality of the paint film. In terms of properties, those skilled in the art are strongly encouraged to carefully select new combinations of dispersants and thickeners and exploit their potential (introduction on page 167).

Furthermore, following the use of mineral fillers in the form of an aqueous suspension, those skilled in the art will appreciate that the intermediate product consists of a simple blend of different constituents of the paint, and by simple blending, the paint corresponds to the set of said different constituents. To develop a formulation of. In this respect, it is known to prepare aqueous suspensions of mineral substances comprising water, mineral fillers and thickening agents. This suspension is then combined with other conventional pate ingredients to obtain the final product.

The person skilled in the art is thus familiar with the document US 2002-050228, which describes the preparation of an aqueous suspension comprising a pigment such as titanium dioxide and calcium carbonate. Such compositions may also include thickening agents and may be used in the formulation of inks and aqueous paints.

One skilled in the art is also familiar with US Pat. No. 6,074,474, which describes an aqueous suspension comprising mineral particles with a specific granular granular distribution, which may be calcium carbonate. In addition, the suspension may comprise a thickening agent and may then be used in the formulation of an aqueous paint.

Thus, for the purpose of preparing stable suspensions of mineral substances in the presence of thickeners, without the use of dispersants which can lead to disadvantageous results in terms of the rheology of the final product (by interaction with thickeners). As a result, the inventors have found in a surprising way a novel process for the preparation of an aqueous suspension of mineral fillers, characterized in that the mineral fillers are ground in water in the presence of thickening agents. The product thus obtained has a completely consistent stability even when used in an aqueous formulation.

Here, the inventors wish to emphasize that the present invention is distinguished from the prior art in the fact that the prior art cited above does not suggest or teach a grinding method of reducing the size of the mineral particles.

In addition, the suspension thus prepared responds to the desire of those skilled in the art in providing a product that already contains some of the thickeners used in the paint. In addition, very surprisingly, the thickener is not denatured in the grinding process, and it correctly fulfills the function of the grinding aid in the present preparation step, thereby reducing the consumption of the grinding aid: in fact, the inventors have found that the particle size of the mineral substance is significantly increased. Was observed to decrease. And it is well known that the choice of mineral particle size in the context of paint formulations is very important to those skilled in the art. Indeed, "Particle-size distribution of fillers and their importance in the preparation of paints", Deutsche Farben-Zeitschrift, 20 (12), 1966, pp. 565-567, particle size greatly influences the mechanical and optical properties of the final film. In addition, the process according to the invention allows a wide range of commercially available paint thickeners to be used.

In addition, the process according to the invention allows an aqueous suspension of mineral material to be obtained, which, when used in paint formulations, has an improved rheological properties compared to the prior art, inter alia increasing the viscosity of ICI ^TM and Stormer ^TM. Allow the prepared paint formulation to be prepared.

In addition, the improved rheological properties have the advantage of improving paint application quality.

Finally, since the optical properties of the paint film produced according to the present invention are not modified, and therefore the compatibility of the formulated paint with the pigment is not modified, the properties of such thickeners are preserved.

Thus, the present invention allows a stable aqueous paint formulation to be obtained over time without the use of dispersants. The present invention also allows the intermediate product to be obtained in the form of an aqueous suspension of mineral substances and thickeners, wherein the thickeners also serve as grinding aids. In this regard, in the course of the process, it is possible to continue to use "traditional" grinding aids. Finally, the aqueous suspension obtained by grinding the mineral material in water in the presence of a thickening agent has stability, which stability is completely consistent even when used in the formulation of aqueous paints.

Therefore, an object of the present invention is a method of grinding mineral material in water in the presence of a thickening agent.

Another object of the present invention is a stable suspension of pulverized mineral material in water obtained according to the process.

Another object of the present invention is to provide for the suspension of the suspension in an aqueous formulation, in particular a lining formulation such as, among others, aqueous paints, priming coatings, inks, coatings, sealants, adhesives, glues, and other aqueous formulations incorporating mineral substances. It is use.

The last object of the present invention is in the aqueous formulations obtained according to the present invention.

Thus, the process according to the invention is intended to yield an aqueous suspension of mineral material having a consistent rheology when used in aqueous formulations, without the use of dispersants.

In addition, the process according to the invention, when used in paint formulations, provides an aqueous suspension of mineral substances which allows for the production of paint formulations which have improved rheological properties over the prior art, inter alia increased ICI ^TM and Stormer ^TM viscosity. Is obtained.

The method also allows the product to be prepared according to the needs of those skilled in the art, which product contains water, one or more mineral fillers, and one or more thickening agents.

In addition, the fineness of the mineral material used is adjusted by grinding the mineral material in the presence of a thickening agent, in which the thickener performs the function of the grinding aid.

In addition, the thickeners do not denature during the grinding process and do not impair the optical properties of the paint film or the compatibility of the paints with which they are formulated with the pigments.

Finally, aqueous suspensions of mineral materials ground in this way and stable over time are used in formulations of aqueous paints which are very satisfactory in stability and have improved rheological properties.

This object is achieved through a novel process for producing a stable suspension of mineral material in water, which is characterized by grinding the mineral material in the presence of a thickening agent.

The inventors intend to clarify that the operation of grinding the mineral substance to be purified is to grind the mineral substance into very fine particles using a pulverized body in an aqueous medium containing a thickening agent.

The thickeners and milling bodies are thus advantageously 0.20 to 4 mm in particle size and added to the aqueous suspension of mineral material for milling. The mill typically has materials in the form of particles, as varied as silicon dioxide, aluminum oxide, zirconium oxide or combinations thereof, together with synthetic resins, steel or the like of high hardness. Examples of the composition of such a pulverized body are given in patent FR 2 203 681, which has 30 to 70% by weight of zirconium oxide, 0.1 to 5% by weight of aluminum oxide and 5 to 20% by weight of silicon dioxide. It describes the grinding member formed by.

The pulverized body is preferably added to the suspension in an amount such that the weight ratio between the pulverized material and the pulverized mineral material is at least 2/1, preferably such that the ratio is 3/1 to 5/1.

The blend of suspension and milled body is then subjected to a mechanical stirring action such as that which occurs in a conventional mill with micro members.

The time required to achieve the desired degree of purification of the mineral material after grinding will be defined by the manufacturer of the suspension of the mineral material depending on the nature and amount of the mineral material to be ground, the medium temperature during the grinding operation and the stirring method used.

Another variant of the invention is characterized in that the process uses one or more grinding aids. The grinding aids will be selected by the manufacturer of the suspension of the mineral substance among all known grinding aids and combinations thereof.

In addition, the process according to the invention is characterized in that the mineral material is either natural or synthetic calcium carbonate, dolomite, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, satin white, aluminum trioxide, or aluminum trioxide, mica, Zinc oxide and iron oxide, barium sulfate and combinations of these fillers with each other such as talc-calcium carbonate blends, calcium carbonate-kaolin blends, or blends of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or with synthetic or natural fibers, or Mineral costructures, such as talc-calcium carbonate co-structures or talc-titanium dioxide co-structures, or combinations thereof.

