Mineral material powder with high dispersion ability and use of said mineral material powder

Abstract

The present invention refers to a mineral matter powder preparation by wet process without acrylic additive or other grinding aid additives and to the use of said mineral matter after an optional hydrophobic treatment. Said mineral material having superior dispersing properties.

Claims

1. A mineral material obtained by a process consisting of the steps of: a) wet grinding mineral material in at least one grinding step in an aqueous suspension or slurry in the absence of a dispersing agent until the mineral material has a weight median particle diameter d.sub.50 from 1.1 μm to 1.5 μm, wherein the mineral material is selected from the group consisting of marble, chalk, dolomite, calcite, limestone, magnesium hydroxide, talc, gypsum, titanium oxide, and any mixture thereof; b) optionally up-concentrating or dewatering the aqueous suspension or slurry of step a) in the absence of a dispersing agent to achieve a solids content of between 50% and 70%; c) drying the aqueous suspension or slurry of step a) or b) to achieve a solids content of 99.8%, wherein no dispersing agent is present in the mineral material so obtained; and d) optionally surface treating the mineral material obtained in step c) with at least one aliphatic carboxylic acid, wherein the mineral material after grinding in step a) and before optional treatment in step d) has a BET/N.sub.2 specific area of from 3 m.sup.2/g to 7 m.sup.2/g, wherein the obtained mineral material has a top cut d.sub.98 from 1.8 μm to 5.9 μm.

2. The mineral material according to claim 1, wherein the mineral material is wet ground in step a) until the mineral material has a weight median particle diameter d.sub.50 of 1.1 μm.

3. The mineral material according to claim 1, wherein the mineral material is wet ground in step a) until the mineral material has a weight median particle diameter d.sub.50 of 1.5 μm.

4. The mineral material according to claim 1, wherein step b) takes place.

5. The mineral material according to claim 1, wherein step d) takes place.

6. The mineral material according to claim 1, wherein the mineral material in step a) is selected from the group consisting of marble, chalk, dolomite, calcite, limestone, and any mixture thereof.

7. The mineral material according to claim 1, wherein the mineral material in step a) is calcium carbonate.

8. The mineral material according to claim 7, wherein the calcium carbonate after grinding in step a) and before optional treatment in step d) has a BET/N.sub.2 specific area of from 3 m.sup.2/g to 6 m.sup.2/g.

9. The mineral material according to claim 7, wherein the calcium carbonate after grinding in step a) and before optional treatment in step d) has a BET/N.sub.2 specific area of from 3 m.sup.2/g to 5.9 m.sup.2/g.

10. The mineral material according to claim 1, wherein the mineral material is wet ground in step a) at a solids content of from 10 wt % to 40 wt %.

11. The mineral material according to claim 1, wherein in step b) the aqueous suspension or slurry is up-concentrated or dewatered to achieve a solids content of between 55% and 65%.

12. The mineral material according to claim 1, wherein step d) takes place and the at least one aliphatic carboxylic acid is selected from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosylic acid, behenic acid, lignoceric acid, and any mixture thereof.

13. A product comprising the mineral material according to claim 1, wherein the product is paper, paint, a coating, a thermoplastic resin, a thermoset resin, a thermoplastic polymer, rubber, food, a food packaging, a cosmetic, a pharmaceutical, concrete, a mortar, a masterbatch, a dry blend, or a granulate.

14. The product according to claim 13, wherein the product is a thermoplastic polymer selected from the group consisting of polyolefins, halogenated polymer resins, styrenic resins, acrylic resins, polycarbonate resins, polyester resins, polyurethane resins, foamed polyurethane, flexible polyurethane foams, unsaturated polyester resins, polyamide resins, and any combination thereof.

15. The product according to claim 13, wherein the product is a thermoplastic polymer selected from the group consisting of a halogenated polymer resin, polyvinylchloride (PVC), post-chlorinated vinyl polychloride (PVCC), vinylidene polyfluoride (PVDF), or any mixture thereof.

16. The product according to claim 13, wherein the product is a thermoplastic polymer comprising homopolymers and/or copolymers of polyethylene and/or propylenes, and any mixtures thereof.

17. The product according to claim 15, wherein the thermoplastic polymer is polyvinylchloride (PVC) and the mineral matter is present in an amount from 1 phr to 200 phr.

18. The product according to claim 17, wherein the product has a charpy impact strength of from 10 kJ/m.sup.2 to about 140 kJ/m.sup.2 measured according to ISO 179/1eA on an extruded sample, and a gloss 60° [−] from about 20 to about 60.

19. The product according to claim 17, wherein the product is incorporated into a window profile, a pipe, a cable, a wire, a wall panel, a ceiling panel, a cladding panel, a fibre or a non-woven.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1a shows a SEM picture of an untreated CaCO.sub.3 obtained by the processes of the prior art. After drying and before de-agglomeration, large agglomerates still are present and thus provide for a less homogeneous dispersion of the CaCO.sub.3 in final products.

(2) FIG. 1b shows a SEM picture which of an untreated CaCO.sub.3 obtained by the process of the present invention. After drying and before de-agglomeration almost no agglomerates are present and thus promote good dispersing ability of the CaCO.sub.3 in final products

(3) FIG. 2a shows pictures of blown film samples according to table 7, wherein two prior art CaCO3 masterbatches are compared to the masterbatch of the present invention at CaCO3 concentrations of 20 wt % of the whole polymer.

(4) FIG. 2b shows pictures of blown film samples according to table 7, wherein a prior art CaCO3 masterbatch is compared to the masterbatch of the present invention at CaCO3 concentrations of 10 wt % of the whole polymer.

EXAMPLES

(5) Measuring Methods

(6) If not otherwise indicated, the parameters mentioned in the present invention are measured according to the measuring methods described below.

(7) Weight Median Particle Diameter d.sub.50 Value

(8) Throughout the present invention, d.sub.50 is the weight median particle diameter by weight, i.e. representing the particles in such a manner that 50 wt-% of the particles are coarser or finer.

(9) The weight median particle diameter was measured according to the sedimentation method. The sedimentation method is an analysis of sedimentation behaviour in a gravimetric field. The measurement is made with a Sedigraph™ 5100 from Micromeritics Instrument Corporation. The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments routinely. The measurement is carried out in an aqueous solution of 0.1 wt % Na4P207. The samples were dispersed using a high speed stirrer and ultrasound.

(10) Specific Surface Area (BET)

(11) The specific surface area was measured using nitrogen and the BET method according to ISO 9277.

(12) Charpy Impact Strength

(13) Charpy notched impact strength was measured according to 179-1:2000 according to conditions 1 fC and 1 eA on V-notched extruded samples which were cut out of the extrudate in machine direction. Measuring conditions: 23° C.±2° C. and 50%±10% relative humidity. The test specimens were prepared by extrusion as described in ISO 3167 Typ A.

