Process of controlled chemical reaction of a solid filler material surface and additives to produce a surface treated filler material product

Abstract

The present invention relates to a process for preparing a surface treated filler material product with succinic anhydride(s), a surface treated filler material product, a polymer composition, a fiber and/or filament and/or film and/or thread comprising the surface treated filler material product and/or the polymer composition, an article comprising the surface treated filler material product and/or the polymer composition and/or the fiber and/or filament and/or film and/or thread as well as the use of a mono-substituted succinic anhydride for decreasing the hydrophilicity of a calcium carbonate-containing filler material surface and the use of a surface-treated filler material product for initiating the crosslinking reaction in epoxide resins.

Claims

1. A surface treated filler material product comprising a) at least one calcium carbonate-containing filler material having i) a weight median particle size d.sub.50 value in the range from 0.1 μm to 7 μm, ii) a top cut (d.sub.98)≤15 μm, iii) a specific surface area (BET) of from 0.5 to 150 m.sup.2/g as measured by the BET nitrogen method, and iv) a residual total moisture content of ≤1 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material, and b) a treatment layer on the surface of the at least one calcium carbonate-containing filler material comprising (A) at least one mono-substituted succinic anhydride, (B) at least one mono-substituted succinic acid, and (C) optionally salty reaction product(s) of the at least one mono-substituted succinic acid and/or the at least one monosubstituted succinic anhydride, wherein the surface treated filler material product comprises the treatment layer in an amount of from 0.1 to 3 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

2. The surface treated filler material product according to claim 1, wherein the molar ratio of the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid to the salty reaction product(s) thereof is from 99.9:0.1 to 0.1:99.9.

3. The surface treated filler material product according to claim 1, wherein the salty reaction product(s) of the at least one mono-substituted succinic acid and/or the at least one mono-substituted succinic anhydride are one or more calcium and/or magnesium salts thereof.

4. The surface treated filler material product according to claim 1, wherein the treatment layer further comprises at least one organic material.

5. The surface treated filler material product according to claim 1, wherein the surface treated filler material product comprises the treatment layer in an amount of from 0.1 to 2.5 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

6. A polymer composition comprising at least one polymeric resin and from 1 to 85 wt.-%, based on the total weight of the polymer composition, of a surface treated filler material product as defined in claim 1.

7. The polymer composition according to claim 6, wherein the at least one polymeric resin is at least one thermoplastic polymer.

8. The polymer composition according to claim 6, wherein the polymer composition is a masterbatch.

9. A fiber and/or filament and/or film and/or thread comprising a surface treated filler material product according to claim 1 and/or a polymer composition comprising the surface treated filler material product.

10. An article comprising a surface treated filler material product according to claim 1 and/or a polymer composition comprising the surface treated filler material product and/or a fiber and/or filament and/or film and/or thread comprising the surface treated filler material product, wherein the article is hygiene products, medical and healthcare products, filter products, geotextile products, agriculture and horticulture products, clothing, footwear and baggage products, household and industrial products, packaging products, or construction products.

11. The surface treated filler material product according to claim 1, wherein the at least one calcium carbonate-containing filler material is selected from ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), modified calcium carbonate (MCC) and mixtures thereof.

12. The surface treated filler material product according to claim 1, wherein the at least one calcium carbonate-containing filler material comprises at least one ground calcium carbonate (GCC) selected from the group consisting of marble, chalk, dolomite, limestone and mixtures thereof and/or at least one precipitated calcium carbonate (PCC) selected from the group consisting of one or more of the aragonitic, vateritic and calcitic mineralogical crystal forms and/or at least one modified calcium carbonate (MCC).

13. The surface treated filler material product according to claim 1, wherein the at least one calcium carbonate-containing filler material has a weight median particle size d.sub.50 from 0.25 μm to 5 μm.

14. The surface treated filler material product according to claim 1, wherein the at least one calcium carbonate-containing filler material has a top cut (d.sub.98)≥12.5 μm.

15. The surface treated filler material product according to claim 1, wherein the at least one calcium carbonate-containing filler material has a specific surface area (BET) of from 0.5 to 50 m.sup.2/g as measured by the BET nitrogen method.

16. The surface treated filler material product according to claim 1, wherein the at least one calcium carbonate-containing filler material has a residual total moisture content of from 0.01 to 1.0 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

17. The surface treated filler material product according to claim 1, wherein the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from C2 to C30 in the substituent.