Preferably, the mineral material is synthetic or natural calcium carbonate, titanium dioxide, or a combination thereof.

More preferably, the mineral material is natural calcium carbonate or synthetic calcium carbonate selected from marble, calcite, chalk or combinations thereof.

In addition, the process according to the invention is characterized in that the thickening agent is a natural thickening agent such as natural gum, CMC (carboxymethylcellulose) and HEC (hydroxyethylcellulose), or a synthetic thickening agent such as synthetic gum, HASE type. (Hydrophobically modified Alkali-swellable Emulsion, or hydrophobically modified Alkali-swellable emulsion) or ASE type (Alkali soluble Emusion), acrylic thickener, polyurethane, polyether, polyester, or PVP (polyvinylpyrroli) Money) is chosen from having a base.

Preferably, the thickener is selected from acrylic thickeners and polyurethane thickeners of the HASE type (hydrophobically modified alkali-swellable emulsions).

The process according to the invention furthermore comprises at least 15 dry weight percent mineral material relative to the total weight of the aqueous suspension, 0.01 to 5 dry weight percent thickener based on the total weight of the aqueous suspension, and 0 to 0 weight relative to the total weight of the aqueous suspension. 5 dry weight% grinding aid is used.

Preferably, the process comprises at least 30 dry weight percent mineral material relative to the total weight of the aqueous suspension, 0.5 to 1.5 dry weight percent thickener based on the total weight of the aqueous suspension, and 0 to 0 weight based on the total weight of the aqueous suspension. 2 dry weight% grinding aid is used.

Even more preferably, the process employs at least 50 dry weight percent mineral substances relative to the total weight of the aqueous suspension and 0.5 to 1.5 dry weight percent thickener based on the total weight of the aqueous suspension and no grinding aids. It is characterized by.

Another object of the invention is obtained by the process according to the invention, at least 15 dry weight% of mineral material relative to the total weight of the aqueous suspension, 0.01 to 5 dry weight% thickener, based on the total weight of the aqueous suspension, and In an aqueous suspension of milled mineral material in the presence of a thickening agent, characterized in that it contains 0 to 5 dry weight percent grinding aid relative to the total weight of the aqueous suspension.

Preferably, the suspension of mineral material comprises at least 30 dry weight percent mineral material relative to the total weight of the aqueous suspension, 0.5 to 1.5 dry weight percent thickener based on the total weight of the aqueous suspension, and the total weight of the aqueous suspension. It is characterized by containing 0 to 2 dry weight% of the grinding aid.

Even more preferably, the suspension of mineral material contains at least 50 dry weight percent mineral material and at least 0.5 to 1.5 dry weight percent thickener based on the total weight of the aqueous suspension and the grinding aid and It is characterized by not.

In addition, the aqueous suspension of mineral material obtained by the process according to the invention ensures that at least 50% of the particles of mineral material have a diameter of 30 μm or less, ie a median diameter d ₅₀ of 30 μm or less. It is characterized by having a particle size to have.

In this application, the particle size of the suspension is determined using a Mastersizer ^™ 2000 particle size meter sold by MALVERN ^™ .

Preferably, the aqueous suspension of mineral material obtained by the process according to the invention is further characterized by having a particle size such that at least 50% of the mineral material particles have a diameter of 15 μm or less.

Even more preferably, the aqueous suspension of mineral material obtained by the process according to the invention is also characterized by having a particle size such that at least 50% of the mineral material particles have a diameter of 10 μm or less.

Finally, most preferably, the aqueous suspension of mineral material obtained by the process according to the invention is also characterized by having a particle size such that at least 50% of the mineral material particles have a diameter of 5 μm or less.

In addition, the aqueous suspension may be a mineral material, natural or synthetic calcium carbonate, dolomite, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, satin white, aluminum trioxide, or aluminum trioxide, mica, zinc oxide and iron oxide, Barium sulfate and combinations of these fillers with each other, such as talc-calcium carbonate blends, calcium carbonate-kaolin blends, or blends of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or blends with synthetic or natural fibers, or mineral co-structures such as Pigment and / or mineral fillers selected from talc-calcium carbonate co-structures or talc-titanium dioxide co-structures, or combinations thereof.

Preferably, the mineral material is synthetic or natural calcium carbonate, titanium dioxide, or a combination thereof.

More preferably, the mineral material is natural calcium carbonate or synthetic calcium carbonate selected from marble, calcite, chalk or combinations thereof.

In addition, aqueous suspensions of mineral substances according to the invention can be prepared by the use of the thickener as a natural thickener, for example natural gums, CMC (carboxymethylcellulose) and HEC (hydroxyethylcellulose), or synthetic thickeners, for example synthetic Among those having an acrylic thickener, polyurethane, polyether, polyester, or PVP (polyvinylpyrrolidone) base of the gum, HASE type (hydrophobically modified alkali-swellable emulsion) or ASE type (alkali soluble emulsion) Is selected.

Preferably, the aqueous suspension of mineral material according to the invention is also selected from acrylic thickeners and polyurethane thickeners of which the thickener is of the HASE type (hydrophobically modified alkali-swellable emulsion).

Another object of the present invention is to provide for the suspension of the suspension in an aqueous formulation, in particular a lining formulation such as, among others, aqueous paints, priming coatings, inks, coatings, sealants, adhesives, glues, and other aqueous formulations incorporating mineral substances. It is use.

The last object of the present invention is the aqueous formulation obtained according to the present invention.

Thus, the aqueous paints, primary coatings, inks, coatings, sealants, adhesives, aqueous formulations and glues incorporating mineral substances according to the invention contain a mineral aqueous suspension according to the invention which is ground in the presence of a thickening agent and Characterized in that there is.

The following examples illustrate the invention, but do not limit the scope of the invention.

Example  One

This example relates to the preparation of an aqueous suspension of mineral material via the grinding method according to the invention in the presence of thickeners (tests 1 to 5) and in the presence of thickeners and conventional grinding aids (test 6). will be. This example also relates to a suspension of mineral substances obtained from the grinding process according to the invention.

In tests 1 to 6, calcium carbonate was used, which was marble (manufactured by Avenza, Italy) and whose initial median diameter d ₅₀ was 10 μm (50% of the calcium carbonate particles had a diameter of 10 μm or less). The calcium carbonate is sold under the trade name Omyacarb ^™ 10 AV by OMYA ^™ .

Using a mill of the Dyno-Mill ^™ type with a fixed cylinder and a rotating pulser, the mill of which consisted of zirconium-based balls ranging in diameter from 0.6 mm to 1 mm.

The total volume occupied by the pulverized body was 1000 cm 3 and its mass was 2,700 g.

The grinding chamber had a volume of 1400 cm 3.

The circumferential speed of the mill was 10 m / sec.

