Ca coated with maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobicizing agentCO3

文档序号：474212 发布日期：2021-12-31 浏览：30次中文

阅读说明：本技术 涂覆有马来酸酐接枝的聚乙烯和/或马来酸酐接枝的聚丙烯和至少一种疏水化剂的CaCO3 (Ca coated with maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobicizing agentCO3 ) 是由 M·韦尔克 J·巴兰格 S·瑞恩特什于 2020-06-04 设计创作，主要内容包括：本发明涉及经表面处理填料材料产品,其包含a)至少一种含碳酸钙填料材料和b)在该至少一种含碳酸钙填料材料的表面上的处理层,该处理层包含i.马来酸酐接枝的聚乙烯和/或马来酸酐接枝的聚丙烯和ii.至少一种疏水化剂。此外还公开了一种用于制备本发明的经表面处理填料材料产品的方法,以及包含至少一种聚合物树脂和本发明的经表面处理填料材料产品的聚合物组合物。额外地,公开了包含本发明的经表面处理填料材料产品的纤维和/或长丝和/或膜和/或丝线和/或片材和/或管材和/或型材和/或模具和/或注塑配混物和/或吹塑配混物,以及本发明的经表面处理的矿物填料产品在聚合物组合物中用于改善该聚合物组合物的机械和/或流变性能的用途。(The present invention relates to a surface-treated filler material product comprising a) at least one calcium carbonate-comprising filler material and b) a treatment layer on the surface of the at least one calcium carbonate-comprising filler material, the treatment layer comprising i. Also disclosed is a method for preparing the surface treated filler material product of the invention, and a polymer composition comprising at least one polymer resin and the surface treated filler material product of the invention. Additionally, fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds comprising the surface treated filler material product of the invention are disclosed, as well as the use of the surface treated mineral filler product of the invention in polymer compositions for improving the mechanical and/or rheological properties of the polymer composition.)

1. A surface treated filler material product comprising

a) At least one calcium carbonate-comprising filler material,

b) a treatment layer on the surface of the at least one calcium carbonate-comprising filler material, the treatment layer comprising

i. Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and

at least one hydrophobicizing agent

Wherein the surface-treated filler material product comprises the treatment layer in an amount of 0.2 to 7% by weight, 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 at least one hydrophobizing agent is selected from the group consisting of succinic anhydride, carboxylic acids, phosphoric monoesters, phosphoric diesters, reaction products thereof, and mixtures thereof.

3. The surface treated filler material product according to any one of the preceding claims, wherein the at least one hydrophobizing agent is at least one of:

monosubstituted succinic anhydrides and/or reaction products thereof, and

aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and/or reaction products thereof.

4. The surface-treated filler material product according to claim 3, wherein the mono-substituted succinic anhydride of step ii) and/or the reaction product thereof consists of succinic anhydride mono-substituted with a group selected from: linear, branched, aliphatic and cyclic groups having from 2 to 30, preferably from 3 to 25 and most preferably from 4 to 20 carbon atoms in the substituents.

5. The surface-treated filler material product according to claims 3 to 4, wherein the mono-substituted succinic anhydride of step ii) and/or the reaction product thereof 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.

6. The surface treated filler material product according to claims 3-5, wherein the aliphatic linear and/or branched carboxylic acid and/or reaction products thereof of step ii) has 8-22, preferably 10-22, more preferably 12-20, even more preferably 14-20 carbon atoms, and most preferably the aliphatic linear and/or branched carboxylic acid and/or reaction products thereof is stearic acid, palmitic acid or a mixture thereof.

7. The surface-treated filler material product according to any one of the preceding claims, wherein the calcium carbonate-containing filler material of step a) is selected from ground calcium carbonate, preferably marble, limestone, dolomite and/or chalk; and/or Precipitated Calcium Carbonate (PCC), preferably vaterite, calcite and/or aragonite, more preferably, the calcium carbonate-containing filler material is ground calcium carbonate.

8. The surface-treated filler material product according to any one of the preceding claims, wherein the at least one calcium carbonate-containing filler material of step a) has

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

b) Top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less₉₈) And/or

c) Measured by the BET nitrogen method to be 0.5 to 150m²Per g, preferably from 0.5 to 50m²In g, more preferably from 0.5 to 35m²In g and most preferably from 0.5 to 10m²Specific surface area per gram (BET), and/or

d) A residual total moisture content of from 0.01 wt% to 1 wt%, preferably from 0.01 to 0.2 wt%, more preferably from 0.02 to 0.2 wt% and most preferably from 0.03 to 0.2 wt%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

9. The surface treated filler material product according to any one of the preceding claims, wherein the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is selected from the group consisting of maleic anhydride grafted Low Density Polyethylene (LDPE), maleic anhydride grafted Linear Low Density Polyethylene (LLDPE), maleic anhydride grafted High Density Polyethylene (HDPE), maleic anhydride grafted atactic polypropylene, maleic anhydride grafted isotactic polypropylene, maleic anhydride grafted syndiotactic polypropylene, maleic anhydride grafted polyethylene wax, maleic anhydride grafted polypropylene wax and mixtures thereof, and preferably maleic anhydride grafted Linear Low Density Polyethylene (LLDPE) and maleic anhydride grafted polyethylene wax, and most preferably maleic anhydride grafted polyethylene wax.

10. The surface treated filler material product according to any one of the preceding claims, wherein the surface treated filler material product is in the form of a powder.

11. A method of preparing a surface treated filler material product, the method comprising at least the steps of:

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

b) provide for

i. Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and

at least one hydrophobizing agent, and

c) forming a treatment layer on the surface of the at least one calcium carbonate-comprising filler material by contacting the surface of the at least one calcium carbonate-comprising filler material of step a) with 0.2 to 7% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material, of the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in any order in one or more steps under mixing, wherein the treatment layer comprises the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least hydrophobizing agent of step ii).

12. The method of preparing a surface-treated filler material product according to any one of the preceding claims, wherein the at least one calcium carbonate-comprising filler material of step a) is preheated before being subjected to the contacting step c), preferably the at least one calcium carbonate-comprising filler material of step a) is preheated at a temperature of 20-250 ℃, more preferably 40-200 ℃, even more preferably 50-150 ℃ and most preferably 60-140 ℃.

13. Process for the preparation of a surface treated filler material product, wherein the contacting step c) is carried out by adding the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5 and most preferably from 4:1 to 1:4, for example in an amount of 1: 1.

14. The process for preparing a surface-treated filler material product according to any one of the preceding claims, wherein the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is added in contacting step c) in a total amount of from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight and most preferably from 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material of step a); and the at least one hydrophobizing agent of step ii) is added in the contacting step c) in a total amount of from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a).

15. The method of preparing a surface treated filler material product according to any of the preceding claims, wherein the contacting step c) is performed at a temperature of 20-250 ℃, preferably 60-180 ℃ and most preferably 80-150 ℃.

16. The method for preparing a surface-treated filler material product according to any one of the preceding claims, wherein the contacting step c) is carried out by adding the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) simultaneously or sequentially, preferably simultaneously, with the proviso that if the compounds are added sequentially, the addition of the first compound does not result in complete coverage of the surface of the at least one calcium carbonate-comprising filler material.

17. A polymer composition comprising at least one polymer resin and from 1 to 95% by weight, based on the total weight of the polymer composition, of a surface treated filler material product according to claims 1 to 10.

18. The polymer composition according to claim 17, further comprising

Natural fibres, preferably wood fibres, cellulose fibres, hemp fibres and/or fibres of agricultural waste, and/or

Synthetic fibers, preferably glass fibers, carbon fibers and/or aramid fibers.

19. Fibres and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or moulds and/or injection moulding compounds and/or blow moulding compounds comprising the surface treated filler material product according to claims 1-10 and/or the polymer composition according to claim 17 or 18.

20. Use of a surface treated mineral filler product according to claims 1-10 in a polymer composition, preferably a polyethylene or polypropylene composition, for improving the mechanical and/or rheological properties of the polymer composition compared to the same polymer composition treated in the same way, wherein the surface treated mineral filler product is treated with at least one hydrophobizing agent only.

