阅读说明：本技术 用包含硬脂酸的脂族线性或支化羧酸的混合物和单取代的琥珀酸酐制备经表面处理的填料材料产品的方法 (Process for preparing a surface-treated filler material product with a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid and monosubstituted succinic anhydride ) 是由 弗朗切斯科·普莱加 皮埃尔·布兰查德 塔齐奥·福尔内拉 马蒂亚斯·韦尔克 于 2018-06-12 设计创作，主要内容包括：本发明涉及用包含硬脂酸的脂族线性或支化羧酸的混合物和单取代的琥珀酸酐制备经表面处理的填料材料产品的方法；经表面处理的填料材料产品；聚合物组合物；包含所述经表面处理的填料材料产品和/或所述聚合物组合物的纤维和/或丝和/或膜和/或线和/或片和/或管和/或型材和/或模具和/或注塑模具和/或吹塑模具；一种制品,其包含所述经表面处理的填料材料产品和/或所述聚合物组合物和/或所述纤维和/或丝和/或膜和/或线和/或片和/或管和/或型材和/或模具和/或注塑模具和/或吹塑模具；以及至少一种单取代的琥珀酸酐和/或其盐反应产物与包含硬脂酸的脂族线性或支化羧酸的混合物和/或其盐反应产物组合用于改善经表面处理的填料材料产品的流动性和用于改善碳酸钙在聚合物组合物的聚合物基体中的分散的用途。(The present invention relates to a process for preparing a surface-treated filler material product with a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid and monosubstituted succinic anhydride; a surface treated filler material product; a polymer composition; fibres and/or filaments and/or films and/or threads and/or sheets and/or tubes and/or profiles and/or moulds and/or injection moulds and/or blow moulds 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 fibers and/or filaments and/or films and/or threads and/or sheets and/or tubes and/or profiles and/or molds and/or injection molds and/or blow molds; and the use of a mixture of at least one monosubstituted succinic anhydride and/or a salt reaction product thereof and an aliphatic linear or branched carboxylic acid comprising stearic acid and/or a salt reaction product thereof in combination for improving the flowability of a surface-treated filler material product and for improving the dispersion of calcium carbonate in the polymer matrix of a polymer composition.)

1. A process for preparing a surface-treated filler material product with a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid and monosubstituted succinic anhydride, said process comprising at least the steps of:

a) providing at least one calcium carbonate-comprising filler material,

b) there is provided at least one monosubstituted succinic anhydride,

c) providing a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid in an amount of at least 10.0 wt% based on the total weight of the mixture; and one or more additional saturated aliphatic linear or branched carboxylic acids having a total amount of carbon atoms from C8 to C24,

d) contacting, in one or more steps, in any order, the surface of the at least one calcium carbonate-comprising filler material of step a) with the mixture of the at least one monosubstituted succinic anhydride of step b) and the aliphatic linear or branched carboxylic acid of step c), under mixing, such that a treated layer comprising the reaction product of the at least one monosubstituted succinic anhydride and/or salt thereof and the mixture of aliphatic linear or branched carboxylic acids and/or salt thereof is formed on the surface of the at least one calcium carbonate-comprising filler material of step a),

wherein the temperature before and/or during the contacting step d) is adjusted such that the mixture of aliphatic linear or branched carboxylic acids and the at least one monosubstituted succinic anhydride are in the molten state or in the liquid state.

2. The process according to claim 1, wherein the calcium carbonate-containing filler material of step a) is selected from: ground calcium carbonate, preferably marble, limestone, dolomite and/or chalk, Precipitated Calcium Carbonate (PCC), preferably vaterite, calcite and/or aragonite, surface-reacted calcium carbonate (MCC) and mixtures thereof, more preferably the calcium carbonate-containing filler material is ground calcium carbonate.

3. The process according to claim 1 or 2, wherein the at least one calcium carbonate-comprising filler material of step a) has

a) A weight median particle diameter d in the range of 0.1 μm to 7 μm, preferably 0.25 μm to 5 μm, and most preferably 0.5 μm to 4 μm₅₀A value, and/or

b) A tip portion (d) of 50 μm or less, preferably 40 μm or less, more preferably 25 μm or less, and most preferably 15 μm or less₉₈) And/or

c) 0.5m as measured by the BET nitrogen adsorption method²G to 150m²Per g, preferably 0.5m²G to 50m²Per g, more preferably 0.5m²G to 35m²In terms of/g, and most preferably 0.5m²G to 10m²Specific surface area per gram (BET), and/or

d) A residual total moisture content of from 0.01 to 1 wt. -%, preferably from 0.01 to 0.2 wt. -%, more preferably from 0.02 to 0.2 wt. -%, and most preferably from 0.04 to 0.2 wt. -%, based on the total dry weight of the at least one calcium carbonate containing filler material.