The pigment suspension was recycled at a rate of 40 l / hr.

At the outlet of the Dyno-Mill ^™ grinder was installed a 200 micron mesh separator which allowed the suspension and the resulting powder to be separated from the mill.

The temperature during each grinding test was maintained at approximately 30 ° C.

The process was started by blending the calcium carbonate dry powder with a thickening agent in water, after which the blend was ground using the apparatus described above. The grinding time was suitably according to the target particle size.

The particle size of the suspension was then determined as follows.

After grinding, a sample of the pigment suspension whose particle size was measured using a Mastersizer ^™ 2000 particle size meter sold by MALVERN ^™ was recovered from the flask. Thereafter, the median diameter d ₅₀ of the purified calcium carbonate particles was determined.

Brookfield ^™ viscosity of the suspension was determined as follows.

The Brookfield ^™ viscosity of the suspension was measured using a Brookfield ^™ viscometer of the RVT type at two rotational speeds of 10 and 100 revolutions / min and a temperature of 25 ° C., using a suitable moving part in a flask that was not stirring. Reading after 1 minute of rotation. Two Brookfield ^™ viscosity measurements were obtained, shown as μ ₁₀ and μ ₁₀₀ , respectively.

The flask was left for 8 days and stirred for 1 minute, then the Brookfield ^™ viscosity of the suspension was measured using the same method.

Test 1

This test illustrates the invention, using an acrylic thickener sold under the trade name Rheo 2000 ^™ by COATEX ^™ at 0.64 dry weight percent, based on the total weight of the suspension. The test also used 64.6 dry weight percent calcium carbonate (manufactured by Avenza) and the balance of water relative to the total weight of the suspension.

Test 2

This test illustrates the invention, using an acrylic thickener sold under the trade name Rheo 2000 ^™ by COATEX ^™ at 0.60 dry weight percent, based on the total weight of the suspension. In addition, this test used 60.0 dry weight% calcium carbonate (made by Avenza) and the balance of water with respect to the total weight of suspension.

Test 3

This test illustrates the invention and AQUALON ^™ Trademark Natrosol ^TM Thickening agent, a cellulosic ether sold at 250 HHR, was used at 0.37 dry weight percent based on the total weight of the suspension. The test also used 52.6 dry weight calcium carbonate (manufactured by Avenza) and the balance of water relative to the total weight of the suspension.

Test 4

This test illustrates the invention, COATEX ^™ A polyurethane thickener of type HEUR sold by the company under the trade name COAPUR ^™ 3025 was used at 0.61 dry weight percent, based on the total weight of the suspension. The test also used 61.0 dry weight percent calcium carbonate (manufactured by Avenza) and the balance of water relative to the total weight of the suspension.

Test 5

This test illustrates the invention, using a polyurethane thickener of type HEUR sold under the trade name COAPUR ^™ 3025 by COATEX ^™ , at 0.51 dry weight percent, based on the total weight of the suspension. The test also used 51.5 dry weight calcium carbonate (manufactured by Avenza) and the balance of water relative to the total weight of the suspension.

Test 6

This test illustrates the invention, using an acrylic thickener sold under the trade name Rheo 2000 ^™ by COATEX ^™ at 0.50 dry weight percent, based on the total weight of the suspension. In addition, this test used 56.7% by weight of calcium carbonate (made by Avenza) based on the total weight of the suspension. The test also used a grinding aid and a residual amount of water that was 0.3% by weight sodium polyacrylate relative to the total weight of the suspension.

The properties of the suspensions obtained in trials 1 to 6 are shown in Table 1 below.

Aqueous Suspension Characteristics of Grinded Calcium Carbonate According to the Present Invention The present invention Exam number One 2 3 4 5 6 CaCO ₃ (dry weight%) 64.6 60.0 52.6 61.0 51.5 56.7 Thickening Agent (Dry Weight%) 0.64 0.60 0.37 0.61 0.51 0.50 Grinding aids (dry weight%) 0 0 0 0 0 0.30 d ₅₀ (㎛) 4.9 2.0 4.7 5.2 2.3 5.3 Viscosity at T = 0 μ ₁₀ (mPa.s) 2550 4740 4540 4720 8800 3360 μ ₁₀₀ (mPa.s) 1580 1550 1240 960 1420 2210 T = viscosity at 8 days μ ₁₀ (mPa.s) 1720 3880 4720 6650 8250 1400 μ ₁₀₀ (mPa.s) 930 1090 1470 1195 2250 910 Dry weight percentages are understood as relative to the total weight of the suspension. d ₅₀ indicates the median diameter of the calcium carbonate particles after grinding (50% of the particles have a diameter below this value). T = 0 indicates the initial time to measure Brookfield ^™ viscosity at 10 and 100 revolutions / min, denoted as μ ₁₀ and μ ₁₀₀ , respectively. T = 8 days refers to time t = 8 days, measured after stirring of Brookfield ^™ viscosity at 10 and 100 revolutions / min, represented by μ ₁₀ and μ ₁₀₀ , respectively.

The median diameter corresponding to Tests 1 to 6 demonstrates that in the process according to the invention, the thickeners used above actually act as grinding aids, in that a marked reduction in the calcium carbonate particle size is observed.

Finally, it is observed that each suspension obtained according to the invention is stable over time.

Example  2

This example relates to the preparation of an aqueous paint according to the invention from an aqueous suspension of calcium carbonate ground in the presence of a thickening agent according to the invention, or from a dry powder of calcium carbonate according to the prior art.

Paints are formulated by blending different components using methods known to those skilled in the art. The inventors have shown only the properties of the carbonates and thickeners used in the following tests. Of course, the paint also contains a number of other additives. A complete list of the components of each paint and their proportions is shown in the summary table.

For each formulated paint, the ICI ^™ , Stormer ^™ and Brookfield ^™ viscosities were determined using the following method.

ICI ^™ viscosity was determined on a cone-plane viscometer sold by ERICHSEN ^™ , known as ICI ^™ Viscometer, using methods known to those skilled in the art. Measurements were made at 25 ° C. and expressed as μ ^I (P).

Stormer ^TM Viscosity is a KU-1 type Stormer ^TM sold by Brookfield ^TM with a single measurement system Determined on viscometer. Measurements were made at 25 ° C. and expressed in μ ^S (KU).

Brookfield ^™ viscosity of the paint was determined at 25 ° C. in the same manner as shown in Example 1 for a suspension of mineral material. The viscosity is expressed in μ ^B ₁₀ (mPa · s) and μ ^B ₁₀₀ (mPa · s), depending on whether it was determined at 10 or 100 revolutions / min.

Test 7

This test relates to the formulation of matt paints according to the prior art in which carbonate is introduced alone in the form of a dry powder.