18. The surface treated filler material product according to claim 1, wherein the at least one mono-substituted succinic anhydride is at least one alkyl mono-substituted succinic anhydride, ethylsuccinic anhydride, propylsuccinic anhydride, butylsuccinic anhydride, triisobutyl succinic anhydride, pentylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic anhydride, octylsuccinic anhydride, nonylsuccinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, hexadecanyl succinic anhydride, octadecanyl succinic anhydride, or mixtures thereof.

19. The surface treated filler material product according to claim 1, wherein the at least one mono-substituted succinic anhydride is at least one alkenyl mono-substituted succinic anhydride, ethenylsuccinic anhydride, propenylsuccinic anhydride, butenylsuccinic anhydride, triisobutenyl succinic anhydride, pentenylsuccinic anhydride, hexenylsuccinic anhydride, heptenylsuccinic anhydride, octenylsuccinic anhydride, nonenylsuccinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, or mixtures thereof.

20. The surface treated filler material product according to claim 1, wherein the salty reaction product(s) of the at least one mono-substituted succinic acid and/or the at least one mono-substituted succinic anhydride on the surface of the at least one calcium carbonate-containing filler material are one or more calcium salts and/or one or more magnesium salts thereof.

21. The surface treated filler material product according to claim 1, wherein the surface treated filler material product has a water pick-up of from 0.1 to 0.8 mg/g at a temperature of 23° C. (±2° C.).

22. The surface treated filler material product according to claim 1, wherein the surface treated filler material product has a volatile onset temperature of ≥250° C.

23. The surface treated filler material product according to claim 1, wherein the surface treated filler material product has a hydrophilicity of below 8:2 volumetric ratio of water:ethanol measured at +23° C. (±2° C.) with the sedimentation method.

24. The surface treated filler material product according to claim 1, wherein the treatment layer on the surface of the at least one calcium carbonate-containing filler material comprises at least one mono-substituted succinic anhydride, at least one mono-substituted succinic acid, and salty reaction product(s) thereof.

25. A process for preparing a surface treated filler material product of claim 1, the process comprising at least the steps of: a) providing at least one calcium carbonate-containing filler material having i) a weight median particle size d.sub.50 value in the range from 0.1 μm to 7 μm, ii) a top cut (d.sub.98) of ≤15 μm, iii) a specific surface area (BET) of from 0.5 to 150 m.sup.2/g as measured by the BET nitrogen method, and iv) a residual total moisture content of ≤1 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material, b) providing at least one mono-substituted succinic anhydride and optionally at least one mono-substituted succinic acid in an amount of from 0.1 to 3 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a), c) contacting the surface of the at least one calcium carbonate-containing filler material of step a) under mixing, in one or more steps, with the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid of step b) such that a treatment layer comprising (A) the at least one mono-substituted succinic anhydride, (B) the at least one mono-substituted succinic acid, and (C) optionally salty reaction product(s) of the at least one mono-substituted succinic acid and/or the at least one monosubstituted succinic anhydride, is formed on the surface of said at least one calcium carbonate-containing filler material of step a), wherein the temperature before and/or during contacting step c) is adjusted such that the temperature is at least 2° C. above the melting point of the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid.

26. The process according to claim 25, wherein the at least one calcium carbonate-containing filler material of step a) is preheated before contacting step c) is carried out.

27. The process according to claim 25, wherein the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid of step b) are provided in a total amount of from 0.1 to 2.5 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

28. The process according to claim 25, wherein the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid of step b) are added in contacting step c) in a total amount of from 0.1 to 2 wt.-%, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a).

29. The process according to claim 25, wherein the at least one mono-substituted succinic acid of step b) is present in an amount of ≤10 mol.-%, based on the molar sum of the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid.

30. The process according to claim 25, wherein contacting step c) is carried out at a temperature of from 30 to 200° C.

31. The process according to claim 25, wherein contacting step c) is carried out in a batch or continuous process.

32. The process according to claim 31, wherein the contacting step c) is a continuous process and comprises one or several contacting steps and the total contacting time is from 0.1 to 20 s.

33. The process according to claim 25, wherein the process further comprises step d) of contacting the at least one calcium carbonate-containing filler material of step a), in one or more steps, with at least one organic material.

34. The process according to claim 33, wherein contacting step d) is carried out during and/or after contacting step c).

35. The process according to claim 33, wherein contacting step d) is carried out at a temperature of from 40 to 200° C.

36. The process according to claim 33, wherein the at least one organic material is added in contacting step d) in an amount of from 100 to 1,000 ppm, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 demonstrates clearly that fibers and/or filaments and/or films and/or threads comprising the inventive surface treated filler material product prepared in accordance with the present invention show increased values in dart drop.

(2) FIG. 2 shows scanning electron micrographs (SEM) of PP multifilament fibers containing calcium carbonate. Fiber surface (top) & fiber cross section (bottom), 500× magnification [40 um].