4. The process according to any one of claims 1 to 3, wherein the at least one calcium carbonate-comprising filler material of step a) is preheated before carrying out the contacting step d), preferably the at least one calcium carbonate-comprising filler material of step a) is preheated at a temperature of from 20 ℃ to 200 ℃, more preferably from 40 ℃ to 200 ℃, even more preferably from 50 ℃ to 150 ℃, and most preferably from 60 ℃ to 130 ℃.

5. The process according to any one of claims 1 to 4, wherein the at least one monosubstituted succinic anhydride of step b) consists of succinic anhydride monosubstituted with a group selected from: the total amount of carbon atoms in the substituents is C2 to C30, preferably C3 to C25, and most preferably C4 to C20 linear, branched, aliphatic, and cyclic groups.

6. The process according to any one of claims 1 to 5, wherein the at least one monosubstituted succinic anhydride of step b) is:

a) at least one alkyl monosubstituted succinic anhydride, preferably at least one alkyl monosubstituted succinic anhydride selected from: ethylsuccinic anhydride, propylsuccinic anhydride, butylsuccinic anhydride, triisobutylsuccinic anhydride, pentylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic anhydride, octylsuccinic anhydride, nonylsuccinic anhydride, decylsuccinic anhydride, dodecylsuccinic anhydride, hexadecylsuccinic anhydride, octadecylsuccinic anhydride, and mixtures thereof, and/or

b) At least one alkenyl monosubstituted succinic anhydride, preferably at least one alkenyl monosubstituted succinic anhydride selected from: vinyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, triisobutenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and mixtures thereof.

7. The process according to any one of claims 1 to 6, wherein the mixture of saturated aliphatic linear or branched carboxylic acids of step C) comprises stearic acid and one or more additional saturated aliphatic linear or branched carboxylic acids having a total amount of carbon atoms of C8 to C22, preferably C10 to C22, more preferably C12 to C20, and most preferably C14 to C20.

8. The process according to any one of claims 1 to 7, wherein contacting step d) is carried out by adding the mixture of the at least one monosubstituted succinic anhydride of step b) and the saturated aliphatic linear or branched carboxylic acid of step c) in a weight ratio [ succinic anhydride/carboxylic acid mixture ] of from 10:1 to 1:10, preferably from 5:1 to 1:5, and most preferably from 4:1 to 1:4, such as from 4:1 to 1: 1.

9. The process according to any one of claims 1 to 8, wherein the at least one monosubstituted succinic anhydride of step b) is added in contacting step d) in a total amount of from 0.1 to 3 wt. -%, preferably from 0.2 to 2 wt. -%, and most preferably from 0.3 to 1.5 wt. -%, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a); and the mixture of saturated aliphatic linear or branched carboxylic acids of step c) is added in contacting step d) in a total amount of from 0.1 to 3 wt. -%, preferably from 0.2 to 2 wt. -%, and most preferably from 0.3 to 1.5 wt. -%, based on the total dry weight of the at least one calcium carbonate-comprising filler material of step a).

10. The process according to any one of claims 1 to 9, wherein contacting step d) is carried out at a temperature of from 20 ℃ to 200 ℃, preferably from 40 ℃ to 150 ℃, and most preferably from 60 ℃ to 130 ℃.

11. The process according to any one of claims 1 to 10, wherein contacting step d) is carried out by simultaneously adding a mixture of the at least one monosubstituted succinic anhydride of step b) and the saturated aliphatic linear or branched carboxylic acid of step c); or by adding the mixture of saturated aliphatic linear or branched carboxylic acids of step c) after the at least one monosubstituted succinic anhydride of step b), preferably by adding the mixture of saturated aliphatic linear or branched carboxylic acids of step c) after the at least one monosubstituted succinic anhydride of step b).