(14) Moisture Content

(15) Moisture content of the inorganic mineral material is determined by thermogravimetric analysis (TGA). TGA analytical methods provide information regarding losses of mass with great accuracy and is common knowledge, and described in “Principles of Instrumental analysis”, fifth edition, Skoog, Holler, Nieman, 1998 (first Ed. 1992) in Chapter 31, pages 798-800, and in many other commonly known references known to the skilled person. In the present invention, thermogravimetric analysis was performed using a Mettler Toledo TGA 851 based on a sample of 500 mg±50 mg and a scanning temperature from 105° C. to 400° C. at a rate of 20° C./minute under an air flow of 70 ml/min.

(16) K-Value of PVC: A measure of the molecular weight of PVC based on measurements of viscosity of a PVC solution. It ranges usually between 35 and 80. Low K-values imply low molecular weight (which is easy to process but has inferior properties) and high K-values imply high molecular weight, (which is difficult to process, but has outstanding properties). In general, K-values for a particular PVC resin are provided by the resin producer either on the packaging or the accompanying technical data sheet.

(17) Brookfield™ Viscosities

(18) The viscosities of the mixtures were measured using a Brookfield™ (model DV-II+) viscometer at 30° C. with spindle n° 5, at 10 rpm and 100 rpm.

(19) Surface Gloss

(20) The surface gloss was measured with a Byk Spectro Guide Sphere Gloss at an angle of 60° from the plane surface according to ISO 2813:1994. The gloss value is determined by calculating the average value of n measurement. In the present set up n=10.

(21) Test 1: Preparation and Testing of Samples (in Rigid PVC)

(22) TABLE-US-00002 TABLE 2 Example C1 C1' (6 hr)* C2 E1 E2 PVC K-value 66 100 (phr) 100 (phr) 100 (phr) 100 (phr) 100 (phr) (Evipol SH6630) Ca—Zn containing stabilizer 4.3 (phr) 4.3 (phr) 4.3 (phr) 4.3 (phr) 4.3 (phr) (Stabilox CZ 2913 GN) Lubricant: 12-Hydroxy 0.2 (phr) 0.2 (phr) 0.2 (phr) 0.2 (phr) 0.2 (phr) stearic acid (Realube AIS) Lubricant: PE wax 0.15 (phr) 0.15 (phr) 0.15 (phr) 0.15 (phr) 0.15 (phr) (Realube 3010) Titanium dioxide 3.5 (phr) 3.5 (phr) 3.5 (phr) 3.5 (phr) 3.5 (phr) (Kronos 2220) Acrylic impact modifier 6 (phr) 6 (phr) 6 (phr) 6 (phr) 6 (phr) (Durastrength 340) Ground natural CaCO.sub.3 8 (phr) 8 (phr) 16 (phr) 8 (phr) 16 (phr) BET [m.sup.2/g] 7.9 7.9 7.9 5.9 5.9 Median d.sub.50 [μm] 0.94 0.94 0.94 0.71 0.71 Top Cut d.sub.98 [μm] 5 5 5 3 3 Charpy impact resistance 51 47 42 56 55 [kJ/m.sup.2] ISO179/1fC Gloss 60°[-] 36 34 22 49 36 L*-value 95.32 95.36 95.48 96.17 96.02 a*/b*-value −0.43/3.43 −0.42/3.41 −0.20/3.95 −0.36/3.64 −0.25/4.02 Torque [Nm] 513 505 482 472 461 (6 hr)* C1' is a reference run after continuous extrusion for 6 hr.

(23) The components for comparative examples C1, C1′, C2 as well as inventive examples E1 and E2 in Test 2 were previously mixed using the usual hot/cold mixing process known to the skilled person, and extruded on a Göttfert extrusion line equipped with a Krauss-Maffei plastification unit, L/D 32, with counter rotating parallel twin screws, the screws having a diameter of 30 mm each.

(24) TABLE-US-00003 TABLE 2 Preparation and testing of samples Example C1 C1' (2 hr)* C2 E1 E2 PVC K-value 65 100 (phr) 100 (phr) 100 (phr) 100 (phr) 100 (phr) (Vestolit P 1982 K) Ca—Zn containing 3* 95 (phr) 3.95 (phr) 3.95 (phr) 3.95 (phr) 3.95 (phr) stabilizer from Bärlocher Calcium stearate 0.2 (phr) 0.2 (phr) 0.2 (phr) 0.2 (phr) 0.2 (phr) Lubricant: PE wax 0.15 (phr) 0.15 (phr) 0.15 (phr) 0.15 (phr) 0.15 (phr) (Realube 3010) Titanium dioxide 3.5 (phr) 3.5 (phr) 3.5 (phr) 3.5 (phr) 3.5 (phr) (Kronos 2220) Ground natural CaCO.sub.3 8 (phr) 8 (phr) 16 (phr) 8 (phr) 16 (phr) BET [m.sup.2/g] 7.9 7.9 7.9 5.9 5.9 Median d.sub.50 [μm] 0.94 0.94 0.94 0.71 0.71 Top Cut d.sub.98 [μm] 5 5 5 3 3 Charpy impact resistance 55 39 49 130 118 [kJ/m.sup.2] ISO179/1eA Gloss 60°[-] 42 43 27 56 47 L*-value 95.23 95.22 96.17 96.82 95.99 a*/b*-value −0.40/3.38 −0.42/3.25 −0.52/3.70 −0.39/3.09 −0.24/3.86 Torque [Nm] 515 520 511 490 475 (2 hr)* C1' is a reference run after continuous extrusion for 2 hr.

(25) The components for comparative examples C1, C1′, C2 as well as inventive examples E1 and E2 in Test 1 were previously mixed using the usual hot/cold mixing process known to the skilled person, and extruded on a Krauss-Maffei KMD 2-90 profile extrusion line, L/D 22, with counter rotating parallel twin screws, the screws having a diameter of 90 mm each.

(26) The CaCO.sub.3 of comparative examples C1, C1′ and C2, is a prior art CaCO.sub.3 having the following characteristics. The CaCO.sub.3 is of natural origin. The BET surface area is 7.9 m.sup.2/g with a mean particle diameter d.sub.50 of 0.94 μm. The CaCO.sub.3 was prepared according to grinding methods known to the skilled person and as described in U.S. Pat. Nos. 5,533,678 or 5,873,935 with the use of dispersing agents during the wet grinding process and treated with 1 wt % of an industrial fatty acid mixture of C.sub.18/C.sub.16 in amounts of 50 wt %/50 wt %. Such industrial fatty acid mixtures can vary in their C.sub.18/C.sub.16 amount from about 30 wt %-70 wt %/70 wt %-30 wt %, as well as in their carbon chain length being from C.sub.14 to C.sub.20.

(27) The CaCO.sub.3 of the inventive examples E1 and E2 have been prepared according to the process of the present invention, thus without relevant processing aids during wet grinding, and with a surface treatment after drying with 1 wt % of an industrial fatty acid mixture of C.sub.18/C.sub.16 in amounts of 50 wt %/50 wt %.