(3) The following examples may additionally illustrate the invention but are not meant to restrict the invention to the exemplified embodiments. The examples below show the reduced total volatiles, the reduced moisture pick up susceptibility and the decreased hydrophilicity of the surface treated filler material product and the good mechanical properties of the fiber and/or filament and/or film and/or thread prepared from the polymer composition according to the present invention:

EXAMPLES

(4) Measurement Methods

(5) The following measurement methods are used to evaluated the parameters given in the examples and claims.

(6) Measurement of the Total Volatiles

(7) For the purpose of the present application, the “total volatiles” associated with mineral fillers and evolved over a temperature range of 25 to 350° C. is characterized according to % mass loss of the mineral filler sample over a temperature range as read on a thermogravimetric (TGA) curve.

(8) TGA analytical methods provide information regarding losses of mass and volatile onset temperatures with great accuracy, and is common knowledge; it is, for example, described in “Principles of Instrumental analysis”, fifth edition, Skoog, Holler, Nieman, 1998 (first edition 1992) in Chapter 31 pages 798 to 800, and in many other commonly known reference works. In the present invention, thermogravimetric analysis (TGA) is performed using a Mettler Toledo TGA 851 based on a sample of 500+/−50 mg and scanning temperatures from 25 to 350° C. at a rate of 20° C./minute under an air flow of 70 ml/min.

(9) The skilled man will be able to determine the “volatile onset temperature” by analysis of the TGA curve as follows: the first derivative of the TGA curve is obtained and the inflection points thereon between 150 and 350° C. are identified. Of the inflection points having a tangential slope value of greater than 45° relative to a horizontal line, the one having the lowest associated temperature above 200° C. is identified. The temperature value associated with this lowest temperature inflection point of the first derivative curve is the “volatile onset temperature”.

(10) The “total volatiles” evolved on the TGA curve is determined using Star.sup.e SW 9.01 software. Using this software, the curve is first normalised relative to the original sample weight in order to obtain mass losses in % values relative to the original sample. Thereafter, the temperature range of 25 to 350° C. is selected and the step horizontal (in German: “Stufe horizontal”) option selected in order to obtain the % mass loss over the selected temperature range.

(11) Particle Size Distribution (Mass % Particles with a Diameter <X) and Weight Median Diameter (d.sub.50) of a Particulate Material

(12) As used herein and as generally defined in the art, the “d.sub.50” value is determined based on measurements made by using a Sedigraph™ 5100 of Micromeritics Instrument Corporation and is defined as the size at which 50% (the median point) of the particle volume or mass is accounted for by particles having a diameter equal to the specified value.

(13) The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt.-% Na.sub.4P.sub.2O.sub.7. The samples are dispersed using a high speed stirrer and supersonics.

(14) BET Specific Surface Area of a Material

(15) Throughout the present document, the specific surface area (in m.sup.2/g) of the mineral filler is determined using the BET method (using nitrogen as adsorbing gas), which is well known to the skilled man (ISO 9277:1995). The total surface area (in m.sup.2) of the mineral filler is then obtained by multiplication of the specific surface area and the mass (in g) of the mineral filler prior to treatment.

(16) Moisture Pick-Up

(17) The term “moisture pick-up susceptibility” in the meaning of the present invention refers to the amount of moisture absorbed on the surface of the mineral filler and is determined in mg moisture/g of the dry treated mineral filler product after exposure to an atmosphere of 10 and 85% of relative humidity, resp., for 2.5 hours at a temperature of +23° C. (±2° C.). The treated mineral filler product is first held at an atmosphere of 10% of relative humidity for 2.5 hours, then the atmosphere is changed to 85% of relative humidity, where the sample is held for another 2.5 hours. The weight increase between 10% and 85% relative humidity is then used to calculate the moisture pick-up in mg moisture/g of dry treated mineral filler product.

(18) Hydrophilicity

(19) The “hydrophilicity” of a mineral filler product is evaluated at +23° C. by determining the minimum water to ethanol ratio in a volume/volume based water/ethanol-mixture needed for the settling of the majority of said mineral filler product, where said mineral filler product is deposited on the surface of said water/ethanol-mixture by passage through a house hold tea sieve. The volume/volume base is related to the volumes of both separate liquids before blending them together and do not include the volume contraction of the blend. The evaluation at +23° C. refers to a temperature of +23° C.±1° C.