12. The process according to any one of claims 1 to 11, wherein the at least one monosubstituted succinic anhydride is provided in step b) in an amount such that the total weight of the at least one monosubstituted succinic anhydride and/or its salt reaction product on the surface of the at least one calcium carbonate-comprising filler material is less than 5mg/m²For example 0.1mg/m²To 5mg/m²Preferably less than 4.5mg/m²More preferably less than 4.0mg/m²For example 0.2mg/m²To 4mg/m²Or 1mg/m²To 4mg/m²The at least one calcium carbonate-comprising filler material provided in step a); and/or providing in step c) the mixture of saturated aliphatic linear or branched carboxylic acids of step c) in an amount such that the total weight of the mixture of saturated aliphatic linear or branched carboxylic acids and/or their salt reaction products on the surface of the surface-treated filler material product is less than 5mg/m²For example 0.1mg/m²To 5mg/m²Preferably less than 4.5mg/m²More preferably less than 4.0mg/m²For example 0.2mg/m²To 4mg/m²Or 1mg/m²To 4mg/m²The at least one calcium carbonate-comprising filler material provided in step a).

13. A surface treated filler material product comprising:

a) at least one filler material comprising calcium carbonate,

b) a treatment layer on the surface of the at least one calcium carbonate-comprising filler material, the treatment layer comprising at least one monosubstituted succinic anhydride and/or a salt thereof reaction product, and a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid in an amount of at least 10.0 wt. -%, based on the total weight of the mixture, and/or a salt reaction product thereof; and one or more additional saturated aliphatic linear or branched carboxylic acids having a total amount of carbon atoms from C8 to C24,

wherein the surface-treated filler material product comprises the treatment layer in an amount of from 0.2 to 6 wt. -%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

14. The surface treated filler material product of claim 13, wherein the surface treated filler material product is in powder form.

15. The surface-treated filler material product according to claim 13 or 14, obtainable by the method according to any one of claims 1 to 12.

16. A polymer composition comprising at least one polymer resin and from 1 to 95 wt% based on the total weight of the polymer composition of the surface treated filler material product of any one of claims 13 to 15.

17. The polymer composition according to claim 16, wherein the at least one polymer resin is at least one thermoplastic polymer, preferably a thermoplastic polymer selected from the group consisting of homopolymers and/or copolymers of polyolefins, polyamides, halogen-containing polymers and/or polyesters.

18. The polymer composition according to claim 16 or 17, wherein the polymer composition is a masterbatch, preferably the masterbatch comprises the surface treated filler material product in an amount of from 50 to 95 wt. -%, preferably from 60 to 85 wt. -%, and more preferably from 70 to 80 wt. -%, based on the total weight of the masterbatch.

19. A fibre and/or filament and/or film and/or thread and/or sheet and/or tube and/or profile and/or mould and/or injection mould and/or blow mould comprising a surface treated filler material product according to any of claims 13 to 15 and/or a polymer composition according to any of claims 16 to 18.

20. An article comprising the surface treated filler material product of any one of claims 13 to 15; and/or the polymer composition according to any one of claims 16 to 18; and/or fibres and/or filaments and/or films and/or threads and/or sheets and/or tubes and/or profiles and/or moulds and/or injection moulds and/or blow moulds according to claim 19, wherein the article is selected from hygiene products, medical and healthcare products, filtration products, geotextile products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, building products and the like.

21. The article of claim 20, being a packaging product selected from the group consisting of: handbags, waste bags, transparent foils, hygiene films, agricultural foils, paper foils, bottles, (thermoformed) foils, extrusion coated paper and board, cartonboard, cardboard boxes, paper bags, sacks, corrugated cartons, flexible tubes for e.g. creams such as skin creams and cosmetics, bags for e.g. household waste and crates, oriented and bi-directional films, trays and the like.

22. Use of at least one monosubstituted succinic anhydride and/or salt reaction product thereof in combination with a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid in an amount of at least 10.0 wt. -%, based on the total weight of the mixture, and one or more additional saturated aliphatic linear or branched carboxylic acids having a total amount of carbon atoms of C8 to C24, and/or salt reaction products thereof for improving the flowability of a surface-treated filler material product.

23. Use of at least one monosubstituted succinic anhydride and/or salt reaction product thereof in combination with a mixture of aliphatic linear or branched carboxylic acids comprising stearic acid in an amount of at least 10.0% by weight, based on the total weight of the mixture, and one or more additional saturated aliphatic linear or branched carboxylic acids having a total amount of carbon atoms of from C8 to C24, and/or salt reaction products thereof, for improving the dispersion of calcium carbonate in the polymer matrix of a polymer composition.