(28) Test 1

(29) E1 provides for a 10% increase in charpy impact resistance (ISO 179/1fC) with same amount (8 phr) of CaCO.sub.3 of the present invention as the comparative example C1. With higher amount E2 (16 phr) of the CaCO.sub.3 of the present invention the charpy impact strength (ISO 179/1fC) on an extruded profile is still about 10% higher than the charpy impact strength of C1 or C1′ and even 20% than comparative example C2 with same amounts of CaCO.sub.3 of 16 phr. A further change can be observed in the torque of the extruder, which is affected positively, as the Torque is decreasing with increasing CaCO.sub.3 content provided according to the present invention. Lower torque means lower energy consumption in first place but also less stress imposed on the polymer matrix during extrusion.

(30) Gloss 60° [−] of E1 (8 phr), and E2 (16 phr) is significantly improved over comparative examples C1 (8 phr) and C2 (16 phr) by about 35% at 8 phr and by about 60% at 16 phr. Further optical properties such as brightness—see L*-value, are not affected to the negative and red-/yellowness-values—see a*/b*-values, remain within the tolerances and thus the overall benefit provided by the present invention is shown. Noteworthy that a thermoplastic PVC resin comprising a mineral filler of the present invention has improved gloss and Charpy impact strength as well as a better processability as lower torque is needed when made into a final product such as window profile.

(31) Test 2

(32) E1 provides for an increase in the Charpy impact resistance (IS0179/1eA) by about 100%, with same amount (8 phr) of CaCO.sub.3 of the present invention as the comparative example C1. With higher amount (16 phr) of the CaCO.sub.3 of the present invention the Charpy impact strength (IS0179/1eA) on an extruded profile is still over 100% higher than the Charpy impact strength of C1, C1′ and C2. A further change can be observed in the torque of the extruder, which is affected positively, as the Torque is decreasing with increasing CaCO.sub.3 content provided according to the present invention. Lower torque means lower energy consumption in first place but also less stress imposed on the polymer matrix during extrusion. Finally optical properties such as gloss or yellowness are within the tolerances and thus the overall benefit provided by the present invention is show, noteworthy the replacement of at least 8 phr of a PVC polymer by a filler without negatively affecting physical and optical properties.

(33) Gloss 60° [−] of E1 (8 phr), and E2 (16 phr) is significantly improved over comparative examples C1 (8 phr) and C2 (16 phr) by about 30% at 8 phr and by about 10% at 16 phr. Further optical properties such as brightness—see L*-value, are not affected to the negative and red-/yellowness-values—see a*/b*-values, remain within the tolerances and thus the overall benefit provided by the present invention is shown. Noteworthy that a thermoplastic PVC resin comprising a mineral filler of the present invention has improved gloss and Charpy impact strength as well as a better processability as lower torque is needed when made into a final product such as window profile.

(34) The thermoplastic PVC polymer product comprising the thermoplastic PVC resin composition comprising the mineral material of the present invention in amounts from 1 phr to 20 phr, preferably from about 5 phr to about 19 phr, still more preferably from about 6 phr to about 18 phr, and still more preferably from about 7 phr to about 17 phr, and further comprising additives such as stabilizers, impact modifiers, lubricating agents, processing aids, pigments and combinations thereof in amounts as previously described has a charpy impact strength at 23° C. of from 80 kJ/m.sup.2 to 150 kJ/m.sup.2, preferably from 100 kJ/m.sup.2 to 140 kJ/m.sup.2 measured according to ISO 179/1eA on extruded samples.

(35) The thermoplastic PVC polymer product comprising the thermoplastic PVC resin composition comprising the mineral material of the present invention in amounts from 1 phr to 20 phr, preferably from about 5 phr to about 19 phr, still more preferably from about 6 phr to about 18 phr, and still more preferably from about 7 phr to about 17 phr, and further comprising additives such as stabilizers, impact modifiers, lubricating agents, processing aids, pigments and combinations thereof in amounts as previously described has a Charpy impact strength at 23° C. of from 50 kJ/m.sup.2 to 80 kJ/m.sup.2, preferably from 50 kJ/m.sup.2 to 70 kJ/m.sup.2 measured according to ISO 179/1fC on extruded samples.

(36) The term “charpy impact strength” within the meaning of the present invention refers to the kinetic energy per unit area required to break a test specimen under flexural impact. Test specimen is held as a simply supported beam and is impacted by a swinging pendulum. The energy lost by the pendulum is equated with the energy absorbed by the test specimen.

(37) Further embodiments comprising the mineral matter according to the present invention are now presented.

(38) Use in Unsaturated Polyester Resins

(39) The mineral material of the present invention is made into unsaturated polyester resins in order to provide for a sheet moulding compound (SMC) or bulk moulding compound (BMC) which is a mould fibre-reinforced polyester material primarily used in compression moulding. The manufacturing of SMCs require in general two steps. The first step consists of providing for a thermoset resin, the second step (conversion operation), known as SMC compression, is the moulding in a hot press. During said conversion operation the combined action of increased temperature and mechanical pressure allows the filling of the mould with the SMC and the crosslinking of the thermoset resin.

(40) An unsaturated polyester resins comprising chopped glass fibres with 2-3 cm length and around 100 μm in diameter is mixed with the mineral material of the present invention, to provide for a sheet like, ductile, non-sticky SMC.

(41) The quality of the filled thermoset resin mainly depends on the contact between the glass fibres and the filled unsaturated polyester resin, which is strongly affected by the rheology of the composition, and therefore depending on a good dispersing ability of the mineral filler of the present invention.

(42) Said mineral material according to the present invention, is preferably an untreated CaCO.sub.3 with a median particle size diameter of about 0.1 μm to about 1.5 μm, preferably from about 0.4 μm to about 1.1 μm, more preferably from about 0.6 μm to about 0.9 μm, and most preferably of 0.8 μm, and wherein the BET/N.sub.2 specific surface area is measured on the untreated mineral material and amounts from 3 m.sup.2/g to 13 m.sup.2/g, preferably from 6 m.sup.2/g to 10 m.sup.2/g, more preferably from 7 m.sup.2/g to 8 m.sup.2/g.

(43) The mineral material according to the present invention has a top cut d.sub.98 equal or below 6 μm, such as from about 5.9 μm to about 1.8 μm, preferably from about 5 μm to about 1.8 μm, more preferably from about 4 μm to about 2.5 μm

(44) The amount of the CaCO.sub.3 according to the present invention used is from about 10 wt % to about 75 wt %, preferably from about 15 wt % to about 60 wt %, more preferably from about 20 wt % to about 50 wt %. The amount of glass fibres is comprised from about 5 wt % to about 45 wt %, preferably from about 10 wt % to about 40 wt %, more preferably from about 15 wt % to about 35 wt %. The unsaturated polyester resin amounts from about 5 wt % to about 35 wt %, preferably from about 10 wt % to about 30 wt %, more preferably from about 10 wt % to about 20 wt %.