(20) A 8:2 volumetric ratio of a water/ethanol-mixture has typically a surface tension of 41 mN/m and a 6:4 volumetric ratio of a water/ethanol-mixture has typically a surface tension of 26 mN/m measured at +23° C. as described in the “Handbook of Chemistry and Physics”, 84.sup.th edition, David R. Lide, 2003 (first edition 1913).

(21) Dart Drop Test

(22) The dart drop test is measured according to ASTM D 1709/A.

(23) Residual Total Moisture Content Measurement of Calcium Carbonate-Containing Material

(24) The residual total moisture content of the filler is measured according to the Karl Fischer coulometric titration method, desorbing the moisture in an oven at 220° C. and passing it continuously into the KF coulometer (Mettler Toledo coulometric KF Titrator C30, combined with Mettler oven DO 0337) using dry N.sub.2 at 100 ml/min for 10 min. A calibration curve using water has to be made and a blind of 10 min gas flow without a sample has to be taken in account.

(25) Measurements Done on Filament Samples

(26) 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.

(27) 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.

(28) 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.

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

(30) Measurements Done on Nonwoven Samples

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

(32) 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.

(33) 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.

(34) 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.

(35) Ash content in [%] of the fibers and the masterbatches is determined by incineration of a sample in an incineration crucible which is put into an incineration furnace at 570° C. for 2 hours. The ash content is measured as the total amount of remaining inorganic residues.

Example 1

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

(37) For the preparation of the surface treated filler material product, lime stone from Omey, France was wet ground at 25 wt.-% in tap water in a horizontal ball mill (Dynomill) and spray dried. The obtained calcium carbonate-containing filler material features a d.sub.50 of approximately 1.7 microns, a top cut (d.sub.98) of 5 μm and a specific surface area of 4.1 m.sup.2/g and a residual moisture content of 0.06 wt.-%.

(38) The obtained spray dried calcium carbonate-containing filler material was further treated as outlined in the following tests:

(39) Test 1 (Prior Art; PA1)

(40) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 5 minutes at 180° C. and 3000 rpm. Thereafter polystyren-co-maleic anhydride having a Mn of 1600 (Aldrich number 442380) was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 180° C. under a stirring speed of 3000 rpm for a period of 5 minutes.

(41) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(42) Test 2 (Prior Art; PA2)

(43) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 5 minutes at 80° C. and 3000 rpm. Thereafter, 1,2-cyclohexanedicarboxylic anhydride (Aldrich number 123463) was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 80° C. under a stirring speed of 3000 rpm for a period of 5 minutes.

(44) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(45) Test 3 (Prior Art; PA3)

(46) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 5 minutes at 80° C. and 3000 rpm. Thereafter, phenyl succinic anhydride (Aldrich number 416622) was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 80° C. under a stirring speed of 3000 rpm for a period of 5 minutes.

(47) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(48) Test 4 (Invention; IE4)

(49) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 10 minutes at 120° C. and 3000 rpm. Thereafter, n-octadecenyl succinic anhydride having a purity of ≥96.5% was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 10 minutes.

(50) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(51) Test 5 (Invention; IE5)

(52) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 10 minutes at 120° C. and 3000 rpm. Thereafter, a mixture of branched hexadecenyl succinic anhydrides (CAS #32072-96-1) and branched octadecenyl succinic anhydrides (CAS #28777-98-2) comprising an amount of branched octadecenyl succinic anhydrides of about 40 wt.-%, based on the total weight of the succinic anhydride mixture was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 10 minutes.

(53) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(54) Test 6 (Invention; IE6)

(55) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 10 minutes at 120° C. and 3000 rpm. Thereafter, n-butylsuccinic anhydride (TCI Europe N.V. product number B2742) was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 10 minutes followed by the addition of 500 ppm of polydimethylsiloxane (Dow Corning 200 Fluid 1000 CS) and mixing at 3000 rpm for 5 minutes at 120° C. The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(56) Test 7 (Invention; IE7)

(57) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 30 minutes at 120° C. and 3000 rpm. Thereafter, n-octenylsuccinic anhydride (cis and trans mixture; TCI Europe N.V. product number O0040) was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 20 minutes followed by the addition of 500 ppm of polydimethylsiloxane (Dow Corning 200 Fluid 1000 CS) and mixing at 3000 rpm for 5 minutes at 120° C.

(58) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(59) Test 8 (Invention; IE8)

(60) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 10 minutes at 120° C. and 3000 rpm. Thereafter, a mixture of branched hexadecenyl succinic anhydrides (CAS #32072-96-1) and branched octadecenyl succinic anhydrides (CAS #28777-98-2) comprising an amount of branched octadecenyl succinic anhydrides of about 40 wt.-%, was introduced to the mixer in a quantity such as indicated in Table 1. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 10 minutes followed by the addition of 500 ppm of polydimethylsiloxane (Dow Corning 200 Fluid 1000 CS) and mixing at 3000 rpm for 5 minutes at 120° C.