The carbonate is a blend of two kinds of calcium carbonate, a marble made by Avenza (Italy), one of which has a median diameter of 5 μm (50% of the particles have a diameter of less than 5 μm), and the other One was a median diameter of 2 μm. These were sold by OMYA ^™ under the trade names Omyacarb ^™ 5-AV and Omyacarb ^™ 2-AV, respectively. The thickener used was an acrylic thickener sold under the trade name Rheo 2000 ^™ by the company COATEX ^™ .

Test 8

This test relates to the formulation of the matte paint according to the invention.

Part of the calcium carbonate was introduced in the form of a dry powder, which was calcium carbonate, a marble made by Avenza (Italy), having a median diameter of 5 μm. This was sold under the trade name Omyacarb ^™ 5-AV by OMYA ^™ .

The other part was introduced in the form of an aqueous suspension according to the invention described in test 1.

Exam 9

This test relates to the formulation of the matte paint according to the invention.

Part of the calcium carbonate was introduced in the form of a dry powder, which was calcium carbonate, a marble made by Avenza (Italy), having a median diameter of 2 μm. This was sold under the trade name Omyacarb ^™ 2-AV by OMYA ^™ .

The other part was introduced in the form of an aqueous suspension according to the invention described in test 2.

Exam 10

This test relates to the formulation of the matte paint according to the invention.

Part of the calcium carbonate was introduced in the form of dry powder. It is a blend of two calcium carbonates, Avenza's marble, one of which has a median diameter of 5 μm (50% of the particles have a diameter of less than 5 μm) and the other has a median diameter of 2 μm. . These were sold by OMYA ^™ under the trade names Omyacarb ^™ 5-AV and Omyacarb ^™ 2-AV, respectively.

The other part was introduced in the form of two aqueous suspensions according to the invention described in Trials 1 and 2.

The list of constituents and their weight ratios is shown in Table 2 for the paints corresponding to tests 7-10.

For the paints corresponding to the four tests, each component was formulated to a constant mass, so that the mass of calcium carbonate was the same in these tests as 500 g and the mass of thickener was equal to 20 g.

Composition of the paint formulated according to tests 7-10 Ingredient Test 7 (Prior art) Test 8 (Invention) Exam 9 (Invention) Exam 10 (Invention) Suspension of carbonate milled according to test 1 0 466.1 0 233.1 Suspension of carbonate ground to test 2 0 0 333.3 166.7 Omyacarb ^TM 5-AV 300.0 0 300.0 150.0 Omyacarb ^TM-2 AV 200.0 200.0 0 150.0 Tiona ^TM RL 68 80.0 80.0 80.0 80.0 Water (additional) 209.3 54.5 83.4 68.6 Rheo 2000 ^TM 20.0 10.0 13.3 11.7 Coatex ^TM P90 4.0 4.0 4.0 4.0 Mergal ^TM K6N 2.0 2.0 2.0 2.0 Nopco ^TM NDW 2.0 2.0 2.0 2.0 Butyl diglycol 10.0 10.0 10.0 10.0 White Spirit 10.0 10.0 10.0 10.0 ammonia 2.7 1.4 2.0 1.7 Acronal ^TM 290 D 160.0 160.0 160.0 160.0 Sum 1000.0 1000.0 1000.0 1000.0 Numbers refer to mass by weight. Tiona ^™ RL 68 refers to titanium dioxide sold by MILLENNIUM ^™ . Coatex ^™ P90 is a polyacrylic dispersant sold by COATEX ^™ . Mergal ^™ K6N is a bactericide sold by TROY ^™ . Nopco ^™ NDW is an antifoaming agent sold by COGNIS ^™ . Acronal ^™ 290 D is an acrylic binder sold by BASF ^™ .

The ICI ^™ , Stormer ^™ and Brookfield ^™ viscosity values measured at different times for the paints formulated in Trials 7-10 are summarized in Table 2b below.

Viscosity measured for paints formulated according to tests 7-10 Viscosity Test 7 (Prior art) Test 8 (Invention) Exam 9 (Invention) Exam 10 (Invention) T = 0 μ ^I (Po) 2.2 2.4 2.2 2.4 μ ^S (KU) 87 91 90 95 μ ^B ₁₀ (mPa.s) 4400 4400 4300 4600 μ ^B ₁₀₀ (mPa.s) 1590 1890 1850 1900 T = 24 hours μ ^I (Po) 2.3 2.5 2.4 2.4 μ ^S (KU) 89 95 94 95 μ ^B ₁₀ (mPa.s) 4500 4800 4700 4800 μ ^B ₁₀₀ (mPa.s) 1630 2010 1950 2010 T = 7 days μ ^B ₁₀ (mPa.s) 4600 5200 5300 4800 μ ^B ₁₀₀ (mPa.s) 1670 2080 2120 1920 μ ^I (P): ICI ^TM viscosity μ ^S (KU): Stormer ^TM viscosity μ ^B ₁₀ (mPas): Brookfield ^TM viscosity measured at 10 revolutions / min μ ^B ₁₀₀ (mPas): 100 revolutions / min Brookfield ^TM viscosity measured by

The results in Table 2b demonstrate that the paints formulated according to the invention have improved rheological properties as compared to the prior art, where an increase in the ICI ^™ and Stormer ^™ viscosity was observed. This improvement allows the paint application quality to be improved.

In addition, the Brookfield ^™ viscosity observed in the paints according to the invention demonstrates that these formulations are stable over time.

In addition, a number of optical properties were determined for paints formulated according to tests 7-10.

Immediately after application of the paint to 150 μm thickness using a standard manual film-stretcher, the wet coverage CPs of the paints formulated according to Tests 7-10 were visually compared on a contrast card. .

It was proved that the coating powers of the tests 8 to 10 according to the present invention were the same as those obtained in the test 7 taken as a reference value.

The color coordinates L and b shown in Table 3 belong to the color spaces (L, a, b, Hunter) and were determined in a test paint dry film, the film being 150 μm thick using a standard manual film-stretcher. It was previously applied to a glass plate and then dried at 23 ° C. for 24 hours surrounded by an atmosphere of 50% humidity.

The value of contrast ratio CR (%) = Y _n / Y _b was measured on a Spectro-Pen ^™ spectrophotometer sold by DR LANGE ^™ . The paint was pre-applied to the contrast card to a 150 μm thickness using a standard manual film-stretcher. Then, the measured reflectance value Y _n in the black part of the Y value of the reflectivity _b of the substrate and in the white part of the substrate. The values obtained in the color space (X, Y, Z) are the average values obtained for three measurements.

Luminance was measured with a Micro-Tri-Gloss ^™ reflectometer sold by BRANDT ^™ company at angles of 60 ° and 85 ° according to French standard NF T 30-064 (BS 60 and BS 85). The paint was pre-applied to the glass plate at 150 μm thickness using a standard manual film-stretcher.