(45) The SMC may further comprise other compounds in usual amounts such as additives to prevent shrinkage, flame retardants, crosslinking promoters such as peroxides, colorants, pigments, electro conducting materials and many more.

(46) According to one embodiment, 75 kg of an unsaturated polyester resin (Palapreg P18-03, from DSM), 50 kg of low profile additive (Parapleg H 852-03, from DSM) and 250 kg of an untreated CaCO.sub.3 according to the present invention were mixed, wherein the CaCO.sub.3 had a mean particle size d.sub.50 of 1.5 μm, a top cut d.sub.98 of 6 μm and BET specific surface area of 3.8 m.sup.2/g. Brookfield™ viscosities of the formulation were measured after 2 hrs at 30° C., at 10 rpm (revolutions per minute) and 100 rpm, using spindle n° 5, and are summarized in Table 3.

(47) TABLE-US-00004 TABLE 3 Brookfield Brookfield viscosity at 10 viscosity at 100 rpm, 30° C. (mPa.$) rpm, 30° C. (mPa.$) Brookfield viscosities 31'120 14'500 (spindle n° 5) of the formulation after 2 hrs

(48) Brookfield™ viscosities of the filled unsaturated polyester resin, comprising the CaCO.sub.3 of the present invention, showed a very good quality of the paste resulting in a good wetting effect of the glass fibers by the unsaturated polyester paste. The SMC and BMC obtained after molding with said glass fiber filled unsaturated polyester resin provided for a high surface quality and good mechanical properties.

(49) Use in Flexible Polyurethane Foam

(50) The mineral material of the present invention is made into flexible polyurethane foam.

(51) In general polyurethane foams are prepared by methods comprising the steps of reacting a polyol with an isocyanate in the presence of water to form a flexible polyurethane foam. The polyol include polyether polyols, obtained, for example by adding propylene oxide or ethylene oxide to glycerine, trimethlyolpropane or diethylene glycol, although the type of the base polyol is not critical. The polyol preferably has a on OH value of 10 to 100, preferably from 20 to 80, more preferably from 30 to 55.

(52) In order to get a good dispersed mineral material according to the present invention in the flexible polyurethane foam, the mineral material of the present invention is introduced into the polyol matrix, prior to mixing with the other components.

(53) The mineral material to be used in the above mentioned process can be any natural or synthetic calcium carbonate or calcium carbonate comprising material selected from the group comprising marble, chalk, dolomite, calcite, limestone, magnesium hydroxide, talc, gypsum, titanium oxide or mixtures thereof.

(54) Said mineral material according to the present invention, is preferably an untreated CaCO.sub.3 with a median particle size diameter of about 0.1 μm to about 1.5 μm, preferably from about 0.4 μm to about 1.1 μm, more preferably from about 0.6 μm to about 0.9 μm, and most preferably of 0.8 μm, and wherein the BET/N.sub.2 specific surface area is measured on the untreated mineral material and amounts from 3 m.sup.2/g to 13 m.sup.2/g, preferably from 4 m.sup.2/g to 12 m.sup.2/g, more preferably from 5 m.sup.2/g to 10 m.sup.2/g, still more preferably from 6 m.sup.2/g to 9 m.sup.2/g, and still more preferably from 7 m.sup.2/g to 8 m.sup.2/g. Said untreated mineral material obtained by the process of the present invention has a top cut d.sub.98 equal or below 6 nm, such as from about 5.9 nm to about 1.8 nm, preferably from about 5 nm to about 1.8 nm, more preferably from about 4 nm to about 2.5 nm.

(55) The amount of the CaCO.sub.3 according to the present invention used is from about 10 wt % to about 75 wt %, preferably from about 15 wt % to about 60 wt %, more preferably from about 20 wt % to about 45 wt %.

(56) According to one embodiment, flexible polyurethane foam was prepared by mixing the components as presented in Table 4.

(57) TABLE-US-00005 TABLE 4 Unit Formulation Polyol I OH = 48 parts 100 CaCO.sub.3 according to the present invention % of polyol 10 Triethylene diamine diluted at 33% (w/w) % of polyol 0.15 in dipropylene glycol Stannous octoate % of polyol 0.22 Tegostab BF 2370 from Evonik % of polyol 0.8 Water % of polyol 4.6 Toluene diisocyante (TDI) 80% % of polyol 56.2 Isocyanate index % 108 Cream time s 18.1 Rise time s 96

(58) The preparation of the flexible polyurethane foam was made according to the following procedure:

(59) In a sealable glass bottle of 220 ml, toluene di-isocyanate (TDI) was weighed after storage for a minimum of 6 hours at room temperature. After weighing, the bottle was closed and stored at room temperature.

(60) In a polyethylene bottle of 800 ml, the following ingredients were weighed in order of citation: the surfactant, polyol, water, amine catalyst, the tin-based catalyst. It should be noted that all these reagents were stored at room temperature at least 6 hours before handling.

(61) The polyethylene bottle was stirred with a mixer GRENIER-CHARVET equipped with a high shear disk. Stirring was carried out at a speed sufficient to create a vortex.

(62) The TDI previously prepared in the glass bottle was then emptied completely in the polyethylene bottle and a stopwatch was put into operation simultaneously (the t=0 of the experiment). After 20 seconds of intensive mixing of the reaction medium, the content of the polyethylene bottle was put promptly and fully into a paper box with a form of cube (side 20 cm). The cream time of the beginning of the expansion was measured and the corresponding rise time at the end of the expansion of the flexible polyurethane foam.

(63) After the end of the rise, the polyurethane foam sample thus prepared was introduced into a ventilated oven at 100° C. for 15 minutes. At the end of the curing, the polyurethane foam sample was stored for at least 24 hours before being cut for the measurement of different physico-chemical and mechanical properties. The values given in table 5 are the average of measurements on five samples of flexible polyurethane foam.

(64) The tests were performed to obtain between 300 and 500 g of polyurethane foam. When the calcium carbonate was introduced in the composition of the foam, it has been incorporated into the polyethylene bottle after the polyol and before the water. Before the introduction into the composition the CaCO.sub.3 of the present invention was dispersed in a part of the polyol used in the composition. The concentration of the calcium carbonate in the polyol was between 40 and 50% by weight.

(65) The CaCO.sub.3 of the present invention used in this example had a mean particle size d.sub.50=1.4 μm, a top cut d.sub.98 equal to 5 μm and a BET specific surface area equal to 5 m.sup.2/g.

(66) The viscosity of the dispersion (45 wt % of CaCO.sub.3) was measured with a Brookfield™ viscometer at 23° C. and was equal to 3800 mPa.Math.s.