Technical Field

The present invention relates to a surface-treated filler material product comprising a) at least one calcium carbonate-comprising filler material and b) a treatment layer on the surface of the at least one calcium carbonate-comprising filler material, the treatment layer comprising i. Also disclosed is a method for preparing the surface treated filler material product of the invention, and a polymer composition comprising at least one polymer resin and the surface treated filler material product of the invention. Additionally, fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds comprising the surface treated filler material products of the present invention are disclosed, as well as the use of the surface treated mineral filler products of the present invention in polymer compositions for improving the mechanical and/or rheological properties of the polymer compositions.

Background

In practice, filler materials, and in particular calcium carbonate-containing filler materials, are often used as particulate fillers in thermoplastic polymer products, such as fibers, filaments, films and/or threads, typically made of Polyethylene (PE), polypropylene (PP), Polyurethane (PU), polyvinyl chloride (PVC), Polyester (PEs) and/or Polyamide (PA). However, additives are introduced to provide the coated filler material and to improve the dispersion of the mineral filler material in the polymer matrix of the polymer composition and possibly to improve the processability of such polymer composition and/or the properties of the end-use product, such as fibers, filaments, films, threads, sheets, profiles, molds, injection molding compounds, blow molding compounds. Eliminating such additives can unacceptably reduce the quality of the resulting fibers, filaments, films, threads, sheets, molds, injection molding compounds, blow molding compounds. Furthermore, there is a need to provide filler materials with good flowability to ensure high productivity in the manufacture of the final treated mineral filler material product and further processing of said product into end-use products.

In the art, several attempts have been made to improve the suitability of mineral filler materials, in particular calcium carbonate-containing mineral filler materials, for example by treating such mineral filler materials with surface treatment agents, such as hydrophobizing agents.

For example, WO 00/20336 relates to ultrafine natural calcium carbonate which can optionally be treated with one or more fatty acids or one or more salts or mixtures thereof as hydrophobizing agent and which is used as rheology modifier for polymer compositions.

Also, US 4,407,986 relates to a precipitated calcium carbonate surface-treated with a dispersant which may comprise higher fatty acids and their metal salts, to limit the addition of lubricating additives when kneading such calcium carbonate with crystalline polypropylene and to avoid the formation of calcium carbonate aggregates which limit the impact strength of the polypropylene.

EP 0998522 relates to surface-treated calcium carbonate fillers for breathable films using fatty acids of at least 10 carbon atoms, wherein the filler before and after the treatment process must be largely free of moisture in the range of less than 0.1% by weight.

In EP 0325114 (relating to a non-sag, under-seal composition for motor vehicles based on polyvinyl chloride with improved rheological and adhesion properties), example 7 discloses mixtures of ammonium salts of 12-hydroxystearic acid in combination with fatty acids (weight ratio 1:1) for the treatment of mineral fillers.

WO 03/082966 relates to crosslinkable and/or crosslinked nanofiller compositions which may in optional embodiments additionally comprise fillers which may or may not be coated with hydrophobizing agents such as stearic acid, stearates, silanes, siloxanes and/or titanates. Such nanofiller compositions are useful for increasing barrier properties, strength and heat distortion temperature, making them useful in medical, automotive, electrical, construction and food applications.

US 2002/0102404 describes dispersible calcium carbonate particles coated on their surface with a combination of saturated and unsaturated aliphatic carboxylic acids and their salts and organic compounds such as phthalates, which are used in adhesive compositions to improve viscosity stability and adhesion properties.

Furthermore, US 2002/0102404 requires the use of mixtures of saturated and unsaturated aliphatic carboxylic acids/salts. The presence of unsaturated aliphatic carboxylic acids/salts increases the risk of undesirable in situ side reactions with the double bonds during processing of any material comprising unsaturated aliphatic carboxylic acids/salts. Furthermore, the presence of unsaturated aliphatic carboxylic acids/salts may cause discoloration or the generation of unwanted odours, especially rancid odours, of the materials in which they are used.

US 4,520,073 describes mineral filler materials with an improved hydrophobic coating prepared by pressure coating of porous minerals using steam as a carrier for the coating material. The coating material may in particular be selected from long chain aliphatic fatty acids and salts thereof.

WO 2008/077156 a2 relates to spun fibers comprising at least one polymer resin and at least one filler having an average particle size of less than or equal to about 5 microns and/or having a top cut of less than about 15 microns, wherein the at least one filler is present in an amount of less than about 40% by weight relative to the total weight of the spun fiber. The coating of the filler is described as being at least one organic material selected from fatty acids and salts and esters thereof, such as stearic acid, stearate salts, ammonium stearate and calcium stearate.

GB 2336366A relates to filled thermoplastic compositions, in particular filled low density polyethylene compositions, which are formed into products or articles by an extrusion process. It is also described that the hydrophobizing agent is preferably an organic carboxylic acid or a partially or fully neutralized salt thereof having at least one saturated or unsaturated hydrocarbon chain having from 8 to 28 carbon atoms, such as calcium carbonate if the particulate mineral filler has a neutral to basic surface reaction.

EP2159258a1 relates to a treated mineral filler product comprising: a) at least one mineral filler; b) a treatment layer on a surface of the mineral filler, the treatment layer comprising: at least one saturated C8-C24 aliphatic carboxylic acid; and at least one salt of a divalent and/or trivalent cation of one or more saturated C8-C24 aliphatic carboxylic acids; the method is characterized in that: all of the aliphatic carboxylic acid salts: all of the aliphatic carboxylic acids in a weight ratio of 51:49 to 75: 25; and the treatment layer is at least 2.5mg/m²The mineral filler is present in an amount.

Another hydrophobicizing agent of choice and of particular relevance is a monosubstituted succinic anhydride or a mixture of monosubstituted succinic anhydrides.

For example, WO 2014/060286 a1 relates to a method for preparing a surface treated filler material product using succinic anhydride, the method comprising at least the steps of: a) providing at least one calcium carbonate-comprising filler material and b) providing at least one monosubstituted succinic anhydride and contacting the surface of the at least one calcium carbonate-comprising filler material of step a) with the at least one monosubstituted succinic anhydride of step b).

WO 2016/023937 a1 relates to a method for producing breathable films. The surface-treated filler material product comprises A) at least one ground calcium carbonate-comprising filler material, and B) a treatment layer comprising at least one monosubstituted succinic anhydride and/or at least one monosubstituted succinic acid and/or a salt thereof, on the surface of the at least one wet-ground calcium carbonate-comprising filler material.

However, there remains a need to provide improved surface treated filler material products. In particular, there is a need to provide surface treated filler material products having good powder flow properties but also having low moisture pick-up sensitivity. Furthermore, there is a need to provide such surface treated filler material products as follows: it can be used in polymer compositions to maintain or improve the mechanical and/or rheological properties such as melt flow rate and/or maximum load performance and/or impact strength and/or flexural modulus and/or tensile properties such as yield strength of polymer compositions comprising such surface treated filler material products and/or end-use products, such as fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds.

Disclosure of Invention

It is therefore an object of the present invention to provide a surface treated filler material product which comprises a hydrophobizing agent and which exhibits good powder flow properties and low moisture uptake. Furthermore, it is another object of the present invention to provide such a surface treated filler material product that can be used in a polymer composition to maintain or improve the mechanical and/or rheological properties, such as melt flow rate and/or maximum load performance and/or impact strength and/or flexural modulus and/or tensile properties, such as yield strength, of the polymer composition and/or end use product. It is a further object to provide a process for the preparation of such a surface treated filler material product. Other objects will be apparent from the following description of the invention.

The foregoing and other objects are solved by the subject matter as defined herein in claim 1.

Advantageous embodiments of the inventive method for preparing a surface-treated filler material product are defined in the respective dependent claims.