Optical Properties Measured for Paints Formulated According to Tests 7-10 Optical properties Test 7 (Prior art) Test 8 (Invention) Exam 9 (Invention) Exam 10 (Invention) CP Reference value Same as reference value Same as reference value Same as reference value M 97.4 97.4 97.5 97.6 B 1.1 1.2 1.1 1.05 CR (%) 97.1 97.3 97.2 97.2 BS 60 3.8 3.9 3.7 3.8 BS 85 4.0 4.0 3.9 4.1 CP: Visual Evaluation wet pibokryeok M with: a brightness b measured in Spectro-Pen ^TM spectral color difference meter sold by DR LANGE ^TM yarn: low measured in Spectro-Pen ^TM spectral color difference meter sold by DR LANGE ^TM four color ( undertone) CR (%): Contrast ratio measured on a Spectro-Pen ^TM spectrophotometer sold by DR LANGE ^TM BS 60, BS 85: BRANDT at angles of 60 ° and 85 ° according to French standard NF T 30-064 sold by ^TM four Micro-Tri-Gloss ^TM reflection luminance was measured to step

The results in Table 3 demonstrate that the optical properties measured for the paints formulated according to the invention are equivalent to those of the prior art.

Finally, for tests 7-10, the compatibility of the formulated paints with the pigments was determined by measuring the parameter delta E (ΔE).

The value of Delta E (ΔE) of the matte colored aqueous formulation was determined by adding 5% by weight of black pigment to the white substrate, ie 50 g of black pigment (190 g of COLANYL ^™ Black, CLARIANT ^™) to 190 g of white paint. Sales)).

This test for measuring ΔE is known to those skilled in the art under the term “rub out”.

This test applied 150 μm colored matt or glossy paint formulation for testing on a contrast card, slowly and without stress, without applying shear using an applicator, waiting for 45 seconds, and then applying a still viscous paint film. It is to apply shear by rubbing with finger for 30 seconds in position.

After drying the film, the color difference between the shear zone (rubbing area) and the non-shear area (zone not rubbing the film) was measured using a Spectro-Pen ^TM spectrometer to determine whether the paint composition tested had satisfactory pigment compatibility. Were evaluated (ΔE values).

The ΔE values determined for the colored formulations prepared with the paints corresponding to Trials 7-10 are shown in Table 4.

ΔE values measured from different colored formulations prepared with white substrates corresponding to tests 7-10 Colored formulations prepared from the white substrate of the test Exam 7 (prior art) Trial 8 (Invention) Trial 9 (Invention) Test 10 (Invention) ΔE 0.6 0.5 0.4 0.5

The values in Table 4 demonstrate that the pigment compatibility of colored paints formulated according to the invention remains the same as the pigment compatibility of those corresponding to the tests according to the prior art.

Test 11

This test relates to the formulation of a satin paint according to the prior art, wherein the carbonate is introduced alone in the form of a dry powder.

This was calcium carbonate, a marble made by Avenza (Italy), having a median diameter of 2 μm. This was sold under the trade name Omyacarb ^™ 2-AV by OMYA ^™ .

The increasing agent used was a growing polyurethane HEUR type of agent that sold under the trademark Coapur ^TM 3025 in four COATEX ^TM.

Test 12

This test relates to the formulation of a glossy paint according to the invention.

Calcium carbonate was introduced in the form of an aqueous suspension according to the invention described in test 5.

A list of the components and their weight ratios is shown in Table 5 for the paints corresponding to Tests 11 and 12.

For paints corresponding to the two tests, the skilled person worked with a constant mass of each component, whereby the mass of calcium carbonate was the same in these tests as 150 g and the mass of thickener was equal to 20 g. .

Composition of the paint formulated according to tests 11 and 12 Ingredient Test 11 (Prior art) Test 12 (Invention) Suspension of carbonate ground to test 5 0 291.3 Omyacarb ^TM-2 AV 150.0 0 Tiona ^TM RL 68 200.0 200.0 Water (additional) 90 .0 0 Coapur ^TM 3025 20.0 14.0 Coatex ^TM BR3 4.0 4.0 Mergal ^TM K6N 2.0 2.0 Nopco ^TM NDW 1.0 1.0 Butyl diglycol 15.0 15.0 ammonia 3.2 3.2 Tego Foamex ^TM 1488 1.0 1.0 Texanol 15.0 15.0 Acronal ^TM 290 D 440.0 440.0 Sum 1000.0 1000.0 Numbers refer to mass by weight. Tiona ^™ RL 68 refers to titanium dioxide sold by MILLENNIUM ^™ . Coatex ^™ P90 is a polyacrylic dispersant sold by COATEX ^™ . Mergal ^™ K6N is a bactericide sold by TROY ^™ . Nopco ^™ NDW is an antifoaming agent sold by COGNIS ^™ . Tego Foamex ^™ 1488 is an antifoaming agent sold by TEGO CHEMIE ^™ . Texanol ^™ is a coalescence agent sold by EASTMAN KODAK ^™ . Acronal ^™ 290 D is an acrylic binder sold by BASF ^™ .

The ICI ^™ , Stormer ^™ and Brookfield ^™ viscosity values measured at different times for the paints formulated in tests 11 and 12 are summarized in Table 5b below.

Viscosity measured for paints formulated according to tests 11 and 12 Viscosity Test 11 (Prior art) Test 12 (Invention) T = 0 μ ^I (Po) 2.3 2.4 μ ^S (KU) 94 96 μ ^B ₁₀ (mPa.s) 4400 4600 μ ^B ₁₀₀ (mPa.s) 1900 2010 T = 24 hours μ ^I (Po) 2.5 2.7 μ ^S (KU) 103 107 μ ^B ₁₀ (mPa.s) 6800 6900 μ ^B ₁₀₀ (mPa.s) 2790 2930 μ ^I (P): ICI ^TM viscosity μ ^S (KU): Stormer ^TM viscosity μ ^B ₁₀ (mPas): Brookfield ^TM viscosity measured at 10 revolutions / min μ ^B ₁₀₀ (mPas): 100 revolutions / min Brookfield ^TM viscosity measured by

The results in Table 5b demonstrate that the paints formulated according to the invention have improved rheological properties compared to the prior art, where an increase in ICI ^TM and Stormer ^TM viscosity was observed. This improvement allows the paint application quality to be improved.

In addition, the Brookfield ^™ viscosity observed in the paints according to the invention demonstrates that these formulations are stable over time.

Trial 13

This test relates to the formulation of matte paints according to the prior art.

Part of the calcium carbonate is introduced in the form of dry powder, which is a marble made by Avenza, which is calcium carbonate with a median diameter of 2 μm. This was sold under the trade name Omyacarb ^™ 2-AV by OMYA ^™ .

The other part is introduced in the form of an aqueous suspension of calcium carbonate, which is an Avenza marble with an initial median diameter of 10 μm. This suspension was obtained from a grinding process according to the prior art in the presence of 0.3 dry weight percent of a conventional grinding agent (sodium polyacrylate). The suspension obtained had a dry matter concentration equal to 75% of its total weight, wherein the calcium carbonate purified and contained in the suspension had a median diameter of 5 μm.