(67) TABLE-US-00006 TABLE 5 Density (kg/m.sup.3) 26 Compression to 40% (NFT 56-110) (N/dm.sup.2) 50 Compression to 50% (NFT 56-110) (N/dm.sup.2) 56.8 Tear resistance (NFT 56-109) (N/m) 767 Tensile strength (NFT 56-108) (N/mm.sup.2) 0.098 Elongation at break (NFT 56-108) (%) 139
Use in LLDPE Masterbatch

(68) The mineral material of the present invention is made into a masterbatch of a polyolefin. In particular the mineral material of the present invention in treated form is compounded into a linear low density polyethylene (LLDPE). The LLDPE is present in amounts of about 10 wt % to about 80 wt % and the treated mineral material of the present invention is present in amounts of about 90 wt % to about 20 wt %. Preferably the LLDPE is present in amount of 20 wt % to about 50 wt % and the treated mineral material according to the present invention is present in amounts of 80 wt % to about 50 wt %. More preferably the LLDPE is present in amounts of 25 wt % to about 45 wt % and the treated mineral material according to the present invention is present in amounts of 85 wt % to about 60 wt %, most preferably the masterbatch is composed of 30 wt % to 40 wt % of the LLDPE and of 70 wt % to about 60 wt % of the treated mineral material according to the present invention, and wherein the median particle diameter d.sub.50 was determined on the untreated mineral material and has a value from about 0.1 μm to about 1.5 μm, preferably from about 0.4 μm to about 1.1 μm, more preferably from about 0.6 μm to about 0.9 μm, and most preferably of 0.8 μm, and wherein the BET/N.sub.2 specific surface area is measured on the untreated mineral material and amounts from 3 m.sup.2/g to 13 m.sup.2/g, preferably from 6 m.sup.2/g to 10 m.sup.2/g, more preferably from 7 m.sup.2/g to 8 m.sup.2/g.

(69) The mineral material can be any natural or synthetic calcium carbonate or calcium carbonate comprising material selected from the group comprising marble, chalk, dolomite, calcite, limestone, magnesium hydroxide, talc, gypsum, titanium oxide or mixtures thereof.

(70) A filter pressure test was performed in order to determine the filter pressure value FPV of a LLDPE masterbatch as described above and compared to the FPV a masterbatch comprising a mineral material of the prior art. An example of a masterbatch is given in Table 6, wherein 30 wt % of an LLDPE was used as carrier resin.

(71) The filter pressure test as herein described provides for the Filter Pressure Value, in the present case, of dispersed mineral material in a LLDPE. The Filter Pressure Value FPV is defined as the increase of pressure per gram filler. This test is performed to determine the dispersion quality and/or presence of excessively coarse particles or agglomerates of mineral materials in a masterbatch. Low Filter Pressure Values refers to a good dispersion and fine material, wherein high Filter Pressure Values refer to bad dispersion and coarse or agglomerated material.

(72) The Filter Pressure test was performed on a commercially available Collin Pressure Filter Test, Teach-Line FT-E20T-IS, according to the standard EN 13900-5. Filter type used was 14 μm and 25 μm, extrusion was carried out at 200° C.

(73) The masterbatch which was tested was composed of 30 wt % of a LLDPE from Dow (Dowlex 2035 G), with a density of 0.919 g/cm.sup.3, and a MFR.sub.2.16 at 190° C. was 6.0 g/10 min, and 70 wt % of treated CaCO.sub.3 from the prior art or treated CaCO.sub.3 made according to the process of the present invention.

(74) TABLE-US-00007 TABLE 6 Masterbatch: LLDPE Dowlex 2035G at 30 wt % + 70 wt % of CaCO.sub.3 Filterpressure Filterpressure Test Test Pore size filter 14 μm 25 μm 70 wt % CaCO.sub.3 0.68 n/a bar/g treated (invention) 70 wt % CaCO.sub.3 2.50 n/a bar/g treated (prior art 1) 70 wt % CaCO.sub.3 6.69 1.07 bar/g treated (prior art 2) 70 wt % CaCO.sub.3 7.34 1.77 bar/g treated (prior art 3)

(75) The CaCO.sub.3 according to the present invention clearly shows its beneficial properties over the CaCO.sub.3 of the prior art 1-3 when made into a masterbatch. The pressure on the pore filter at 14 μm shows that the CaCO.sub.3 of the prior art causes clogging of the filter due to bad dispersed and/or coarse CaCO.sub.3 particles, whereas the CaCO.sub.3 according to the present invention, causes no clogging and thus also no significant pressure build up at the pore size filter, thus nicely demonstrating the advantageous properties, the improved dispersion of the CaCO.sub.3 particles in the polymer matrix.

(76) Further to this, said filled LLDPE masterbatches were made into blown film by means known to the skilled person. Samples of the said blown films comprising the CaCO.sub.3 according to the present invention and samples of blown films comprising the prior art CaCO.sub.3 are compared hereafter in table 7. Different amounts of filled masterbatch were mixed with a further LLDPE (Dowlex 5056G) and blown films were made from these mixtures.

(77) TABLE-US-00008 TABLE 7 Formulation of examples 1 2 3 4 5 6 7 Aqua- trac ppm g/cm.sup.3 LLDPE 0.919 100.0 85.7 71.4 85.7 71.4 66.7 71.4 Dowlex 5056G 70% MB 484 1.730 14.3 28.6 Invention 70% MB PA1 460 1.730 14.3 28.6 60% MB 1.540 33.3 Invention 70% MB PA2 618 1.730 28.6 Weight of kg 100.0 100.0 100.0 100.0 100.0 100.0 100.0 the mixture Density of g/cm.sup.3 0.92 0.99 1.06 0.99 1.06 1.06 1.06 the mixture Universal tests Tensile ISO N/mm.sup.2 10.3 10.4 10.4 10.3 10.2 10.7 10.0 strength at 527 yield, MD.sup.1 Tensile ISO N/mm.sup.2 9.4 9.3 9.7 9.9 8.9 10.3 9.8 strength at 527 yield, CD.sup.2 Elongation at ISO % 13.7 9.8 9.2 11.1 8.6 9.2 9.9 yield, MD.sup.1 527 Elongation at ISO % 9.5 8.0 6.9 8.1 6.5 6.8 7.4 yield, CD.sup.2 527 Tensile ISO N/mm.sup.2 60.3 53.7 45.3 44.4 38.0 36.5 31.7 strength at 527 break, MD.sup.1 Tensile ISO N/mm.sup.2 55.1 45.1 35.7 33.2 29.5 35.2 25.1 strength at 527 break, CD.sup.2 Elongation at ISO % 561 514 509 502 487 507 448 break, MD.sup.1 527 Elongation at ISO % 609 581 558 519 526 570 488 break, CD.sup.2 527 Elmendorf ISO cN 287 298 362 328 391 461 393 tear 6383/ propagation 2 resistance, MD.sup.1 Elmendorf ISO cN 406 397 522 453 522 564 531 tear 6383/ propagation 2 resistance, CD.sup.2 E-modulus, ISO N/mm.sup.2 246 280 299 282 317 314 298 MD.sup.1 527 E-modulus, ISO N/mm.sup.2 246 270 304 297 315 347 316 CD.sup.2 527 Opacity 13.4 16.6 20.9 15.7 18.7 20.6 18.4 Dart drop grams 441 609 561 453 348 621 219 impact Thickness, μm 23 20 21 24 23 23 24 MD.sup.1 Thickness, μm 22 21 22 22 22 22 23 CD.sup.2 .sup.1MD refers to machine direction, .sup.2CD refers to cross direction.