(61) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. The results are presented in table 2.

(62) TABLE-US-00001 TABLE 1 PA PA PA IE IE IE IE IE Test 1 2 3 4 5 6 7 8 treatment level 1.0 1.0 1.0 0.5 0.6 0.6* 0.6* 0.6* [wt.-%] preheating 5/180 5/80 5/80 10/120 10/120 10/120  30/120  5/120 Time/temperature ([min]/[° C.]) treatment 5/180 5/80 5/80 10/120 10/120 10/120# 20/120# 10/180# time/temperature ([min]/[° C.]) *comprises an additional treatment level of 0.05 wt.-% of siloxane, based on the total weight of calcium carbonate-containing filler material. #comprises an additional treatment step with siloxane for 5 min at 120° C.

(63) The results for the analysis of the surface treated filler material product as described above are outlined in table 2.

(64) TABLE-US-00002 TABLE 2 PA PA PA IE IE IE IE IE Test 1 2 3 4 5 6 7 8 Moisture pick- — — — 0.31 0.33 0.21 0.29 0.27 up [mg/g] OST [° C.] — — — 278 283 335 — — Hydrophilicity 100 100 100 60 60 60 70 50 [vol/vol-%]

(65) From the data given in Table 2, it can be gathered that the surface treated filler material product prepared in accordance with the present invention shows excellent properties. In particular, it is shown that the surface treated filler material product prepared in accordance with the present invention has a moisture pick up susceptibility of less than 0.8 mg/g, a volatile onset temperature of ≥250° C., and a hydrophilicity of below 8:2 volumetric ratio of water:ethanol.

Example 2

(66) This example relates to the preparation of a blown film comprising the surface treated filler material product prepared in accordance with the present invention and at least one polymeric resin.

(67) The details regarding the blown film polymer compositions, based on the total weight of the obtained film, are described in Table 3.

(68) TABLE-US-00003 TABLE 3 Formulation [g/cm.sup.3] F0 F1 F2 F3 Polymer resin 0.924 100 40 40 40 Treated carbonate A 2.7 60 IE4 2.7 60 IE5 2.7 60

(69) The polymer compositions used for preparing the blown film were afterwards diluted to 20 wt.-% calcium carbonate-containing material, based on the total weight of the obtained film.

(70) Treated carbonate A is a stearic acid treated dry ground calcium carbonate (marble from Italy) with a medium diameter (d.sub.50) of 1.7 μm and a top cut (d.sub.98) of 6.8 μm. 57 wt.-% of the particles have a diameter of below 2 μm. This treated filler material is used as an internal reference.

(71) Polymer resin relates to a linear low density polyethylene resin (LLDPE) which is commercially available as Dowlex NG 5056G from Dow Chemical Company, Dow Europe GmbH, Horgen, Switzerland.

(72) Polymer composition FO contains only the pure polymer resin, no surface treated filler material product is included.

(73) The blown film was prepared on a Collin blown film line with a film grammage of 37.5 g/m.sup.2 and a film thickness of 40 μm.

(74) The fiber and/or filament and/or film and/or thread comprising the inventive surface treated filler material product prepared in accordance with the present invention show excellent mechanical properties such as shown in FIG. 1.

(75) FIG. 1 demonstrates clearly that fibers and/or filaments and/or films and/or threads comprising the inventive surface treated filler material product prepared in accordance with the present invention show increased values in dart drop. In particular, it is shown that the values determined for the dart drop of the fibers and/or filaments and/or films and/or threads comprising the inventive surface treated filler material product prepared in accordance with the present invention are significantly higher than the values determined for the sample consisting only of the polymeric resin as well as for the reference sample.

(76) It is further appreciated that the polymer composition comprising the inventive surface treated filler material product prepared in accordance with the present invention and which is used for preparing the fiber and/or filament and/or film and/or thread also shows an excellent filter pressure value (FPV) as can be gathered from Table 4.

(77) TABLE-US-00004 TABLE 4 Sample FPV, 16 g GCC, 14 μm screen [bar/g] F1 1.8 F2 0.7 F3 0.8

Example 3

(78) This example relates to the preparation of a nonwoven fabric comprising the surface treated filler material product prepared in accordance with the present invention and at least one polymeric resin.

(79) 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 5 and 6. Different amounts of the filled masterbatches

(80) 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.