Exam 14

This test relates to the formulation of the matte paint according to the invention.

Part of the calcium carbonate is introduced in the form of dry powder, which is a marble made by Avenza, which is calcium carbonate with a median diameter of 2 μm. This was sold under the trade name Omyacarb ^™ 2-AV by OMYA ^™ .

The other part is introduced in the form of an aqueous suspension from test 6.

A list of the components and their weight ratios is shown in Table 6 for the paints corresponding to tests 13 and 14.

For paints corresponding to the two tests, those skilled in the art worked with a constant mass of each component, whereby the mass of calcium carbonate was the same in these tests as 500 g and the mass of the binder was equal to 160 g.

Composition of the paint formulated according to tests 13 and 14 Ingredient Trial 13 (Prior art) Exam 14 (Invention) Suspension of carbonate ground to test 6 0 518.7 Suspension of carbonate milled in the presence of sodium polyacrylate (prior art) 400.0 0 Omyacarb ^TM-2 AV 200.0 200.0 Tiona ^TM RL 68 80.0 80.0 Water (additional) 113.3 3.3 Rheo 2000 ^TM 20.0 11.3 Mergal ^TM K6N 2.0 2.0 Acronal ^TM 290 D 160.0 160.0 Nopco ^TM NDW 2.0 2.0 Butyl diglycol 10.0 10.0 White Spirit 10.0 10.0 ammonia 2.7 2.7 Sum 1000.0 1000.0 Numbers refer to mass in g. ES refers to the dry extract, ie a% by weight of the dry matter weight fraction. Tiona ^™ RL 68 refers to titanium dioxide sold by MILLENNIUM ^™ . Coatex ^™ P90 is a polyacrylic dispersant sold by COATEX ^™ . Mergal ^™ K6N is a bactericide sold by TROY ^™ . Nopco ^™ NDW is an antifoaming agent sold by COGNIS ^™ . Acronal ^™ 290D is an acrylic binder sold by BASF ^™ .

The ICI ^™ , Stormer ^™ and Brookfield ^™ viscosity values measured at different times for the paints formulated in tests 13 and 14 are summarized in Table 6b below.

Viscosity measured for paints formulated according to tests 13 and 14 Viscosity Trial 13 (Prior art) Exam 14 (Invention) T = 0 μ ^I (P) 2.2 2.8 μ ^S (KU) 89 90 μ ^B ₁₀ (mPa.s) 5500 5600 μ ^B ₁₀₀ (mPa.s) 1640 1760 T = 24 hours μ ^I (P) 2.4 2.7 μ ^S (KU) 92 99 μ ^B ₁₀ (mPa.s) 5500 6400 μ ^B ₁₀₀ (mPa.s) 1870 2300 T = 7 days μ ^B ₁₀ (mPa.s) 5700 6500 μ ^B ₁₀₀ (mPa.s) 1850 1950 T = 1 month μ ^B ₁₀ (mPa.s) 5700 6200 μ ^B ₁₀₀ (mPa.s) 1780 1900 μ ^I (P): ICI ^TM viscosity μ ^S (KU): Stormer ^TM viscosity μ ^B ₁₀ (mPas): Brookfield ^TM viscosity measured at 10 revolutions / min μ ^B ₁₀₀ (mPas): 100 revolutions / min Brookfield ^TM viscosity measured by

The results in Table 6b demonstrate that the paints formulated according to the invention have improved rheological properties as compared to the prior art, where an increase in ICI ^TM and Stormer ^TM viscosity was observed. This improvement allows the paint application quality to be improved.

In addition, the Brookfield ^™ viscosity observed in the paints according to the invention demonstrates that these formulations are stable over time.

Example  3

This example relates to the preparation of an aqueous suspension of mineral material via a milling process in the presence of thickeners (tests 15 and 17 to 19) or a combination of two thickeners (test 16) according to the invention. This example also relates to a suspension of mineral substances obtained from the grinding process according to the invention.

In tests 15 to 18, calcium carbonate was used which was marble (manufactured by Avenza, Italy) and whose initial median diameter d ₅₀ was 10 μm (50% of the calcium carbonate particles had a diameter of 10 μm or less). The calcium carbonate is sold under the trade name Omyacarb ^™ 10 AV by OMYA ^™ .

In test 19, precipitated calcium carbonate having an initial median diameter d ₅₀ of 4.8 μm (50% of the calcium carbonate particles had a diameter of 4.8 μm or less) was used. It is sold under the trade name Socal ^™ P3 by SOLVAY ^™ .

The mineral material was ground according to the method of the present invention as described in Example 1.

In tests 15 to 19, the particle size of the aqueous suspension was determined in the same manner as described in Example 1 after grinding.

Then, using the same method as used in the procedure of Example 1, Brookfield ^TM viscosity (expressed as μ ₁₀ and μ ₁₀₀ , respectively) at two rotational speeds of 10 and 100 revolutions per minute was expressed as time t = 0 and t = Determined on day 8 (after 1 min stirring).

Exam 15

The test is illustrative of the present invention, in the trade name COATEX ^TM used ^TM Viscoatex An acrylic thickener of type ASE sold as V46 was used at 0.25 dry weight percent based on the total weight of the suspension. In addition, this test used 50.0 dry weight% calcium carbonate (made by Avenza) and the balance of water with respect to the total weight of suspension.

Exam 16

This test HEUR illustrating, and trade name sold as Coapur ^TM 2025 from COATEX ^TM Corporation under the trade name Rheo 2000 ^TM HASE type of acrylic thickened suspension the subject 0.25 dry weight%, based on the total weight, and COATEX ^TM Corporation sold as in the present invention A type of polyurethane thickener was used at 0.25 dry weight percent, based on the total weight of the suspension. In addition, this test used 50.0 dry weight% calcium carbonate (made by Avenza) and the balance of water with respect to the total weight of suspension.

Exam 17

This test illustrates the present invention, using an ASE type acrylic thickener sold under the trade name Rheo 2000 ^™ by COATEX ^™ at 0.10 dry weight percent, based on the total weight of the suspension. In addition, this test used 20.0 dry weight% calcium carbonate (made by Avenza) and the balance of water with respect to the total weight of suspension.

Exam 18

The test is illustrative of the present invention, in the trade names AQUALON ^TM used ^TM Aquaflow A polyether thickener sold as NHS 300 was used at 0.25 dry weight percent based on the total weight of the suspension. In addition, this test used 50.0 dry weight% calcium carbonate (made by Avenza) and the balance of water with respect to the total weight of suspension.

Exam 19

The test is illustrative of the present invention, in the trade name COATEX ^TM used ^TM Coapur A polyurethane thickener of type HEUR sold at 2025 was used at 0.25 dry weight percent based on the total weight of the suspension. The test also used 50.0 dry weight percent precipitated calcium carbonate Socal ^™ P3 and the balance of water relative to the total weight of the suspension.