(78) 70% MB Invention refer to 70 wt % of a masterbatch of 30 wt % LLDPE Dowlex 2035G and 70 wt % of CaCO3 according to the present invention, wherein the treated CaCO.sub.3 has a median particles size diameter d.sub.50 of 0.8 μm, a top cut of d.sub.98 of 3 μm, and a BET specific surface area of 6 m.sup.2/g.

(79) 70% of MA PA1 refers to 70 wt % of a masterbatch of 30 wt % LLDPE Dowlex 2035 and 70 wt % of a ground surface treated CaCO.sub.3 of the prior art, comprising an acrylic dispersing agent, wherein the surface treating agent is stearic acid, and the CaCO.sub.3 has a median particle size diameter d.sub.50 of 1.6 μm and a top cut of d.sub.98 of 6 μm.

(80) 70% MA PA2 refers to 70 wt % of a masterbatch of 30 wt % LLDPE Dowlex 2035 and 70 wt % of a ground surface treated CaCO.sub.3 of the prior art, comprising an acrylic dispersing agent, wherein the surface treating agent is stearic acid, and the CaCO.sub.3 has a median particle size diameter d.sub.50 of 0.8 μm and a top cut of d.sub.98 of 5 μm, and a BET specific surface area of 10 m.sup.2/g.

(81) As can be seen from the inventive examples 2, 3 and 6 from table 7, the tensile strength at break as well as the dart drop impact are significantly improved, while at the same time the film thickness reduced, compared to the comparative examples of the prior art 4, 5 and 7. Example 1 being the unfilled LLDPE Dowlex 5056G.

(82) It lies within the scope of the present invention that the LLDPE mentioned are not the only one and that other LLDPE polymers are suitable as well to be used for producing a masterbatch comprising the CaCO.sub.3 of the present invention.

(83) Therefore, the masterbatch comprising the CaCO.sub.3 of the present invention can be used not only in blown films, but also in the extrusion of pipes, tubes, or hoses, in sheet extrusion, in cast film for subsequent thermoforming, and other processed known to the skilled person.

(84) Use in PP Masterbatch

(85) Still another embodiment of the mineral matter according to the present invention is now presented. The mineral material of the present invention is made into a masterbatch of a polyolefine. In particular the mineral material of the present invention in treated form is compounded into a polypropylene (PP). The PP is present in amounts of about 10 wt % to about 80 wt % and the treated mineral material of the present invention is present in amounts of about 90 wt % to about 20 wt %. Preferably the PP is present in amount of 20 wt % to about 50 wt % and the treated mineral material according to the present invention is present in amounts of 80 wt % to about 50 wt %. More preferably the PP is present in amounts of 25 wt % to about 45 wt % and the treated mineral material according to the present invention is present in amounts of 85 wt % to about 60 wt %, most preferably the masterbatch is composed of 30 wt % to 40 wt % of the PP and of 70 wt % to about 60 wt % of the treated mineral material according to the present invention, and wherein the median particle diameter d.sub.50 was determined on the untreated mineral material and has a value from about 0.1 μm to about 1.5 μm, preferably from about 0.4 μm to about 1.1 μm, more preferably from about 0.6 μm to about 0.9 μm, and most preferably of 0.8 μm, and wherein the BET/N2 specific surface area is measured on the untreated mineral material and amounts from 4 m2/g to 15 m2/g, preferably from 6 m2/g to 10 m2/g, more preferably from 7 m2/g to 8 m2/g.

(86) Suitable PP materials are commercial products including, but are not limited to: PPH 9099 homopolymer polypropylene having a melt flow rate of 25 g/10 min, available from Total Petrochemicals; PPH 10099 homopolymer polypropylene having a melt flow rate of 35 g/10 min, available from Total Petrochemicals; Lumicene MR 2001 homopolymer polypropylene having a melt flow rate of 25 g/10 min, available from Total Petrochemicals; Moplen HP462R polypropylene having a melt flow rate of 25 g/10 min, available from LyondellBasell; Moplen HP561R polypropylene having a melt flow rate of 34 g/10 min, available from LyondellBasell; HG455FB homopolymer polypropylene having a melt flow rate of 27 g/10 min, available from Borealis.

(87) The mineral material can be any natural or synthetic calcium carbonate or calcium carbonate comprising material selected from the group comprising marble, chalk, dolomite, calcite, limestone, magnesium hydroxide, talc, gypsum, titanium oxide or mixtures thereof.

(88) A filter pressure test was performed in order to determine the filter pressure value FPV of a PP masterbatch as described above and compared to the FPV a masterbatch comprising a mineral material of the prior art.

(89) The filter pressure test as herein described provides for the Filter Pressure Value, in the present case, of dispersed mineral material, tested with Borealis HF 136 MO, a polypropylene homopolymer with a MFR of 20 g/10 min. The Filter Pressure Value FPV is defined as the increase of pressure per gram filler. This test is performed to determine the dispersion quality and/or presence of excessively coarse particles or agglomerates of mineral materials in a masterbatch. Low Filter Pressure Values refers to a good dispersion and fine material, wherein high Filter Pressure Values refer to bad dispersion and coarse or agglomerated material.

(90) The Filter Pressure test was performed on a commercially available Collin Pressure Filter Test, Teach-Line FT-E20T-IS, according to the standard EN 13900-5. Filter type used was 14 μm; extrusion was carried out at 230° C. The masterbatch which was tested was composed of 25 wt % of a PP, with a MFR 2.16 at 230° C. of 25 g/10 min.

(91) Further to this, said filled PP masterbatches were used by melt extrusion processes to form fiber and filaments and continuous filament nonwoven fabrics by means known to the skilled person.

(92) In accordance with known technology such as the continuous filament spinning for yarn or staple fiber, and nonwoven processes such as spunbond production and meltblown production, the fibers and filaments are formed by extrusion of the molten polymer through small orifices. In general, the fibers or filaments thus formed are then drawn or elongated to induce molecular orientation and affect crystallinity, resulting in a reduction in diameter and an improvement in physical properties.

(93) Spunmelt is a generic term describing the manufacturing of nonwoven webs (fabrics) directly from thermoplastic polymers. It encompasses 2 processes (spunlaid and meltblown) and the combination of both.

(94) In this process polymer granules are melted and molten polymer is extruded through a spinneret assembly which creates a plurality of continuous polymeric filaments. The filaments are then quenched and drawn, and collected to form a nonwoven web. Some remaining temperature can cause filaments to adhere to one another, but this cannot be regarded as the principal method of bonding. There are several methods available for forming the collected web of continuous filaments into a useful product by a bonding step, which includes, but is not be limited to calendaring, hydroentangling, needling and/or bonding by means of chemicals or adhesives.