According to one aspect of the present application, there is provided a surface treated filler material product comprising

a) At least one calcium carbonate-comprising filler material,

b) a treatment layer on the surface of the at least one calcium carbonate-comprising filler material, the treatment layer comprising

i. Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and

at least one hydrophobicizing agent

The present inventors have surprisingly found that the surface treated filler material products described above have good powder flow properties but also have low moisture pick-up sensitivity. Furthermore, when the surface treated filler material products of the present invention are used in polymer compositions, they maintain or improve the mechanical and/or rheological properties of the polymer compositions and/or end-use products, particularly as compared to surface treated filler material products that have been surface treated with only the same hydrophobizing agent. The polymer compositions and/or end-use products comprising the surface treated filler material products of the present invention especially have maintained or lower melt flow rates and/or maintained or higher maximum load performance, maintained or higher impact strength and/or maintained or higher flexural modulus and/or maintained or higher tensile properties such as yield strength-especially compared to polymer compositions and/or end-use products comprising surface treated filler material products that have been surface treated with only the same hydrophobizing agent.

According to another aspect of the present invention, there is provided a method for preparing a surface treated filler material product, the method comprising at least the steps of:

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

b) provide for

i. Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and

at least one hydrophobicizing agent

c) Forming a treatment layer on the surface of the at least one calcium carbonate-comprising filler material by contacting the surface of the at least one calcium carbonate-comprising filler material of step a) with 0.2 to 7% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material, of the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in any order in one or more steps under mixing, wherein the treatment layer comprises the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least hydrophobizing agent of step ii).

The present inventors have surprisingly found that by the above process it is possible to provide a surface treated filler material product comprising both maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobising agent on the surface of the filler material. Furthermore, the above-described process is simple and economical and results in the production of the surface treated filler material product of the present invention as described above.

According to another aspect of the present invention, there is provided a polymer composition comprising at least one polymer resin and from 1 to 95% by weight, based on the total weight of the polymer composition, of a surface treated filler material product as defined above.

According to another aspect of the present invention, there is provided a fiber and/or filament and/or film and/or filament and/or sheet and/or pipe and/or profile and/or mould and/or injection moulding compound (compound) and/or blow moulding compound comprising a surface treated filler material product as defined above and/or a polymer composition as defined above.

According to another aspect of the invention, the surface-treated mineral filler material product as defined above is used in a polymer composition, preferably a polyethylene or polypropylene composition, for improving the mechanical and/or rheological properties of the polymer composition compared to the same polymer composition treated in the same manner, wherein the surface-treated mineral filler material product is treated with at least one hydrophobizing agent only.

Advantageous embodiments of the above-mentioned aspect are defined in the respective dependent claims.

According to one embodiment of the invention, the at least one hydrophobizing agent is selected from the group consisting of succinic anhydrides, carboxylic acids, phosphoric monoesters, phosphoric diesters, reaction products thereof and mixtures thereof.

According to another embodiment of the invention, the at least one hydrophobizing agent is at least one of:

monosubstituted succinic anhydrides and/or reaction products thereof, and

aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and/or reaction products thereof.

According to another embodiment of the present invention, the mono-substituted succinic anhydride of step ii) and/or the reaction product thereof consists of succinic anhydride mono-substituted with a group selected from: linear, branched, aliphatic and cyclic groups having from 2 to 30, preferably from 3 to 25 and most preferably from 4 to 20 carbon atoms in the substituents.

According to another embodiment of the present invention, the monosubstituted succinic anhydride of step ii) and/or the reaction product thereof is

According to another embodiment of the present invention, the aliphatic linear and/or branched carboxylic acid and/or reaction products thereof of step ii) has 8 to 22, preferably 10 to 22, more preferably 12 to 20, even more preferably 14 to 20 carbon atoms, and most preferably the aliphatic linear and/or branched carboxylic acid and/or reaction products thereof is stearic acid, palmitic acid or a mixture thereof.

According to another embodiment of the present invention, the calcium carbonate-containing filler material of step a) is selected from ground calcium carbonate, preferably marble, limestone, dolomite and/or chalk; and/or Precipitated Calcium Carbonate (PCC), preferably vaterite, calcite and/or aragonite, more preferably, the calcium carbonate-containing filler material is ground calcium carbonate.

According to another embodiment of the invention, the at least one calcium carbonate-comprising filler material of step a) has

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

b) Top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less₉₈) And/or

d) A residual total moisture content of from 0.01 wt% to 1 wt%, preferably from 0.01 to 0.2 wt%, more preferably from 0.02 to 0.1 wt% and most preferably from 0.03 to 0.2 wt%, based on the total dry weight of the at least one calcium carbonate-containing filler material.

According to another embodiment of the present invention, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is selected from the group consisting of maleic anhydride grafted Low Density Polyethylene (LDPE), maleic anhydride grafted Linear Low Density Polyethylene (LLDPE), maleic anhydride grafted High Density Polyethylene (HDPE), maleic anhydride grafted atactic polypropylene, maleic anhydride grafted isotactic polypropylene, maleic anhydride grafted syndiotactic polypropylene, maleic anhydride grafted polyethylene wax, maleic anhydride grafted polypropylene wax and mixtures thereof, and preferably maleic anhydride grafted Linear Low Density Polyethylene (LLDPE) and maleic anhydride grafted polyethylene wax, and most preferably maleic anhydride grafted polyethylene wax.

According to another embodiment of the invention, the surface treated filler material product is in the form of a powder.

According to another embodiment of the invention, in the process for preparing the surface-treated filler material product, the at least one calcium carbonate-comprising filler material of step a) is preheated before contacting step c), preferably the at least one calcium carbonate-comprising filler material of step a) is preheated at a temperature of 20-250 ℃, more preferably 40-200 ℃, even more preferably 50-150 ℃ and most preferably 60-140 ℃.

According to another embodiment of the invention, in the process for preparing the surface-treated filler material product, the contacting step c) is carried out by adding the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5 and most preferably from 4:1 to 1:4, for example in an amount of 1: 1.

According to another embodiment of the invention, in the process for preparing the surface-treated filler material product, the maleic anhydride-grafted polyethylene and/or the maleic anhydride-grafted polypropylene of step i) is added in a contacting step c) in a total amount of 0.1 to 4% by weight, preferably 0.2 to 3% by weight and most preferably 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a); and the at least one hydrophobizing agent of step ii) is added in the contacting step c) in a total amount of from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate-containing filler material of step a).

According to another embodiment of the invention, in the process for preparing the surface-treated filler material product, the contacting step c) is carried out at a temperature of 20 to 250 ℃, preferably 60 to 180 ℃ and most preferably 80 to 150 ℃.

According to another embodiment of the invention, in the process for preparing the surface-treated filler material product, the contacting step c) is carried out by adding the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) simultaneously or sequentially, preferably simultaneously, with the proviso that if the compounds are added sequentially, the addition of the first compound does not result in complete coverage of the surface of the at least one calcium carbonate-comprising filler material.

According to another embodiment of the invention, the polymer composition further comprises natural fibers, preferably wood fibers, cellulose fibers, hemp fibers and/or agricultural waste fibers and/or synthetic fibers, preferably glass fibers, carbon fibers and/or aramid fibers.

It is to be understood that for the purposes of this invention, the following terms have the following meanings:

for the purposes of the present invention, the term "filler material" in the meaning of the present invention refers to substances of mineral origin which are added to materials such as paper, plastics, rubber, paints and adhesives in order to reduce the consumption of more expensive materials such as binders or to improve the technical properties of the product. Typical filler materials used in the respective fields are well known to those skilled in the art. Furthermore, the term "calcium carbonate-comprising filler material" refers to a material comprising at least 80% by weight of calcium carbonate, based on the total dry weight of the calcium carbonate-comprising filler material.

The term "surface-treated filler material product" in the meaning of the present invention refers to the following calcium carbonate-containing filler materials: which has been contacted with, for example, a surface treatment agent to obtain a coating on at least a part of the surface of the calcium carbonate-comprising filler material.

By "treatment layer" in the context of the present invention is meant a layer, preferably a monolayer, of a treatment agent on the surface of the surface treated filler material product. The "treatment layer" comprises maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobising agent, wherein the surface treated filler material product comprises the treatment layer in an amount of 0.2 to 7 wt. -%, based on the total dry weight of the at least one calcium carbonate containing filler material.