24. The use according to claim 22 or 23, wherein the improvement is achieved if the Unconfined Yield Strength (UYS) is reduced by at least 7% or the Flow Factor (FF) is increased by at least 7% when the powder flowability is measured by the shear unit method against stress at 15kPa on an FT4 powder rheometer (astm d7891-15) compared to the same surface treated filler material product treated with the at least one monosubstituted succinic anhydride alone, and/or the Basic Flow Energy (BFE) is reduced by at least 7% when the powder flowability is measured by the stability and variable flow rate methods on an FT4 powder rheometer.

Drawings

FIG. 1 relates to the powder flow-stability and variable flow-rates of the powders 1 to 4

The following examples may additionally illustrate the invention, but are not meant to limit the invention to the illustrated embodiments. The following examples illustrate the improved flow of the surface treated filler material product and its improved dispersion in the polymer matrix of the polymer composition.

Examples

A) Measuring method

The following measurement methods were used to evaluate the parameters given in the examples and claims.

Particle size distribution (diameter) of particulate material<Mass% of particles of X) and weight median diameter (d)₅₀)

As used herein and as generally defined in the art, "d" is₅₀"values are based on Sedigraph by using micromeritics Instrument Corporation^TM5100 and is defined as the size at which particles having a diameter equal to the specified value account for 50% of the mass of the particles (median point).

Methods and apparatus are known to the skilled person and are commonly used to determine the particle size of fillers and pigments. Measured at 0.1 wt.% Na₄P₂O₇In an aqueous solution of (a). The sample was dispersed using a high speed stirrer and ultrasound.

BET specific surface area of the Material

Throughout this document, the BET method (using nitrogen as the adsorbed gas), well known to the skilled person (ISO9277:1995) is used to determine the specific surface area (in m) of a mineral filler²In terms of/g). The total surface area of the mineral filler (in m) is then obtained by multiplying this specific surface area by the mass of the mineral filler (in g) before treatment²Meter).

Amount of surface treatment layer

The amount of the treated layer on the calcium carbonate-comprising filler material is theoretically calculated from the BET value of the untreated calcium carbonate-comprising filler material and the amount of mono-substituted succinic anhydride and the mixture of aliphatic linear or branched carboxylic acids comprising stearic acid used for the surface treatment. It is assumed that 100% of the mixture of aliphatic linear or branched carboxylic acids comprising stearic acid and monosubstituted succinic anhydride added to the calcium carbonate-comprising filler material is present as a surface treatment layer on the surface of the calcium carbonate-comprising filler material.

Degree of water absorption

The moisture absorption sensitivity of the materials as referred to herein is measured in mg moisture/g after exposure to an atmosphere of 10% and 85% relative humidity at a temperature of +23 ℃ (± 2 ℃) for 2.5 hours, respectively. For this purpose, the sample was first kept under an atmosphere of 10% relative humidity for 2.5 hours, then the atmosphere was changed to 85% relative humidity, at which the sample was kept for a further 2.5 hours. The increase in weight between 10% and 85% relative humidity was then used to calculate the hygroscopicity in mg moisture/g sample.

Powder flow-stability and variable flow method

The Basic Flow Energy (BFE), Stability Index (SI), Specific Energy (SE), Flow Rate Index (FRI) and regulated bulk density (CBD) were measured using the stability and variable flow rate method on an FT4 powder rheometer (Freeman Technology, uk) equipped with powder rheometer software (v5.000.00012) and Freeman Technology data analysis software version 4.0.17.

The method involves filling a cylindrical container (25mm × 25mL glass container).

The first stage of the testing process is to obtain a uniform adjusted powder state to allow highly repeatable measurements to be made. The conditioning cycle involved a dynamic test blade cutting down through the powder and then traversing up, lifting the powder and dropping it onto the blade. This process helps to eliminate the effects of different sampling methods and powder storage times.

After this initial conditioning step, the powder volume was adjusted to the container size to remove excess powder ("split"), and the mass was recorded after the splitting step. After this, 8 repeated conditioning cycles and measurements were carried out with a 23.5mm blade. For each test cycle, the blade was inserted downward (counter clockwise, tip speed-100 mm/sec, helix angle 5 °/target height 5mm) and upward into the powder bed. For the conditioning step, the blade was inserted downward (tip speed-40 mm/sec/helix angle 5 °, target height 5mm) and upward into the powder bed. After those 8 tests, another 3 cycles (conditioning + test) were performed at variable flow rate, i.e. at a tip speed of 70 mm/sec (test 9), 40 mm/sec (test 10) and finally 10 mm/sec (test 11). Energy and torque were recorded and various flow parameters defined as follows were calculated:

-basic flow energy (BFE, mJ): energy cycle 7 (downwards)

-stability index: (energy test 7)/(energy cycle 1)

-specific energy (SE, mJ/g): (upward energy cycle 6+ upward energy cycle 7)/(2X separation Mass)

-Flow Rate Index (FRI): (energy test 11)/(energy test 8)

-adjusting bulk density (CBD, g/mL): (separation quality)/(separation volume)

Powder flow-shear cell process

Shear cell properties were measured according to ASTM D7891-15 using an FT4 powder rheometer (Freeman Technology, UK) using a cylindrical vessel (50 mm. times.85 mL or 25 mm. times.10 mL glass vessel), a 48 mm or 24mm shear cell, and a 15kPa pre-shear normal stress.

The following stepwise method was used for the measurements.

Initial powder conditioning:

the first stage of the testing procedure is to obtain a uniformly adjusted powder state to allow highly repeatable measurements. The conditioning cycle involved a dynamic test blade cutting down through the powder and then traversing up, lifting the powder and dropping it onto the blade. This process helps to eliminate the effects of different sampling methods and powder storage times.

Initial compaction

The conditioned powder column was compacted using a vented compaction piston (allowing entrapped air to escape) with a force equal to the pre-shear normal stress.

Critical consolidation

The point on the yield trace represents the shear stress value corresponding to incipient failure at each normal stress level. To achieve incipient failure, the specimens must be over-consolidated with respect to the normal stress applied during shear. This is achieved by reaching a critical consolidation level at steady state flow and then reducing the normal stress for shear. Thus, the shear test is a two-stage process consisting of:

1. pre-shearing

The purpose of pre-shearing is to achieve critical consolidation at a given pre-shear stress level. During this process, shear is continued until steady state flow is reached, at which point the pre-shear is complete.

2. Shear test

Reducing the normal stress causes the sample to now over-consolidate relative to the now applied normal stress. Shear was then resumed and the incipient failure point measured.

Five measurements were made for each pre-shear normal stress at five normal stresses (9 kPa; 8 kPa; 7 kPa; 6kPa and 5kPa) defined by the standard. Shear stress measurements were also made at a pre-shear normal stress level (i.e., 15 kPa).

The five measurements made constitute the yield trajectory for each pre-shear normal to stress level. The yield trace is plotted on a shear stress versus normal stress plot, where a morel circle can be added to extrapolate various flow data.

The extrapolated data includes:

cohesion (C, kPa) -shear stress at the intersection of the best fit line with the y-axis (i.e. normal stress equal to 0)

Unconfined yield strength (UYS, kPa) -the larger of 2 values (also referred to as σ c) at which the smaller morse circle intersects the x-axis

Large Principal Stress (MPS, kPa) -the larger of two values at which the larger morel circle intersects the x-axis (also referred to as σ 1).

Internal friction angle (AIF, °) -the angle produced by the best fit line with the transverse axis

-Flow Factor (FF): corresponding to MPS/UYS

Bulk density (BD, g/mL): adjusted bulk density after initial compaction

Extrusion simulation

Extrusion simulations were developed to evaluate mineral dispersion in polymer compositions. The tests were performed on a commercially available CollinPress Filter Test course-Line FT-E20T-IS.

The test method was used for each of the respective polymer compositions, wherein the extruder screw speed was maintained at 100rpm without using a melt pump, and wherein the melt temperature was 225 ℃ to 230 ℃ (extruder temperature setting: 190 ℃ -210 ℃ -230 ℃; die temperature setting: 230 ℃ -230 ℃).

Each corresponding polymer composition (900g of the effective powder A or B/2500g of the final sample obtained by diluting the polymer composition in LLDPEExxon Mobil LL 1001 VX) was measured using a 40 μm filter (GKD Gebr. Kufferath AG, Duren, Germany, product number 12102170055).

The results are expressed in bar and can be calculated by subtracting the final melt pressure (measured after 5 minutes of washing with the neat polymer material) from the initial pressure of the neat polymer material (LLDPE ExxonMobil LL 1001 VX).

Ash content

The ash content test was carried out by burning 5g to 30g of the corresponding polymer composition at 570 ℃ for 120 minutes.