(95) The spunlaid process (also known as spunbonded) has the advantage of giving nonwovens greater strength. Co-extrusion of second components is used in several spunlaid processes, usually to provide extra properties or bonding capabilities. In meltblown web formation, low viscosity polymers are extruded into a high velocity airstream on leaving the spinneret. This scatters the melt, solidifies it and breaks it up into a fibrous web.

(96) It is known to those skilled in the art to combine processes or the fabrics from different processes to produce composite fabrics which possess certain desirable characteristics. Examples of this are combining spunbond and meltblown to produce a laminate fabric that is best known as SMS, meant to represent two outer layers of spunbond fabric and an inner layer of meltblown fabric. Additionally either or both of these processes may be combined in any arrangement with a staple fiber carding process or bonded fabrics resulting from a nonwoven staple fiber carding process. In such described laminate fabrics, the layers are generally at least partially consolidated by one of the bonding steps listed above.

(97) Processes are well known in the art, and are commercially available, for producing spunbond fabric of polypropylene polymeric resin. The two typical processes are known as the Lurgi process and the Reifenhäuser process.

(98) The Lurgi process is based on the extrusion of molten polymer through spinneret orifices followed by the newly formed extruded filaments being quenched with air and drawn by suction through Venturi tubes. Subsequent to formation, the filaments are disbursed on a conveyor belt to form a nonwoven web.

(99) The Reifenhäuser process differs from the Lurgi process in that the quenching area for the filaments is sealed, and the quenched air stream is accelerated, thus inducing more effective entrainment of the filaments into the air stream.

(100) In the above-described systems, nonwoven fabrics are generally produced using polypropylene resins having a melt flow index of about 25 to 40 grams/10 minutes. A Lurgi line was used to produce polypropylene nonwovens. Extruder temperatures are between 230° and 250° C. The four spin beams are equipped with melt pumps and spinnerets which contain 600 orifices each with a diameter of 0.8 millimeters. The extruded filaments are formed to a nonwoven web. The conveyor belt speed was adjusted to 20 meters/minute and hydroentangling was used to bond the nonwoven web. Hydroentangling, also known as spunlacing, is a process which employs high pressure water jets to entangle fibers in a loose web thereby creating a fabric held together by frictional forces between the said fibers. The final bonded nonwoven web with a width of 100 cm has a fabric weight of 385 g/m.sup.2.

(101) Samples of the said nonwoven fabrics comprising the CaCO.sub.3 according to the present invention and samples of nonwoven fabrics comprising the prior art CaCO.sub.3 are compared hereafter in tables 8 and 9. Different amounts of the filled masterbatches were mixed with further polypropylene (PP HF420FB, a homo-polypropylene with MFR 19 g/10 min. (230° C., 2.16 kg, ISO 1133) from Borealis) and nonwoven fabrics were made from these mixtures.

(102) Measuring Methods

(103) If not otherwise indicated, the parameters mentioned in the present invention are measured according to the measuring methods described below.

(104) Measurements Done on Filament Samples

(105) Titer or Linear density [dtex] may be measured according to EN ISO 2062 and corresponds to the weight in grams of 10'000 m yarn. A sample of 25 or 100 meters is wound up on a standard reel under a pretension of 0.5 cN/tex and weighted on an analytical scale. The grams per 10'000 m yarn length are then calculated.

(106) Tenacity is calculated from the breaking force and the linear density, and expressed in centinewton per tex [cN/tex]. The test is carried out on a dynamometer with a constant stretching speed, applicable standards for this test are EN ISO 5079 and ASTM D 3822.

(107) Breaking force and elongation at break: The breaking force is the force needed to be applied on a yarn to make it break. It is expressed in Newton [N]. The elongation at break is the increase of the length produced by stretching a yarn to its breaking point. It is expressed as a percentage [%] of its initial length.

(108) Tensile index is the product of tenacity [cN/tex] and the square root of the elongation at break [%].

(109) Measurements Done on Nonwoven Samples

(110) Fabric weight or mass per unit area [g/m.sup.2] is measured according to EN ISO 9864.

(111) Tensile properties of geotextiles are measured according to EN ISO 10319 using a wide-width strip with 200 mm width and 100 mm length on a tensile testing machine. Tensile strength [kN/m] and the elongation at maximum load [%] are measured in machine direction (MD) and in cross machine direction (CD). The energy value according to EN ISO 10319 is calculated by the tensile strength (MD+CD)/2.

(112) Static puncture resistance (CBR test) in [kN] is measured according to EN ISO 12236. This method specifies the determination of the puncture resistance by measuring the force required to push a flat-ended plunger through geosynthetics.

(113) TABLE-US-00009 TABLE 8 Formulation 1 2 3 4 5 Polypropylene 100 96 96 96 96 HF420FB 70% MB 4 Invention1 70% MB PA1 4 70% MB 4 Invention2 70% MB PA2 4 Tests Norm Unit On Filaments Linear density dtex 8.46 8.64 9.3 8.59 Tenacity cN/ 26.9 26.0 24.2 24.3 tex Elongation % 217 211 206 207 Tensile index — 395 377 347 349 On Nonwoven Fabric weight EN ISO g/m.sup.2 379 387 396 393 9864 Coefficient CBR EN ISO N/g 8.4 8.3 7.7 8.0 12236 Tensile Strength EN ISO N/g 11.2 10.9 10.6 11.0 (MD + CD)/2 12319 Elongation MD .sup.1 EN ISO % 77 78 76 83 12319 Elongation CD .sup.2 EN ISO % 98 105 92 99 12319 .sup.1 MD refers to machine direction, .sup.2 CD refers to cross direction.

(114) TABLE-US-00010 TABLE 9 Formulation 1 2 3 4 5 Polypropylene 100 96 96 96 96 HF420FB 70% MB 4 Invention1 70% MB PA1 4 70% MB 4 Invention2 70% MB PA2 4 Tests Norm Unit On Filaments Linear density dtex 9.7 9.6 9.9 10.1 Tenacity cN/ 22.6 21.2 20.5 21.7 tex Elongation % 260 235 248 234 Tensile index — 364 325 323 332 On Nonwoven Fabric weight EN ISO g/m.sup.2 354 382 359 378 9864 Coefficient CBR EN ISO N/g 6.8 6.9 6.9 7.7 12236 CBR EN ISO N 2383 2632 2483 2899 12236 Tensile Strength EN ISO N/g 10.3 9.2 9.5 9.1 (MD + CD)/2 12319 .sup.1 MD refers to machine direction, .sup.2 CD refers to cross direction.

(115) 70% MB Invention1 refers to 70 wt % of a masterbatch of 28 wt % PP Lumicene MR 2001 a metallocene homo-polypropylene with MFR 25 g/10 min. (230° C., 2.16 kg, ISO 1133) from Total Petrochemicals and 2 wt % Irgastab FS 301, processing and thermal stabilizer from BASF and 70 wt % of CaCO.sub.3 according to the present invention, wherein the treated CaCO.sub.3 has a median particles size diameter d.sub.50 of 0.8 μm, a top cut of d.sub.98 of 3 μm, and a BET specific surface area of 6 m.sup.2/g.