(81) TABLE-US-00005 TABLE 5 Formulation 1 2 3 4 Polypropylene HF420FB 100 96 96 96 70% MB Invention 1 4 70% MB Invention 2 4 70% MB Prior Art 1 4 Tests Norm Unit On Filaments Linear density dtex 9.3 10.1 9.3 9.7 Tenacity cN/dtex 2.26 2.08 2.03 2.09 Elongation % 252 251 239 229 Tensile index — 359 330 314 316 On Nonwoven Fabric weight EN ISO 9864 g/m.sup.2 372 388 367 387 Coefficient CBR EN ISO12236 N/g 7.5 5.9 6.7 7.1 CBR EN ISO12236 N 2766 2271 2449 2741 Tensile Strength (MD + CD)/2 EN ISO 12319 N/g 10.6 9.5 10.2 9.3 Ash content % 0 2.4 2.5 3.0 .sup.1 MD refers to machine direction, .sup.2 CD refers to cross direction.

(82) TABLE-US-00006 TABLE 6 Formulation 1 2 3 4 Polypropylene HF420FB 100 90 90 90 70% MB Invention1 10 70% MB Invention 2 10 70% MB Prior Art 1 10 Tests Norm Unit On Filaments Linear density dtex 9.3 10.4 10.0 10.0 Tenacity cN/dtex 2.26 1.97 1.99 1.87 Elongation % 252 244 239 226 Tensile index — 359 308 308 281 On Nonwoven Fabric weight EN ISO 9864 g/m.sup.2 372 405 385 401 Coefficient CBR EN ISO12236 N/g 7.5 6.2 5.6 6.2 CBR EN ISO12236 N 2766 2522 2142 2479 Tensile Strength (MD + CD)/2 EN ISO 12319 N/g 10.6 8.3 8.3 7.6 Ash content % 0 5.9 5.9 7.0 .sup.1 MD refers to machine direction, .sup.2 CD refers to cross direction

(83) 70% MB Invention 1 refers to 70 wt % of a masterbatch of 28 wt % PP HH450 FB homo-polypropylene with MFR 37 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 d50 of 1.7 μm, a top cut of d98 of 6 μm. Treatment of the CaCO.sub.3: 0.5 wt % of Hydrores AS 1000 (KEMIRA; CAS number 68784-12-3): 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 10 minutes at 120° C. and 3000 rpm. Thereafter, Hydrores AS 1000 (Kemira) was introduced to the mixer in a quantity of 0.5 wt %. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 10 minutes.

(84) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. T onset: 289° C.; Water-pick-up: 0.7 mg/g

(85) 70% MB Invention 2 refers to 70 wt % of a masterbatch of 28 wt % PP HH450 FB homo-polypropylene with MFR 37 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 d50 of 1.7 μm, a top cut of d98 of 6 μm. Treatment of the CaCO.sub.3: 0.6 wt % Hydrores AS 1100 (KEMIRA, CAS number 68784-12-3):

(86) 500 g of the spray dried calcium carbonate-containing filler material was added to an MTI Mixer and the sample was activated for 10 minutes at 120° C. and 3000 rpm. Thereafter, Hydrores AS 1100 (Kemira) was introduced to the mixer in a quantity a quantity of 0.6 wt %. The contents of the mixer were mixed at 120° C. under a stirring speed of 3000 rpm for a period of 10 minutes.

(87) The obtained surface treated filler material product was stored in a closed plastic bag. For analysis purposes the sample was taken out of the closed plastic bag and analyzed immediately. T onset: 300° C.; Water-pick-up: 0.8 mg/g 70% of MA PA1 refers to 70 wt % of a masterbatch of 28 wt % PP HH450 FB homo-polypropylene with MFR 37 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 a wet ground surface treated CaCO.sub.3 of the prior art, and the CaCO.sub.3 has a median particle size diameter d50 of 1.7 μm and a top cut of d98 of 6 μm.

(88) As can be seen from the inventive examples 2 and 3 from tables 5 and 6, samples of polypropylene nonwoven fabrics comprises the CaCO.sub.3 according to the present invention and as seen in example 4 from tables 5 and 6, samples of nonwoven fabrics comprising the prior art CaCO.sub.3 can be produced in good quality with slightly reduced mechanical properties compared to Example 1 being the unfilled polypropylene PP HF420FB.

(89) 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.

Example 4

(90) This example relates to the preparation of multifilament fibers comprising the surface treated filler material product prepared in accordance with the present invention and at least one polymeric resin.