The term "dry or dry" calcium carbonate-containing filler material is understood to mean a filler material having less than 1.0% by weight of water relative to the weight of the filler material. The water% (equal to "residual total moisture content") was determined according to the coulomeric Karl Fischer measurement method, wherein the filler material was heated to 220 ℃ and the water content released as steam and separated using a nitrogen stream (at 100 ml/min) was determined in a coulomeric Karl Fischer unit.

The "Specific Surface Area (SSA)" of a calcium carbonate-comprising filler material in the meaning of the present invention is defined as the surface area of the calcium carbonate-comprising filler material divided by its mass. Specific surface area as used herein was measured by nitrogen adsorption using BET isotherms (ISO9277:2010) and in m²The/g is given in detail.

The "particle size" of a particulate material (e.g., the surface treated filler material product herein) is determined by its particle size d_xThe distribution of (c). In which the value d_xThe following diameters are indicated: x% by weight of the particles, relative to the diameter, having a value of less than d_xOf (c) is measured. This means for example d₂₀The values refer to the following particle sizes: wherein 20% by weight of all particles are smaller than the particle size. d₅₀The value is thus the weight median particle size, i.e. 50% by weight of all particles are larger than this particle size, while the remaining 50% by weight are smaller than this particle size. For the purposes of the present invention, unless otherwise specified, the particle size is designated as weight median particle size d₅₀。d₉₈The values refer to the following particle sizes: wherein 98% by weight of all particles are smaller than the particle size. d₉₈The value is also referred to as "top cut". Particle size was determined by using a Sedigraph from Micromeritics Instrument Corporation^TM5100 or 5120 instruments. Methods and apparatus are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. At 0.1% by weight Na₄P₂O₇Is measured in an aqueous solution of (a). The samples were dispersed using a high speed stirrer and ultrasound.

For the purposes of the present invention, the "viscosity" as measured by means of a rotational rheometer according to DIN 53019 is that of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.

When the term "comprising" is used in the present description and claims, it does not exclude other elements of primary or secondary functional importance that are not specifically mentioned. For the purposes of the present invention, the term "consisting of … … (of) is to be considered as a preferred embodiment of the term" comprising or comprising ". If in the following it is defined that a group set (group) comprises at least a certain number of embodiments, this is also to be understood as disclosing a group set, which preferably only consists of these embodiments.

Wherever the terms "comprising" or "having" are used, these terms are considered equivalent to "comprising" as defined above.

Where an indefinite or definite article is used when referring to a singular noun e.g. "a", "an" or "the", this includes a plural of that noun unless something else is specifically stated.

When referring to the surface treated filler material product hereinafter, it is to be understood that preferred embodiments and technical details also relate to the inventive method, the inventive polymer composition, the inventive product comprising the surface treated filler material product and/or the polymer composition, and the inventive use.

Surface treated filler material product

As described above, the surface-treated filler material product of the present invention comprises a) at least one calcium carbonate-containing filler material and b) a treatment layer comprising i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and ii) at least one hydrophobizing agent on the surface of the at least one calcium carbonate-containing filler material, wherein the surface-treated filler material product comprises the treatment layer in an amount of from 0.2 to 7 wt. -%, based on the total dry weight of the at least one calcium carbonate-containing filler material. In the following, further details of the invention will be referred to, in particular the above-mentioned compounds of the surface-treated filler material product.

Characterization of at least one calcium carbonate-comprising filler material

According to step a) of the present invention, the surface-treated filler material product comprises a) at least one calcium carbonate-containing filler material.

The expression "at least one" calcium carbonate-comprising filler material means that one or more, for example two or three, calcium carbonate-comprising filler materials may be provided. According to a preferred embodiment, the at least one calcium carbonate-comprising filler material provided in step a) comprises only one calcium carbonate-comprising filler material.

According to a preferred embodiment of the present invention, the calcium carbonate-comprising filler material is selected from Ground Calcium Carbonate (GCC), preferably marble, limestone, dolomite and/or chalk; precipitated Calcium Carbonate (PCC), preferably vaterite, calcite and/or aragonite, more preferably, the at least one calcium carbonate-comprising filler material is ground calcium carbonate.

GCC is understood to mean calcium carbonate in naturally occurring form, mined from sedimentary rocks such as limestone or chalk, or metamorphic marble rocks, and processed by treatments in wet and/or dry form such as grinding, screening and/or classification (for example by means of cyclones or classifiers). In one embodiment of the invention, the GCC is selected from marble, chalk, dolomite, limestone and mixtures thereof.

In contrast, PCC type calcium carbonates include synthetic calcium carbonate products obtained by carbonating a calcium hydroxide slurry (commonly referred to as lime slurry or milk when derived from finely divided calcium oxide particles in water) or precipitating out of an ionic salt solution. PCC may be rhombohedral and/or scalenohedral and/or aragonitic; preferred synthetic or precipitated calcium carbonates include aragonite, vaterite or calcite mineralogical forms or mixtures thereof.

In a preferred embodiment, the at least one calcium carbonate-containing filler material is ground calcium carbonate and preferably marble.

It is to be understood that the amount of calcium carbonate in the at least one calcium carbonate-comprising filler material is at least 80% by weight, such as at least 95% by weight, preferably from 97 to 100% by weight, more preferably from 98.5 to 99.95% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material.

The at least one calcium carbonate-comprising filler material is preferably in the form of a particulate material and may have a particle size distribution as conventionally used for materials involved in the type of product to be produced. Generally, it is preferredThe at least one calcium carbonate-comprising filler material having a weight median particle size d in the range from 0.1 to 7 μm₅₀The value is obtained. For example, the at least one calcium carbonate-comprising filler material has a weight median particle size d of from 0.25 μm to 5 μm and preferably from 0.5 μm to 4 μm₅₀。

Additionally or alternatively, the at least one calcium carbonate-comprising filler material has a top cut (d) of ≦ 100 μm₉₈). For example, the at least one calcium carbonate-comprising filler material has a top cut (d) of ≦ 40 μm, preferably ≦ 25 μm, and most preferably ≦ 15 μm₉₈)。

Additionally or alternatively, the at least one calcium carbonate-comprising filler material has a BET nitrogen method of from 0.5 to 150m²BET specific surface area in g. For example, the at least one calcium carbonate-comprising filler material has a BET nitrogen method of 0.5 to 50m²In g, more preferably from 0.5 to 35m²In g and most preferably from 0.5 to 10m²Specific surface area (BET) in g.

Additionally or alternatively, the at least one calcium carbonate-comprising filler material has a residual total moisture content of from 0.01 to 1% by weight, preferably from 0.01 to 0.2% by weight, more preferably from 0.02 to 0.2% by weight and most preferably from 0.03 to 0.2% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material.

Thus, preferably, the at least one calcium carbonate-comprising filler material has

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

b) Top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less₉₈) And/or

d) A residual total moisture content of from 0.01 to 1% by weight, preferably from 0.01 to 0.2% by weight, more preferably from 0.02 to 0.2% by weight and most preferably from 0.03 to 0.2% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material.

For example, the at least one calcium carbonate-comprising filler material has

a) A weight median particle size d in the range from 0.1 μm to 7 μm, preferably from 0.25 μm to 5 μm and most preferably from 0.5 μm to 4 μm₅₀Value, or

b) Top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less₉₈) Or is or

c) Measured by the BET nitrogen method to be 0.5 to 150m²Per g, preferably from 0.5 to 50m²In g, more preferably from 0.5 to 35m²In g and most preferably from 0.5 to 10m²A specific surface area per gram (BET), or

Alternatively still, the at least one calcium carbonate-comprising filler material has

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

b) top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less₉₈) And are and

c) measured by the BET nitrogen method to be 0.5 to 150m²Per g, preferably from 0.5 to 50m²In g, more preferably from 0.5 to 35m²In g and most preferably from 0.5 to 10m²Specific surface area per gram (BET), and

d) a residual total moisture content of from 0.01 to 1% by weight, preferably from 0.01 to 0.2% by weight, more preferably from 0.02 to 0.2% by weight and most preferably from 0.03 to 0.2% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material.

In one embodiment of the invention, the at least one calcium carbonate-comprising filler material has a weight median particle size d of from 0.1 μm to 7 μm, preferably from 0.25 μm to 5 μm and most preferably from 0.5 μm to 4 μm, for example about 1.9 μm₅₀A value and has a top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less, for example 5.8 μm₉₈). According to a preferred embodiment, theThe at least one calcium carbonate-containing filler material is ground calcium carbonate.