The value of the median diameter d ₅₀ is determined after grinding, and the values of Brookfield ^™ viscosity μ ₁₀ and μ ₁₀₀ are measured at the time t = 0 and t = 8 days after grinding (after 1 min stirring) and are shown in Table 7.

Median diameter d ₅₀ after grinding, and Brookfield ^TM viscosity μ ₁₀ and μ ₁₀₀ after grinding (at time t = 0 and t = 8 days (after 1 min stirring)) The present invention Exam number 15 16 17 18 19 Calcium Carbonate (Dry Weight%) 50 50 20 50 50 Thickening Agent (Dry Weight%) 0.25 0.50 0.10 0.25 0.25 d ₅₀ (㎛) 5.6 4.9 2.5 4.3 2.1 Viscosity at T = 0 　 μ ₁₀ (mPa.s) 160 50 40 800 1630 　 μ ₁₀₀ (mPa.s) 73 30 10 110 250 Viscosity at T = 8 days μ ₁₀ (mPa.s) 110 45 40 760 3120 μ ₁₀₀ (mPa.s) 90 30 10 175 110

The median diameter corresponding to tests 15 to 19 demonstrates that in the process according to the invention, the thickeners used actually act as grinding aids, in that a marked reduction in the calcium carbonate particle size is observed.

Finally, it is observed that each suspension obtained according to the invention is stable over time.

Example  4

This example illustrates the invention and relates to the preparation of a priming coating, a coating, and a glue according to the invention.

Exam 20

This test illustrates the invention and relates to the preparation of a primary coating according to the invention.

To complete this test, primary coatings with the compositions shown in Table 8 were prepared using methods known to those skilled in the art.

This test uses, in particular, an aqueous suspension of mineral material ground in accordance with the invention obtained in the course of test 15.

Composition of Primary Coating Formulations According to the Invention Ingredient Weight (g) Aqueous suspension of mineral material according to test 15 259.5 Coatex ^TM P90 3.0 Mergal ^TM K6N 2.0 TiO2 RL68 60.0 Hydrocarb 35.0 Durcal ^TM 130 110.0 Rhodopas ^TM DS 910 (50%) 200.0 Mono-ethylene glycol 10.0 White spirit 10.0 Granicalcium 300.0 ammonia 2.5 Viscoatex ^TM 46 18.0 Coatex ^™ P90 is an acrylic dispersant sold by COATEX ^™ . Mergal ^™ K6N is a biocide sold by TROY ^™ . TiO ₂ RL68 is titanium dioxide sold by MILLENIUM ^™ . Hydrocarb ^TM And Durcal ^™ 130 is a calcium carbonate sold by OMYA ^™ . Rhodopas ^™ DS 910 is a styrene acrylic binder sold by RHODIA ^™ . Viscoatex ^™ 46 is an acrylic thickener sold by COATEX ^™ .

This was used to obtain a formulation, and its Brookfield ^™ viscosity measured at 1, 10, and 100 revolutions per minute (using the method described above) was 600,000 mPa.s, 115,000 mPa., At time t = 0, respectively. s, 15,000 mPa · s.

The viscosity measured at time t = 24 hours was 400,000 mPa * s, 82,000 mPa * s, and 14,500 mPa * s, respectively.

These values demonstrate that the Brookfield ^™ viscosity obtained is completely constant even with the use of the formulations according to the invention in the field of primary coatings.

Exam 21

This test illustrates the invention and relates to the preparation of a coating according to the invention.

To complete this test, coatings having the compositions shown in Table 9 were prepared using methods known to those skilled in the art.

This test uses, in particular, an aqueous suspension of mineral material ground in accordance with the invention obtained in the course of test 15.

Composition of Coating Formulations According to the Invention Ingredient Weight (g) Aqueous suspension of mineral material according to test 15 798.4 Nopco ^TM NDW 2.0 Mergal ^TM K6N 0.6 Myanit ^TM 120.0 Acronal ^TM 290D (50%) 12.0 Soda 20% 20.0 Viscoatex ^TM 46 (32%) 70.0 Nopco ^™ NDW is an antifoaming agent sold by COGNIS ^™ . Mergal ^™ K6N is a biocide sold by TROY ^™ . Myanit ^TM is a calcium carbonate sold by OMYA ^TM four. Acronal ^TM 290D is a styrene acrylic thickener sold by BASF ^™ .

This gave a formulation and its Brookfield ^TM viscosity measured at 1, 10, and 100 revolutions per minute (using the method described above, but in this case using a module of the Helipath ^TM type), the time t = At 0, it was 440,000 mPa * s, 59,000 mPa * s, and 18,000 mPa * s, respectively.

The viscosity measured at time t = 24 hours was 570,000 mPa * s, 70,000 mPa * s, and 20,500 mPa * s, respectively.

These values demonstrate that the Brookfield ^™ viscosity obtained is completely constant even with the use of the formulations according to the invention in the field of coatings.

Exam 22

This test illustrates the invention and relates to the preparation of the glue according to the invention.

To complete this test, glues having the compositions shown in Table 10 were prepared using methods known to those skilled in the art.

This test uses, in particular, an aqueous suspension of mineral material ground in accordance with the invention obtained in the course of test 15.

Composition of Glue Formulations According to the Invention Ingredient Weight (g)  Aqueous suspension of mineral material according to test 15 199.6 Mergal ^TM K6N 2.0  Nopco^TM NDW 1.0 Rhodopas ^TM DS 910 (50%) 160.0 Durcal ^TM 2 140.0 Durcal ^TM 130 524.4  Butyl diglycol 14.0  ammonia 10.0 Viscoatex ^TM 46 70.0 Nopco ^™ NDW is an antifoaming agent sold by COGNIS ^™ . Rhodopas ^™ DS 910 is a styrene acrylic binder sold by RHODIA ^™ . Durcal ^™ 2 and Durcal ^™ 130 are calcium carbonates sold by OMYA ^™ . Viscoatex ^™ 46 is an acrylic thickener sold by COATEX ^™ .

This gave a formulation and its Brookfield ^TM viscosity measured at 1, 10, and 100 revolutions per minute (using the method described above, but in this case using a module of the Helipath ^TM type), the time t = 0 was 975,000 mPa * s, 210,000 mPa * s, and 42,000 mPa * s, respectively.

The viscosity measured at time t = 24 hours was 1,070,000 mPa * s, 350,000 mPa * s, and 94,000 mPa * s, respectively.

These values demonstrate that the Brookfield ^™ viscosity obtained is completely constant even with the use of the formulations according to the invention in the glue field.