(91) Samples of the said multifilament fibers comprising the CaCO.sub.3 according to the present invention and samples of multifilament fibers comprising the prior art CaCO.sub.3 are summarized hereafter in tables 8 to 14. Different amounts of the filled masterbatches were mixed with further polypropylene (Moplen HP 561R, a homo-polypropylene with MFR 25 g/10 min. (230° C., 2.16 kg, ISO 1133) from LyondellBasell) and multifilament fibers were made from these mixtures using a Collin Multifilament Lab Line CMF 100 (produced by Dr. Collin GmbH, Ebersberg, Germany), equipped with a single screw extruder with melt pump, spinneret diameter 50 mm with 34 filaments Ø 0.3 mm, Drawing conditions are summarized in table 7. Limanol BF29 (from Schill+Seilacher GmbH, Böblingen, Germany) is used as spinning oil.

(92) TABLE-US-00007 TABLE 7 Drawing temperatures: Condition 1 Condition 2 Condition 3 Roll 1 80° C. 100° C. 110° C. Roll 2 85° C. 105° C. 115° C. Roll 3 90° C. 105° C. 115° C. Roll 4 90° C. 110° C. 120° C.

(93) TABLE-US-00008 TABLE 8 Inventive masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 1  2% MB Inv. 3 1 2 1.23 223 754 1.3 2  5% MB Inv. 3 1 2 1.01 221 796 10.8 3 10% MB Inv. 3 1 2 1.14 171 742 9.7 4 15% MB Inv. 3 1 2 1.05 202 848 14.2 5 20% MB Inv. 3 1 2 0.76 215 904 23.1 6 25% MB Inv. 3 1 2 0.73 180 962 28.0 7 30% MB Inv. 3 1 2 0.57 218 1012 30.6 8 40% MB Inv. 3 1 2 0.53 201 1042 38.9 9 10% MB Inv. 3 1 3 1.51 134 554 8.1 10 10% MB Inv. 3 1 4 1.94 81 434 9.5 11 10% MB Inv. 3 1 5 2.35 38 355 10.9 12 10% MB Inv. 3 1 6 2.82 15 310 10.7 13 15% MB Inv. 3 1 3 0.89 99 578 17.0 14 15% MB Inv. 3 1 4 1.33 94 425 17.0 15 15% MB Inv. 3 1 5 1.74 76 350 16.5 16 15% MB Inv. 3 1 6 1.79 60 309 17.1 17 20% MB Inv. 3 1 3 0.84 105 610 22.9 18 20% MB Inv. 3 1 4 1.09 111 449 19.8 19 20% MB Inv. 3 1 5 1.34 93 350 21.6 20 20% MB Inv. 3 1 6 1.78 58 293 19.4

(94) TABLE-US-00009 TABLE 9 Inventive masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 21 10% MB Inv. 3 2 2 0.54 219 792 9.7 22 10% MB Inv. 3 2 3 0.89 183 519 10.2 23 10% MB Inv. 3 2 4 1.25 107 426 11.3 24 10% MB Inv. 3 2 5 1.71 77 350 12.7 25 15% MB Inv. 3 2 2 0.5 207 822 16.6 26 15% MB Inv. 3 2 3 0.79 152 560 18.2 27 15% MB Inv. 3 2 4 1.35 73 428 17.2 28 15% MB Inv. 3 2 5 1.9 74 359 16.1 29 20% MB Inv. 3 2 2 0.51 217 868 20.9 30 20% MB Inv. 3 2 3 0.89 193 561 21.1 31 20% MB Inv. 3 2 4 1.17 112 451 22.8 32 20% MB Inv. 3 2 5 1.4 84 362 17.8

(95) TABLE-US-00010 TABLE 10 Inventive masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 33 10% MB Inv. 3 3 2 0.91 196 678 10.5 34 10% MB Inv. 3 3 3 1.17 126 499 10.3 35 10% MB Inv. 3 3 4 1.2 104 390 9.5 36 10% MB Inv. 3 3 5 1.92 66 335 8.3 37 15% MB Inv. 3 3 2 0.89 170 679 12.0 38 15% MB Inv. 3 3 3 1.08 146 499 14.3 39 15% MB Inv. 3 3 4 1.73 97 402 15.5 40 15% MB Inv. 3 3 5 1.82 19 362 16.0 41 20% MB Inv. 3 3 2 0.72 183 846 21.2 42 20% MB Inv. 3 3 3 1.11 117 572 21.1 43 20% MB Inv. 3 3 4 1.34 71 427 20.5 44 20% MB Inv. 3 3 5 1.66 66 348 19.2