Preferably, the at least one calcium carbonate-comprising filler material is a dry ground material, a wet ground and dried material or a mixture of the above materials. In general, the grinding step can be carried out with any conventional grinding device, for example under conditions such that the refining results mainly from the impact with the auxiliary body, that is to say in one or more of the following: ball mills, rod mills, vibratory mills, crushers, centrifugal impact mills, vertical bead mills, attritors, pin mills, hammer mills, pulverizers, shredders, delumpers, cutters (knife cutters), or other such equipment known to those skilled in the art.

In case the at least one calcium carbonate-comprising filler material is a wet ground calcium carbonate-comprising filler material, the grinding step may be performed under conditions such that autogenous grinding occurs and/or by horizontal ball milling and/or other such methods known to the skilled person. The wet processed calcium carbonate-comprising filler material thus obtained can be washed and dewatered by well known methods, e.g. by flocculation, filtration or forced evaporation (before drying). The subsequent drying step may be performed in a single step (such as spray drying), or in at least two steps, such as subjecting the calcium carbonate-comprising filler material to a first heating step to reduce the associated moisture content to a level of no greater than about 1% by weight based on the total dry weight of the at least one calcium carbonate-comprising filler material. The residual total moisture content of the filler can be determined by Karl Fischer coulometry by desorbing the water in an oven at 195 ℃ and using dry N₂This was measured by passing it continuously through a KF coulometer (Mettler Toledo colorimetric KF Titrator C30, in combination with a Mettler oven DO 0337) at 100ml/min for 10 min. The residual total moisture content can be determined using a calibration curve and can also take into account the 10min dead zone of the gas flow with no sample. The residual total moisture content may be further reduced by subjecting the at least one calcium carbonate-comprising filler material to a second heating step. In the case where the drying is carried out by more than one drying step, this first step may be carried out by heating in a stream of hot air, while the second and further drying steps are carried outThe steps are preferably carried out by indirect heating, wherein the atmosphere in the respective container comprises a surface treatment agent. It is also common that the at least one calcium carbonate-comprising filler material is subjected to a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.

In one embodiment of the present invention, the at least one calcium carbonate-comprising filler material comprises a dry ground calcium carbonate-comprising filler material. In another preferred embodiment of the present invention, the at least one calcium carbonate-comprising filler material is the following such material: the material was wet milled in a horizontal ball mill and then dried by using a well known spray drying method.

For example, in case the at least one calcium carbonate-comprising filler material is a wet-milled and spray-dried calcium carbonate, the residual total moisture content of the at least one calcium carbonate-comprising filler material is preferably from 0.01 to 1% by weight, preferably from 0.01 to 0.2% by weight, more preferably from 0.02 to 0.2% by weight and most preferably from 0.03 to 0.2% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material, and the at least one calcium carbonate-comprising filler material has a weight median particle size d of from 0.1 μm to 7 μm, preferably from 0.25 μm to 5 μm and most preferably from 0.5 μm to 4 μm, for example about 1.9 μm₅₀A value and has a top cut (d) of 100 μm or less, preferably 40 μm or less, more preferably 25 μm or less and most preferably 15 μm or less, for example 5.8 μm₉₈)。

Characterization of the treatment layer on the surface of the at least one calcium carbonate-comprising filler material

According to step b) of the present invention, the surface-treated filler material product comprises a treatment layer on the surface of the at least one calcium carbonate-comprising filler material.

The surface treatment layer comprises i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent.

Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene

The term "maleic anhydride grafted polyethylene" refers to a polyethylene backbone that has been grafted with maleic anhydride, and the term "maleic anhydride grafted polypropylene" refers to a polypropylene backbone that has been grafted with maleic anhydride.

Polyethylene in the meaning of the present invention refers to a polymer comprising ethylene units. Polypropylene in the meaning of the present invention refers to a polymer comprising propylene units.

According to one embodiment of the invention, the polyethylene and/or polypropylene may be selected from the group consisting of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene, polyethylene wax, polypropylene wax and mixtures thereof, and preferably Linear Low Density Polyethylene (LLDPE) and polyethylene wax, and most preferably polyethylene wax.

According to one embodiment of the invention, the polyethylene backbone comprises only one polymer. According to another embodiment, the polyethylene backbone comprises two or more different polymers selected from the group consisting of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE) and polyethylene wax.

According to a preferred embodiment, the polyethylene backbone consists of only one polymer and is preferably a polyethylene wax.

According to one embodiment of the invention, the polypropylene backbone comprises only one polymer. According to another embodiment, the polypropylene backbone comprises two or more different polymers selected from the group consisting of atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene and polypropylene waxes.

According to a preferred embodiment, the polypropylene backbone consists of only one polymer and is preferably a polypropylene wax.

The term "maleic anhydride" in the meaning of the present invention means a compound of the formula C₂H₂(CO)₂O and is an anhydride of maleic acid. The term "graft" in the meaning of the present invention refers to the following polymers: the polymer comprises a backbone, i.e. a polypropylene or polyethylene backbone, and a compound, i.e. maleic anhydride, randomly distributed and attached to the backbone.

According to one embodiment of the invention, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is selected from the group consisting of maleic anhydride grafted Low Density Polyethylene (LDPE), maleic anhydride grafted Linear Low Density Polyethylene (LLDPE), maleic anhydride grafted High Density Polyethylene (HDPE), maleic anhydride grafted atactic polypropylene, maleic anhydride grafted isotactic polypropylene, maleic anhydride grafted syndiotactic polypropylene, maleic anhydride grafted polyethylene wax, maleic anhydride grafted polypropylene wax and mixtures thereof, and preferably maleic anhydride grafted Linear Low Density Polyethylene (LLDPE) and maleic anhydride grafted polyethylene wax, and most preferably maleic anhydride grafted polyethylene wax.

In one embodiment of the invention, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has a melting temperature T_mBelow 250 c, more preferably below 200 c, for example below 170 c. For example, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has a melting temperature of 50 to 250 ℃, more preferably 75 to 200 ℃ and most preferably 100-170 ℃.

It will furthermore be appreciated that the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has a melt flow rate MFR (190 ℃) of from 0.1 to 3000g/10min, more preferably from 0.2 to 2500g/10 min. For example, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has a melt flow rate MFR (190 ℃) of 0.3 to 2000g/10min or 0.3 to 1600g/10 min. Additionally or alternatively, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has a melt flow rate MFR (230 ℃) of 0.1 to 3000g/10min, more preferably 0.2 to 2500g/10 min. For example, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has a melt flow rate MFR (230 ℃) of 0.3 to 2000g/10min or 0.3 to 1600g/10 min.

Additionally or alternatively, it is noted that the maleic anhydride-grafted polyethylene and/or the maleic anhydride-grafted polypropylene have a viscosity at +140 ℃ (± 2 ℃) of 100-.

Additionally or alternatively, it is noted that the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene has an acid number of from 10 to 200mgKOH/g, preferably from 30 to 80mgKOH/g and most preferably from 40 to 60 mgKOH/g. This acid number, also referred to as the neutralization or acid number or acidity, is the mass (in milligrams) of potassium hydroxide (KOH) required to neutralize one gram of chemical species, such as one gram of dry maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene. In other words, acid number is a measure of the number of carboxylic acid groups in a compound. In a typical procedure, a known amount of sample is dissolved in an organic solvent (preferably isopropanol) and titrated with a known concentration of potassium hydroxide (KOH) solution using phenolphthalein as a color indicator.

According to a preferred embodiment, the maleic anhydride-grafted polyethylene and/or the maleic anhydride-grafted polypropylene have a viscosity at +140 ℃ (± 2 ℃) of 100-. According to another preferred embodiment, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene is a maleic anhydride grafted polyethylene wax.