B) Material

Filler material containing calcium carbonate

Filler material 1 containing calcium carbonate (powder 1; comparative)

0.7kg of wet-milled and spray-dried marble from Carrara, Italy (d)₅₀1.6 μm, BET specific surface area 4.1m²Per g) are placed in a high-speed mixer (Somakon MP LB mixer, Somakon Verfahrenstechnik, Germany) and adjusted by stirring for 10 minutes (1000rpm, 120 ℃). Thereafter, the amount of the catalyst is adjusted to 100 parts by weight of CaCO₃0.6 parts by weight of monosubstituted succinic anhydride 1 are added to the mixture. Stirring and heating was then continued for a further 15 minutes (120 ℃, 1000 rpm). After that, the mixture was cooled and the powder (powder 1) was collected.

Filler material 2 (powder 2; of the invention) containing calcium carbonate

0.7kg of wet-milled and spray-dried marble from Carrara, Italy (d)₅₀1.6 μm, BET specific surface area 4.1m²Per g) are placed in a high-speed mixer (Somakon MP LB mixer, Somakon Verfahrenstechnik, Germany) and adjusted by stirring for 10 minutes (1000rpm, 120 ℃). In-line with the aboveThereafter, the amount of the catalyst is adjusted to 100 parts by weight of CaCO₃0.5 parts by weight of monosubstituted succinic anhydride 1 and with respect to 100 parts by weight of CaCO₃0.2 parts by weight of carboxylic acid mixture 2 are simultaneously added to the mixture. Stirring and heating was then continued for a further 15 minutes (120 ℃, 1000 rpm). After that, the mixture was cooled and the powder (powder 2) was collected.

Filler material 3 (powder 3; of the invention) containing calcium carbonate

0.7kg of wet-milled and spray-dried marble from Carrara, Italy (d)₅₀1.6 μm, BET specific surface area 4.1m²Per g) are placed in a high-speed mixer (Somakon MP LB mixer, Somakon Verfahrenstechnik, Germany) and adjusted by stirring for 10 minutes (1000rpm, 120 ℃). Thereafter, the amount of the catalyst is adjusted to 100 parts by weight of CaCO₃0.4 parts by weight of monosubstituted succinic anhydride 1 and relative to 100 parts by weight of CaCO₃To the mixture was added simultaneously 0.4 parts by weight of carboxylic acid mixture 2. Stirring and heating was then continued for a further 15 minutes (120 ℃, 1000 rpm). After that, the mixture was cooled and the powder (powder 3) was collected.

Calcium carbonate-containing filler material 4 (powder 4; of the invention)

0.7kg of wet-milled and spray-dried marble from Carrara, Italy (d)₅₀1.6 μm, BET specific surface area 4.1m²Per g) are placed in a high-speed mixer (Somakon MP LB mixer, Somakon Verfahrenstechnik, Germany) and adjusted by stirring for 10 minutes (1000rpm, 120 ℃). Thereafter, the amount of the catalyst is adjusted to 100 parts by weight of CaCO₃0.4 parts by weight of monosubstituted succinic anhydride 1 are added to the mixture. Stirring and heating was then continued for a further 15 minutes (120 ℃, 1000 rpm). Then, the amount of the catalyst is adjusted to 100 parts by weight of CaCO₃To the mixture, then stirring and heating were continued for a further 15 minutes (120 ℃, 1000 rpm). After that, the mixture was cooled and the powder (powder 4) was collected.

Monosubstituted succinic anhydrides

Monosubstituted succinic anhydride (ASA)1

Monosubstituted alkenyl succinic anhydrides (2, 5-furandione, dihydro-, mono-C15-20-alkenyl derivative, CAS No. 68784-12-3) are blends of predominantly branched octadecenyl succinic anhydride (CAS #28777-98-2) and predominantly branched hexadecenyl succinic anhydride (CAS # 32072-96-1). Greater than 80% of the blend was branched octadecenyl succinic anhydride. The purity of the blend was >95 wt%. The residual olefin content is less than 3% by weight.

Carboxylic acid mixture 2

The carboxylic acid mixture 2 is a 1:1 mixture of stearic acid and palmitic acid.

Powder A (of the invention): dry ground limestone (d) from Nocera Umbria₅₀3.2, tip end 12 μm; BET specific surface area of 3.0m²Per g), treated with 0.35% by weight of monosubstituted succinic anhydride 1 and 0.15% by weight of carboxylic acid mixture 2.

Powder B (prior art): dry ground limestone (d) from Nocera Umbria₅₀3.2, tip end 12 μm; BET specific surface area of 3.0m²Per g), treated with 0.45% by weight of monosubstituted succinic anhydride 1.

Analysis and test results