(96) TABLE-US-00011 TABLE 11 Prior art masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 45  2% MB PA2 1 2 1.36 223 736 1.8 46  5% MB PA2 1 2 0.95 222 774 4.6 47 10% MB PA2 1 2 0.94 169 623 12.1 48 20% MB PA2 1 2 0.78 205 555 21.2 49 10% MB PA2 1 3 1.61 144 533 4.9 50 10% MB PA2 1 4 2.09 70 386 2.4 51 10% MB PA2 1 5 2.56 59 338 8.9 52 10% MB PA2 1 6 2.97 14 287 10.3 53 15% MB PA2 1 3 1.83 124 597 17.0 54 15% MB PA2 1 4 1.88 73 458 17.0 55 15% MB PA2 1 5 2.35 38 366 14.3 56 15% MB PA2 1 6 3.17 16 306 14.3 57 20% MB PA2 1 3 1.29 116 606 20.1 58 20% MB PA2 1 4 1.51 63 465 20.7 59 20% MB PA2 1 5 2.11 32 378 19.2 60 20% MB PA2 1 6 2.36 13 339 22.5

(97) TABLE-US-00012 TABLE 12 Prior art masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 61 10% MB PA2 2 2 0.48 219 820 10.1 62 10% MB PA2 2 3 1.36 109 539 10.8 63 10% MB PA2 2 4 1.69 83 414 8.7 64 10% MB PA2 2 5 2.11 77 319 8.7 65 15% MB PA2 2 2 0.55 219 861 19.9 66 15% MB PA2 2 3 0.71 89 587 17.6 67 15% MB PA2 2 4 1.66 95 424 15.9 68 15% MB PA2 2 5 1.74 77 351 14.6 69 20% MB PA2 2 2 0.68 214 870 18.8 70 20% MB PA2 2 3 0.9 89 588 15.8 71 20% MB PA2 2 4 1.51 69 432 16.2 72 20% MB PA2 2 5 1.72 47 354 15.6

(98) TABLE-US-00013 TABLE 13 Prior art masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 73 10% MB PA2 3 2 0.74 206 786 9.8 74 10% MB PA2 3 3 1.46 72 529 7.7 75 10% MB PA2 3 4 1.96 85 406 6.7 76 10% MB PA2 3 5 2.2 17 326 8.5 77 15% MB PA2 3 2 0.63 197 819 13.6 78 15% MB PA2 3 3 0.99 145 550 11.2 79 15% MB PA2 3 4 1.42 63 438 12.2 80 15% MB PA2 3 5 2.27 18 340 12.1 81 20% MB PA2 3 2 0.54 147 898 24.2 82 20% MB PA2 3 3 0.99 100 598 19.8 83 20% MB PA2 3 4 1.36 74 459 18.6 84 20% MB PA2 3 5 2.11 15 361 16.8

(99) TABLE-US-00014 TABLE 14 neat polymer without masterbatch Elongation Linear Ash Draw temp. Draw Tenacity at max. load density content Example Masterbatch condition ratio [cN/dtex] [%] [dtex] [%] 85 None 1 2 1.34 210 732 0 86 None 1 3 1.99 151 530 0 87 None 1 4 2.56 92 409 0 88 None 1 5 2.66 49 356 0 89 None 1 6 3.57 15 286 0 90 None 1 7 4.03 15 234 0

(100) 70% MB Invention 3 refers to 70 wt % of a masterbatch produced on industrial scale wherein the treated CaCO.sub.3 has a median particles size diameter d50 of 1.7 μm, a top cut of d98 of 6 μm. Treatment of the CaCO.sub.3: 0.5 wt % of Hydrores AS 1000 (KEMIRA; CAS number 68784-12-3). The precise filler content of the masterbatch was determined by the ash content: 72.2 wt % and the melt flow rate (MFR, 230° C., 2.16 kg, ISO 1133) of the masterbatch is 9.13 g/10 min.

(101) 70% of MB PA2 refers to a masterbatch produced on industrial scale wherein 70 wt % of a wet ground surface treated CaCO.sub.3 of the prior art is used and the CaCO.sub.3 has a median particle size diameter d50 of 1.7 μm and a top cut of d98 of 6 μm. The precise filler content of the masterbatch was determined by the ash content: 72.2 wt % and the melt flow rate (MFR, 230° C., 2.16 kg, ISO 1133) of the masterbatch is 9.04 g/10 min.

(102) As can be seen in tables 8 to 10, samples of polypropylene multifilament fibers comprises the CaCO.sub.3 according to the present invention and as seen in tables 11 to 13, samples of polypropylene multifilament fibers comprising the prior art CaCO.sub.3 can be produced in good quality under various processing conditions by varying the amount of CaCO.sub.3 addition, the draw ratio and the draw temperatures. Table 14 shows the results of polypropylene multifilament fibers comprising no CaCO.sub.3.