Hydrophobizing agent

The term "hydrophobizing agent" refers to an agent that hydrophobizes the surface of the at least one calcium carbonate-comprising filler material. The term "hydrophobization" is well known and describes the tendency of molecules or particles to be repelled by a body of water. In other words, hydrophobic molecules or particles tend to be non-polar and therefore more compatible with other neutral molecules and non-polar solvents such as non-polar polymer compositions because water molecules are polar and therefore the hydrophobe does not dissolve well therein. The hydrophobizing agent according to the invention is different from the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene.

Hydrophobizing agents are well known to those skilled in the art and those skilled in the art know how to select a suitable hydrophobizing agent depending on the filler material and the polymer resin in which the surface treated filler material is used.

The term "succinic anhydride", also known as dihydro-2, 5-furandione, anhydride of succinic acid or succinylated oxygen, has the formula C₄H₄O₃And is the anhydride of succinic acid. "succinic anhydride" according to the invention is a compound comprising succinic anhydride, such as substituted succinic anhydride, and preferably monosubstituted succinic anhydride.

"carboxylic acids" in the meaning of the present invention are organic compounds containing a carboxyl group (C (═ O) OH) and having the general formula R — COOH, where R refers to the rest of the molecule, e.g. an aliphatic chain.

"phosphoric monoester" in the meaning of the present invention refers to an orthophosphoric acid molecule monoesterified with one alcohol molecule selected from unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms in the alcohol substituents of C6 to C30, preferably C8 to C22, more preferably C8 to C20 and most preferably C8 to C18.

"phosphodiester" in the meaning of the present invention refers to an orthophosphoric acid molecule di-esterified with two alcohol molecules selected from the same or different unsaturated or saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms in the alcohol substituents of C6 to C30, preferably C8 to C22, more preferably C8 to C20 and most preferably C8 to C18.

According to a preferred embodiment of the present invention, the at least one hydrophobizing agent is selected from the group consisting of succinic anhydride, carboxylic acids, reaction products thereof and mixtures thereof.

According to another preferred embodiment of the invention, the at least one hydrophobizing agent is at least one of:

monosubstituted succinic anhydrides and/or reaction products thereof, and

aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and/or reaction products thereof.

"at least one" in the meaning of the present invention means that the hydrophobicizing agent comprises one or more compounds selected from the group consisting of monosubstituted succinic anhydrides and/or reaction products thereof and aliphatic linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and/or reaction products thereof.

According to one embodiment of the invention, the hydrophobizing agent is a monosubstituted succinic anhydride and/or a reaction product thereof. According to another embodiment of the invention, the hydrophobizing agent is an aliphatic linear and/or branched carboxylic acid having 8 to 24 carbon atoms and/or reaction products thereof. According to another embodiment, the hydrophobizing agent is a mixture of monosubstituted succinic anhydrides and/or reaction products thereof with aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and/or reaction products thereof.

Monosubstituted succinic anhydride

The mono-substituted succinic anhydride may comprise one or more types of mono-substituted succinic anhydride, and thus, the mono-substituted succinic anhydride may be one or more types of mono-substituted succinic anhydride. Alternatively still, the mono-substituted succinic anhydride may be a mixture of two or more types of mono-substituted succinic anhydride. For example, the monosubstituted succinic anhydride may be a mixture of two or three types of monosubstituted succinic anhydride (e.g., two types of monosubstituted succinic anhydride).

According to a preferred embodiment of the invention, the monosubstituted succinic anhydride is one type of monosubstituted succinic anhydride.

The term "monosubstituted" succinic anhydride in the meaning of the present invention refers to succinic anhydride substituted by one substituent.

The term "reaction product" of a monosubstituted succinic anhydride in the meaning of the present invention refers to a product obtained by contacting a calcium carbonate-comprising filler material with one or more monosubstituted succinic anhydrides. The reaction product is formed between the monosubstituted succinic acid formed from the applied monosubstituted succinic anhydride and the reactive molecule located at the surface of the calcium carbonate-comprising filler material.

It is understood that the mono-substituted succinic anhydride represents a surface treatment agent and consists of succinic anhydride mono-substituted with a group selected from: any linear, branched, aliphatic, and cyclic group having 2 to 30 carbon atoms in the substituent.

In one embodiment of the present invention, the mono-substituted succinic anhydride and/or reaction products thereof consists of succinic anhydride mono-substituted with a group selected from: linear, branched, aliphatic, and cyclic groups having 3 to 25 carbon atoms in the substituents. For example, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with a group selected from: linear, branched, aliphatic, and cyclic groups having 4 to 20 carbon atoms in the substituents.

In one embodiment of the invention, the monosubstituted succinic anhydride and/or reaction product thereof consists of succinic anhydride monosubstituted with a group being a linear and aliphatic group having 2-30 carbon atoms in the substituent, preferably 3-25 and most preferably 4-20 carbon atoms in the substituent. Additionally or alternatively, the monosubstituted succinic anhydride and/or reaction products thereof consist of succinic anhydride monosubstituted with a group being a branched and aliphatic group having 2-30 carbon atoms in the substituent, preferably 3-25 and most preferably 4-20 carbon atoms in the substituent.

Preferably, therefore, the at least one monosubstituted succinic anhydride and/or reaction product thereof consists of succinic anhydride monosubstituted with a group being a linear or branched alkyl group having 2-30 carbon atoms in the substituent, preferably 3-25 and most preferably 4-20 carbon atoms in the substituent.

For example, the monosubstituted succinic anhydride and/or reaction products thereof consist of succinic anhydride monosubstituted with a group being a linear alkyl group having 2-30 carbon atoms in the substituent, preferably 3-25 and most preferably 4-20 carbon atoms in the substituent. Additionally or alternatively, the mono-substituted succinic anhydride and/or reaction products thereof consists of succinic anhydride mono-substituted with a group which is a branched alkyl group having 2 to 30 carbon atoms in the substituent, preferably 3 to 25 and most preferably 4 to 20 carbon atoms in the substituent.

"alkyl" in the meaning of the present invention means a linear or branched, saturated organic compound consisting of carbon and hydrogen. In other words, an "alkyl monosubstituted succinic anhydride" consists of a linear or branched saturated hydrocarbon chain containing pendant succinic anhydride groups.

In one embodiment of the present invention, the mono-substituted succinic anhydride and/or reaction products thereof is at least one linear or branched alkyl mono-substituted succinic anhydride. For example, the at least one alkyl monosubstituted succinic anhydride is selected from the group consisting of 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.

It is further understood that, for example, the term "hexadecyl succinic anhydride" includes linear as well as branched hexadecyl succinic anhydrides. One specific example of linear hexadecyl succinic anhydride is n-hexadecyl succinic anhydride. Specific examples of branched hexadecyl succinic anhydrides are 14-methylpentadecyl succinic anhydride, 13-methylpentadecyl succinic anhydride, 12-methylpentadecyl succinic anhydride, 11-methylpentadecyl succinic anhydride, 10-methylpentadecyl succinic anhydride, 9-methylpentadecyl succinic anhydride, 8-methylpentadecyl succinic anhydride, 7-methylpentadecyl succinic anhydride, 6-methylpentadecyl succinic anhydride, 5-methylpentadecyl succinic anhydride, 4-methylpentadecyl succinic anhydride, 3-methylpentadecyl succinic anhydride, 2-methylpentadecyl succinic anhydride, 1-methylpentadecyl succinic anhydride, 13-ethyltetradecyl succinic anhydride, 12-ethyltetradecyl succinic anhydride, 11-ethyltetradecyl succinic anhydride, 10-ethyltetradecylsuccinic anhydride, 9-ethyltetradecylsuccinic anhydride, 8-ethyltetradecylsuccinic anhydride, 7-ethyltetradecylsuccinic anhydride, 6-ethyltetradecylsuccinic anhydride, 5-ethyltetradecylsuccinic anhydride, 4-ethyltetradecylsuccinic anhydride, 3-ethyltetradecylsuccinic anhydride, 2-ethyltetradecylsuccinic anhydride, 1-ethyltetradecylsuccinic anhydride, 2-butyldodecylsuccinic anhydride, 1-hexyldecylsuccinic anhydride, 1-hexyl-2-decylsuccinic anhydride, 2-hexyldecylsuccinic anhydride, 6, 12-dimethyltetradecylsuccinic anhydride, 2, 2-diethyldodecylsuccinic anhydride, 4,8, 12-trimethyltridecylsuccinic anhydride, 2,2,4,6, 8-pentamethylundecylsuccinic anhydride, 2-ethyl-4-methyl-2- (2-methylpentyl) -heptylsuccinic anhydride and/or 2-ethyl-4, 6-dimethyl-2-propylnonylsuccinic anhydride.