Claims (31)

A process for producing a stable suspension of mineral material in water, characterized in that the mineral material is ground in the presence of a thickening agent. The method of claim 1, wherein the mineral material is natural or synthetic calcium carbonate, dolomite, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, satin white, aluminum trioxide, or aluminum trioxide, mica, zinc oxide And combinations of these fillers with each other, such as iron oxide, barium sulfate, and talc-calcium carbonate blends, calcium carbonate-kaolin blends, or blends of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or blends with synthetic or natural fibers, or talc A pigment and / or mineral filler selected from mineral costructures, such as calcium carbonate costructures or talc-titanium dioxide costructures, or combinations thereof. The method of claim 2 wherein the mineral material is synthetic or natural calcium carbonate, titanium dioxide, or a combination thereof. 4. The process of claim 3 wherein the mineral material is natural calcium carbonate or synthetic calcium carbonate selected from marble, calcite, chalk or combinations thereof. The thickening agent of claim 1, wherein the thickener is selected from natural thickeners such as natural gums, CMC (carboxymethylcellulose) and HEC (hydroxyethylcellulose), or from synthetic thickeners, In particular with synthetic gums, acrylic thickeners of the HASE type (hydrophobically modified alkali-swellable emulsions) or ASE type (alkali soluble emulsions), polyurethanes, polyethers, polyesters or PVP (polyvinylpyrrolidone) bases It is selected from among the method. 6. The process of claim 5 wherein the thickener is selected from acrylic thickeners and polyurethane thickeners of the HASE type (hydrophobically modified alkali-swellable emulsions). The method according to claim 1, wherein at least one grinding aid is further used. 8. A method according to any one of claims 1 to 7, wherein at least 15 dry weight percent mineral material relative to the total weight of the aqueous suspension, 0.01 to 5 dry weight percent thickener based on the total weight of the aqueous suspension, and aqueous suspension 0 to 5 dry weight percent grinding aid based on total weight is used. The method of claim 8, wherein at least 30 dry weight percent mineral material relative to the total weight of the aqueous suspension, 0.5 to 1.5 dry weight percent thickener based on the total weight of the aqueous suspension, and 0 to 2 dryness relative to the total weight of the aqueous suspension. Weight% grinding aid is used. 10. A method according to claim 9, characterized in that at least 50 dry weight percent mineral substances relative to the total weight of the aqueous suspension and 0.5 to 1.5 dry weight percent thickener based on the total weight of the aqueous suspension are used, and no grinding aid is used. Way. Characterized by containing at least 15 dry weight percent mineral material, 0.01 to 5 dry weight percent thickener, and 0 to 5 dry weight percent grinding aid, based on the total weight of the aqueous suspension, An aqueous suspension of milled mineral material in the presence of a thickening agent. 12. The composition of claim 11, comprising at least 30 dry weight percent mineral material, 0.5 to 1.5 dry weight percent thickener, and 0 to 2 dry weight percent grinding aid, based on the total weight of the aqueous suspension. An aqueous suspension of mineral material ground in the presence of a thickening agent. 13. The presence of a thickening agent in accordance with claim 12, characterized in that it contains at least 50 dry wt% mineral material and 0.5 to 1.5 dry wt% thickener and no grinding aid, based on the total weight of the aqueous suspension. Aqueous suspension of milled mineral material. The particle size according to any one of claims 11 to 13, wherein at least 50% of the particles of the mineral substance have a diameter of 30 μm or less, that is, a median diameter d ₅₀ of 30 μm or less ( granules), which is an aqueous suspension of mineral material ground in the presence of a thickening agent. The grinding in the presence of a thickener according to claim 14, characterized in that at least 50% of the particles of mineral material have a particle size such that they have a diameter of 15 μm or less, ie, have a median diameter d ₅₀ of 15 μm or less. Suspension of refined mineral substances. The grinding in the presence of a thickener according to claim 15, characterized in that at least 50% of the mineral substance particles have a particle size such that they have a diameter of 10 μm or less, ie, have a median diameter d ₅₀ of 10 μm or less. Suspension of refined mineral substances. 17. The presence of thickener according to claim 16, characterized in that at least 50% of the particles of mineral material have a particle size such that they have a diameter of 5 μm or less, ie, have a median diameter d ₅₀ of 5 μm or less. Aqueous suspension of milled mineral material. The method of claim 11, wherein the mineral material is natural or synthetic calcium carbonate, dolomite, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, satin white, aluminum trioxide, or aluminum trioxide, Combinations of these fillers with each other, such as mica, zinc oxide and iron oxide, barium sulfate, and talc-calcium carbonate blends, calcium carbonate-kaolin blends, or blends of calcium carbonate and aluminum trihydroxide or aluminum trioxide, or with synthetic or natural fibers A mineral material ground in the presence of a thickening agent, characterized in that the compound is a pigment and / or mineral filler selected from a combination, or a mineral costructure, such as a talc-calcium carbonate co-structure or a talc-titanium dioxide co-structure, or a combination thereof. Aqueous suspension. 19. The aqueous suspension of mineral material pulverized in the presence of a thickener according to claim 18, characterized in that the mineral material is synthetic or natural calcium carbonate, titanium dioxide, or combinations thereof. 20. The aqueous suspension of mineral material pulverized in the presence of a thickener according to claim 19, characterized in that the mineral material is natural calcium carbonate or synthetic calcium carbonate selected from marble, calcite, chalk or combinations thereof. The thickener according to claim 11, wherein the thickener is selected from natural thickeners such as natural gums, CMC (carboxymethylcellulose) and HEC (hydroxyethylcellulose), or from synthetic thickeners, In particular with synthetic gums, acrylic thickeners of the HASE type (hydrophobically modified alkali-swellable emulsions) or ASE type (alkali soluble emulsions), polyurethanes, polyethers, polyesters or PVP (polyvinylpyrrolidone) bases Aqueous suspension, characterized in that selected from. The aqueous suspension of claim 21 wherein the thickener is selected from acrylic thickeners and polyurethane thickeners of the HASE type (hydrophobically modified alkali-swellable emulsions). In aqueous formulations such as lining formulations, such as aqueous paints, renderers, inks, coatings, sealants, adhesives, glues, and aqueous formulations incorporating mineral substances, Use of an aqueous suspension of mineral material ground in the presence of a thickening agent according to any one of the preceding claims. An aqueous paint, characterized in that it contains an aqueous suspension of milled mineral material in the presence of a thickening agent according to claim 11. 23. A primary coating, characterized in that it contains an aqueous suspension of mineral material comminuted in the presence of a thickening agent according to any one of claims 11 to 22. An ink characterized in that it contains an aqueous suspension of milled mineral material in the presence of a thickening agent according to any one of claims 11 to 22. 23. A coating agent comprising an aqueous suspension of milled mineral material in the presence of a thickening agent according to any one of claims 11 to 22. Sealant, characterized in that it contains an aqueous suspension of milled mineral material in the presence of a thickening agent according to any one of claims 11 to 22. 23. Adhesive, characterized in that it contains an aqueous suspension of milled mineral material in the presence of a thickening agent according to claim 11. Glue characterized in that it contains an aqueous suspension of milled mineral material in the presence of a thickening agent according to claim 11. An aqueous formulation incorporating mineral material, characterized in that it contains an aqueous suspension of ground mineral material in the presence of a thickening agent according to claim 11.