(116) 70% MB Invention2 refers to 70 wt % of a masterbatch of 28 wt % PP HF420FB, a homo-polypropylene with MFR 19 g/10 min. (230° C., 2.16 kg, ISO 1133) from Borealis and 2 wt % Irgastab FS 301, processing and thermal stabilizer from BASF and 70 wt % of CaCO.sub.3 according to the present invention, wherein the treated CaCO.sub.3 has a median particles size diameter d.sub.50 of 0.8 μm, a top cut of d.sub.98 of 3 μm, and a BET specific surface area of 6 m.sup.2/g.

(117) 70% of MA PA1 refers to 70 wt % of a masterbatch of 28 wt % PP Lumicene MR 2001 a metallocene homo-polypropylene with MFR 25 g/10 min. (230° C., 2.16 kg, ISO 1133) from Total Petrochemicals and 2 wt % Irgastab FS 301, processing and thermal stabilizer from BASF and 70 wt % of a wet ground surface treated CaCO.sub.3 of the prior art, and the CaCO.sub.3 has a median particle size diameter d.sub.50 of 1.7 μm and a top cut of d.sub.98 of 6 μm.

(118) 70% of MA PA2 refers to 70 wt % of a masterbatch of 28 wt % PP Lumicene MR 2001 a metallocene homo-polypropylene with MFR 25 g/10 min. (230° C., 2.16 kg, ISO 1133) from Total Petrochemicals and 2 wt % Irgastab FS 301, processing and thermal stabilizer from BASF and 70 wt % of a wet ground surface treated CaCO.sub.3 of the prior art, and the CaCO.sub.3 has a median particle size diameter d.sub.50 of 1.7 μm and a top cut of d.sub.98 of 6 μm.

(119) As can be seen from the inventive example 2 from table 8, the tensile properties, especially the tenacity and the tensile index are significantly improved compared to the comparative examples 3 and 5. The inventive examples 2 and 4 from table 9 show the same improvement compared to the comparative example 5. Example 1 being the unfilled polypropylene PP HF420FB.

(120) It lies within the scope of the present invention that the polypropylenes mentioned are not the only one and that other PP polymers or PE polymers or a mix of PP and PE polymers are suitable as well to be used for producing a masterbatch comprising the CaCO.sub.3 of the present invention.

(121) The polypropylene masterbatch comprising the CaCO.sub.3 according to the present invention can be used for the production of monofilaments, tapes, multifilaments. Such filaments can either be spundbond or meltblown and be readily made in to non-woven such as listed here below. Hygiene (baby diapers, feminine hygiene, adult incontinence, nursing pads Wipes (medical wipes, industrial wipes, household wipes) Agro textiles (crop protection, capillary mats, greenhouse shading, root, control, seed blankets) Geotextiles (road/rail building, dam/canal lining, sewer liners, soil stabilization, drainage, golf/sport surfaces, roofing, insulation) Medical (face masks, head wear, shoe covers, disposable clothing, wound dressings, sterilisation aids) Filtration (air filters, liquid filters, tea bags, coffee filters) Technical (cable wrapping, floppy disk liners) Automotive (head liners, insulation door panels, air filters, battery separators, floor coverings) Upholstery (artificial leather) Household (wall covering, table decoration, floor coverings)
Use in Concrete

(122) TABLE-US-00011 TABLE 10 shows the use of the mineral material of the present invention in different amounts in a standard concrete mixture compared with a filler of the prior art. Sand Cement SAN099 CEM099 CaCO3 (density (density (density added mass mass Water/ 2.65 g/ml) 3.1 g/ml) 2.7 g/ml) water additive air water density Rc24h Rc28d binder Designation g g wt % g g g g g g/ml Mpa Mpa ratio Ref 1750 525 0.0 0 157 0 1032 598 2.38 11.4 22.6 0.30 PA1 1655 525 10.0 52.5 173 0 1085 623 2.35 13.8 22.5 0.33 PA1 1608 525 15.0 78.8 181 0 1132 639 2.30 22.4 35.3 0.34 Ref 1750 525 0.0 0 157 0 1042 603 2.37 11.6 21.8 0.30 IN1 1655 525 10.0 52.5 173 0 1117 634 2.31 17.4 33.3 0.33 IN1 1608 525 15.0 78.8 181 0 1194 683 2.34 37.8 72.5 0.34

(123) In a specific embodiment the CaCO.sub.3 of the present invention is a non-treated natural ground CaCO.sub.3 having a medium particle size diameter of d.sub.50 of 0.8 μm a top cut d.sub.98 of 3 μm and a BET surface area of 6 m.sup.2/g which was mixed with a standard sand SAN099 as defined in Standard EN 196-1, Cement CEM I 42.5N (CEM099), with different amount of CaCO.sub.3 filler, wherein 0 wt %, 10 wt % and 15 wt % of CaCO.sub.3 fillers are based on the weight of the cement binder. The concrete mixture further comprised water in amounts adapted to achieve the same workability. The present examples were prepared without further additives. The concrete mixture have the same volume of 986 ml. Said volume being calculated as: [mass sand]/[density sand]+[mass cement]/[density cement]+[volume water].

(124) Of course, other additives well known in the art could be added to the concrete mix without departing from the scope of the present invention. For example one could add water reducing agents, retarding agents, accelerating agents, super-plasticizers, corrosion inhibiting agents, pigments, surfactants, air entraining agents and others well known to the skilled person.

(125) The method of preparing the concrete mixture according to table 10 and evaluation of the results is made according to the description of the US patent application US 2012/0227632 of the same applicant.

(126) PA1 refers to a non-treated natural ground CaCO.sub.3 of the prior art having a medium particle size diameter of d.sub.50 of 1.4 μm a top cut d.sub.98 of 5 μm and a BET surface area of 5.5 m.sup.2/g.

(127) IN1 refers to a non-treated natural ground CaCO3 of the present invention, wherein the CaCO3 has medium particle size diameter of d.sub.50 of 0.8 μm a top cut d.sub.98 of 3 μm and a BET surface area of 6 m.sup.2/g.

(128) Ref refers to a concrete mixture reference without CaCO.sub.3 at all.

(129) Rc refers to compression resistance also known as compressive strength measurements after 24 hrs and 28 days of maturation of the concrete samples, which were carried out according to the method as described in US 2012/0227632 of the same applicant and EN 196-1. With the CaCO.sub.3 of the present inventions the stabilities compared to the prior art were increased by about 25% at 10 wt % of filler, and about 270% at 15 wt % of filler after 24 hrs. After 28 days, the stability was increased by about 50% at 10 wt % of filler and by about 100% at 15 wt % of filler compared to the filler of the prior art.