It is further understood that, for example, the term "octadecyl succinic anhydride" includes linear as well as branched octadecyl succinic anhydrides. One specific example of linear octadecyl succinic anhydride is n-octadecyl succinic anhydride. Specific examples of the branched hexadecyl succinic anhydride are 16-methylheptadecyl succinic anhydride, 15-methylheptadecyl succinic anhydride, 14-methylheptadecyl succinic anhydride, 13-methylheptadecyl succinic anhydride, 12-methylheptadecyl succinic anhydride, 11-methylheptadecyl succinic anhydride, 10-methylheptadecyl succinic anhydride, 9-methylheptadecyl succinic anhydride, 8-methylheptadecyl succinic anhydride, 7-methylheptadecyl succinic anhydride, 6-methylheptadecyl succinic anhydride, 5-methylheptadecyl succinic anhydride, 4-methylheptadecyl succinic anhydride, 3-methylheptadecyl succinic anhydride, 2-methylheptadecyl succinic anhydride, 1-methylheptadecyl succinic anhydride, 14-ethylhexadecyl succinic anhydride, 13-ethylhexadecylsuccinic anhydride, 12-ethylhexadecylsuccinic anhydride, 11-ethylhexadecylsuccinic anhydride, 10-ethylhexadecylsuccinic anhydride, 9-ethylhexadecylsuccinic anhydride, 8-ethylhexadecylsuccinic anhydride, 7-ethylhexadecylsuccinic anhydride, 6-ethylhexadecylsuccinic anhydride, 5-ethylhexadecylsuccinic anhydride, 4-ethylhexadecylsuccinic anhydride, 3-ethylhexadecylsuccinic anhydride, 2-ethylhexadecylsuccinic anhydride, 1-ethylhexadecylsuccinic anhydride, 2-hexyldodecylsuccinic anhydride, 2-heptylundecylsuccinic anhydride, isooctadecyl succinic anhydride and/or 1-octyl-2-decylsuccinic anhydride.

In one embodiment of the present invention, the alkyl monosubstituted succinic anhydride and reaction products thereof are selected from the group consisting of hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, and mixtures and reaction products thereof.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is one type of alkyl monosubstituted succinic anhydride. For example, the one alkyl monosubstituted succinic anhydride is butyl succinic anhydride. Alternatively, the one alkyl monosubstituted succinic anhydride is hexyl succinic anhydride. Alternatively, the one alkyl monosubstituted succinic anhydride is heptyl succinic anhydride or octyl succinic anhydride. Alternatively, the one alkyl monosubstituted succinic anhydride is hexadecyl succinic anhydride. For example, the one alkyl monosubstituted succinic anhydride is a linear hexadecyl succinic anhydride such as n-hexadecyl succinic anhydride or a branched hexadecyl succinic anhydride such as 1-hexyl-2-decyl succinic anhydride. Alternatively, the one alkyl monosubstituted succinic anhydride is octadecyl succinic anhydride. For example, the one alkyl monosubstituted succinic anhydride is a linear octadecyl succinic anhydride such as n-octadecyl succinic anhydride or a branched octadecyl succinic anhydride such as iso-octadecyl succinic anhydride or 1-octyl-2-decyl succinic anhydride.

In one embodiment of the invention, the one alkyl monosubstituted succinic anhydride is butyl succinic anhydride, such as n-butyl succinic anhydride.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride and reaction products thereof is a mixture of two or more types of alkyl monosubstituted succinic anhydrides and reaction products thereof. For example, the at least one monosubstituted succinic anhydride is a mixture of two or three types of alkyl monosubstituted succinic anhydrides.

In one embodiment of the present invention, the at least one monosubstituted succinic anhydride consists of succinic anhydride monosubstituted with a group being a linear or branched alkenyl group having 2-30 carbon atoms in the substituent, preferably 3-25 and most preferably 4-20 carbon atoms in the substituent.

The term "alkenyl" in the meaning of the present invention refers to a linear or branched unsaturated organic compound consisting of carbon and hydrogen. The organic compound also contains at least one double bond, preferably one double bond, in the substituent. In other words, an "alkenyl monosubstituted succinic anhydride" consists of a linear or branched unsaturated hydrocarbon chain containing pendant succinic anhydride groups. It is to be understood that the term "alkenyl" in the meaning of the present invention includes both cis and trans isomers.

In one embodiment of the present invention, the mono-substituted succinic anhydride and reaction products thereof are at least one linear or branched alkenyl mono-substituted succinic anhydride and reaction products thereof. For example, the at least one alkenyl monosubstituted succinic anhydride is selected from the group consisting of 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.

It is therefore understood, for example, that the term "hexadecenyl succinic anhydride" and reaction products thereof includes both linear and branched hexadecenyl succinic anhydrides and reaction products thereof. One specific example of a linear hexadecenyl succinic anhydride is n-hexadecenyl succinic anhydride, such as 14-hexadecenyl succinic anhydride, 13-hexadecenyl succinic anhydride, 12-hexadecenyl succinic anhydride, 11-hexadecenyl succinic anhydride, 10-hexadecenyl succinic anhydride, 9-hexadecenyl succinic anhydride, 8-hexadecenyl succinic anhydride, 7-hexadecenyl succinic anhydride, 6-hexadecenyl succinic anhydride, 5-hexadecenyl succinic anhydride, 4-hexadecenyl succinic anhydride, 3-hexadecenyl succinic anhydride and/or 2-hexadecenyl succinic anhydride. Specific examples of branched hexadecenyl succinic anhydrides are 14-methyl-9-pentadecenyl succinic anhydride, 14-methyl-2-pentadecenyl succinic anhydride, 1-hexyl-2-decenyl succinic anhydride and/or isocetyl succinic anhydride.

It is further understood that, for example, the term "octadecenyl succinic anhydride" and reaction products thereof includes both linear and branched octadecenyl succinic anhydrides and reaction products thereof. A specific example of a linear octadecenyl succinic anhydride is n-octadecenyl succinic anhydride, such as 16-octadecenyl succinic anhydride, 15-octadecenyl succinic anhydride, 14-octadecenyl succinic anhydride, 13-octadecenyl succinic anhydride, 12-octadecenyl succinic anhydride, 11-octadecenyl succinic anhydride, 10-octadecenyl succinic anhydride, 9-octadecenyl succinic anhydride, 8-octadecenyl succinic anhydride, 7-octadecenyl succinic anhydride, 6-octadecenyl succinic anhydride, 5-octadecenyl succinic anhydride, 4-octadecenyl succinic anhydride, 3-octadecenyl succinic anhydride and/or 2-octadecenyl succinic anhydride. Specific examples of branched octadecenyl succinic anhydride are 16-methyl-9-heptadecenyl succinic anhydride, 16-methyl-7-heptadecenyl succinic anhydride, 1-octyl-2-decenyl succinic anhydride and/or isosteadenyl succinic anhydride.

In one embodiment of the present invention, the alkenyl monosubstituted succinic anhydride and reaction products thereof are selected from hexenyl succinic anhydride, octenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and mixtures and reaction products thereof.

In one embodiment of the present invention, the mono-substituted succinic anhydride and reaction product thereof is an alkenyl mono-substituted succinic anhydride and reaction product thereof. For example, the one alkenyl monosubstituted succinic anhydride is hexenyl succinic anhydride. Alternatively, the one alkenyl monosubstituted succinic anhydride is octenyl succinic anhydride. Alternatively, the one alkenyl monosubstituted succinic anhydride is hexadecenyl succinic anhydride or octadecenyl succinic anhydride. For example, the one alkenyl monosubstituted succinic anhydride is a linear hexadecenyl succinic anhydride such as n-hexadecyl succinic anhydride or a branched hexadecenyl succinic anhydride such as 1-hexyl-2-decenyl succinic anhydride. Alternatively, the one alkenyl monosubstituted succinic anhydride is octadecenyl succinic anhydride. For example, the one alkenyl monosubstituted succinic anhydride is a linear octadecenyl succinic anhydride such as n-octadecenyl succinic anhydride or a branched octadecenyl succinic anhydride such as iso-octadecenyl succinic anhydride, or 1-octyl-2-decenyl succinic anhydride.

If the monosubstituted succinic anhydride and its reaction product is alkenyl monosubstituted succinic anhydride, it is understood that the one alkenyl monosubstituted succinic anhydride is present in an amount of ≥ 92% by weight and preferably ≥ 95% by weight, based on the total weight of the monosubstituted succinic anhydride.

In one embodiment of the invention, the mono-substituted succinic anhydride is a mixture of two or more types of alkenyl mono-substituted succinic anhydrides. For example, the at least one monosubstituted succinic anhydride is a mixture of two or three types of alkenyl monosubstituted succinic anhydrides.

If the monosubstituted succinic anhydride and its reaction product are a mixture of two or more types of alkenyl monosubstituted succinic anhydrides, one alkenyl monosubstituted succinic anhydride is a linear or branched octadecenyl succinic anhydride and its reaction product, and each other alkenyl monosubstituted succinic anhydride is selected from the group consisting of vinyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl succinic anhydride, and mixtures and reaction products thereof. For example, the monosubstituted succinic anhydride and reaction products thereof are a mixture of two or more types of alkenyl monosubstituted succinic anhydrides, wherein one alkenyl monosubstituted succinic anhydride is a linear octadecenyl succinic anhydride and each other alkenyl monosubstituted succinic anhydride is selected from the group consisting of vinyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl succinic anhydride, and mixtures and reaction products thereof. Alternatively, the mono-substituted succinic anhydride and its reaction product is a mixture of two or more types of alkenyl mono-substituted succinic anhydrides, wherein one alkenyl mono-substituted succinic anhydride is a branched octadecenyl succinic anhydride and each other alkenyl mono-substituted succinic anhydride is selected from the group consisting of vinyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, heptenyl succinic anhydride, nonenyl succinic anhydride, hexadecenyl succinic anhydride and mixtures thereof.

For example, the monosubstituted succinic anhydrides and reaction products thereof are mixtures of two or more types of alkenyl monosubstituted succinic anhydrides and reaction products thereof, including one or more hexadecenyl succinic anhydrides, such as linear or branched hexadecenyl succinic anhydride, and one or more octadecenyl succinic anhydrides, such as linear or branched octadecenyl succinic anhydride.

In one embodiment of the present invention, the mono-substituted succinic anhydride and reaction products thereof are a mixture of two or more types of alkenyl mono-substituted succinic anhydrides and reaction products thereof, including linear hexadecenyl succinic anhydride and linear octadecenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride and reaction products thereof are a mixture of two or more types of alkenyl mono-substituted succinic anhydrides and reaction products thereof, including branched hexadecenyl succinic anhydride and branched octadecenyl succinic anhydride. For example, the one or more hexadecenyl succinic anhydride is a linear hexadecenyl succinic anhydride such as n-hexadecenyl succinic anhydride and/or a branched hexadecenyl succinic anhydride such as 1-hexyl-2-decenyl succinic anhydride. Additionally or alternatively, the one or more octadecenyl succinic anhydrides are linear octadecenyl succinic anhydrides such as n-octadecenyl succinic anhydride and/or branched octadecenyl succinic anhydrides such as iso-octadecenyl succinic anhydride and/or 1-octyl-2-decenyl succinic anhydride.

If the mono-substituted succinic anhydride and its reaction products are a mixture of two or more types of alkenyl mono-substituted succinic anhydrides and their reaction products, it is to be understood that one alkenyl mono-substituted succinic anhydride is present in an amount of 10 to 90% by weight and preferably 20 to 85% by weight, based on the total weight of the mono-substituted succinic anhydride and its reaction products.

For example, if the monosubstituted succinic anhydride and its reaction product are a mixture of two or more types of alkenyl monosubstituted succinic anhydrides and their reaction products, including one or more hexadecenyl succinic anhydrides, such as linear or branched hexadecenyl succinic anhydride, and one or more octadecenyl succinic anhydrides, such as linear or branched hexadecenyl succinic anhydride, it is understood that octadecenyl succinic anhydride and its reaction product are present in an amount of 10 to 90% by weight and preferably 20 to 85% by weight, based on the total weight of the monosubstituted succinic anhydride and its reaction product.

It is also to be understood that the monosubstituted succinic anhydrides and reaction products thereof may be mixtures of alkyl monosubstituted succinic anhydrides and reaction products thereof with alkenyl monosubstituted succinic anhydrides and reaction products thereof.

If the mono-substituted succinic anhydride and its reaction product are a mixture of alkyl mono-substituted succinic anhydride and its reaction product and alkenyl mono-substituted succinic anhydride and its reaction product, it is to be understood that the alkyl substituent of the alkyl mono-substituted succinic anhydride and the alkenyl substituent of the alkenyl mono-substituted succinic anhydride are preferably the same. For example, the mono-substituted succinic anhydride is a mixture of ethylsuccinic anhydride and vinylsuccinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of propyl succinic anhydride and propenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of butylsuccinic anhydride and butylenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of triisobutyl succinic anhydride and triisobutenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of pentylsuccinic anhydride and pentenylsuccinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of hexyl succinic anhydride and hexenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of heptyl succinic anhydride and heptenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of octyl succinic anhydride and octenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of nonyl succinic anhydride and nonenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of decyl succinic anhydride and decenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of dodecyl succinic anhydride and dodecenyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of hexadecyl succinic anhydride and hexadecyl succinic anhydride. For example, the mono-substituted succinic anhydride is a mixture of linear hexadecyl succinic anhydride and linear hexadecyl succinic anhydride or a mixture of branched hexadecyl succinic anhydride and branched hexadecyl succinic anhydride. Alternatively, the mono-substituted succinic anhydride is a mixture of octadecylsuccinic anhydride and octadecylsuccinic anhydride. For example, the mono-substituted succinic anhydride is a mixture of linear octadecylsuccinic anhydride and linear octadecylsuccinic anhydride or a mixture of branched octadecylsuccinic anhydride and branched octadecylsuccinic anhydride.

If the mono-substituted succinic anhydride and the reaction product thereof is a mixture of alkyl mono-substituted succinic anhydride and alkenyl mono-substituted succinic anhydride and the reaction product thereof, the weight ratio between the alkyl mono-substituted succinic anhydride and the alkenyl mono-substituted succinic anhydride is between 90:10 and 10:90 (% weight/% weight). For example, the weight ratio between the alkyl monosubstituted succinic anhydride and the alkenyl monosubstituted succinic anhydride is between 70:30 and 30:70 (% weight/% weight) or between 60:40 and 40: 60.

Optionally, the monosubstituted succinic anhydride and reaction products thereof are present in combination with monosubstituted succinic acid and reaction products thereof. The monosubstituted succinic acid may be one type of monosubstituted succinic acid or a mixture of two or more types of monosubstituted succinic acid.

It is understood that the mono-substituted succinic acid represents a surface treatment agent and consists of succinic acid mono-substituted with a group selected from: any linear, branched, aliphatic and cyclic group having from 2 to 30, preferably from 3 to 25 and most preferably from 4 to 20 carbon atoms in the substituent.

If the monosubstituted succinic anhydride and reaction products thereof are present in combination with monosubstituted succinic acid and reaction products thereof, it is understood that the monosubstituted succinic anhydride and the monosubstituted succinic acid may comprise identical or different substituents.

In one embodiment of the present invention the succinic acid molecules of the monosubstituted succinic acid and reaction products thereof and the succinic anhydride molecules of the monosubstituted succinic anhydride and reaction products thereof are monosubstituted with the same group selected from any linear, branched, aliphatic and cyclic group having from 2 to 30, preferably from 3 to 25 and most preferably from 4 to 20 carbon atoms in the substituent.

If the mono-substituted succinic anhydride and reaction products thereof are present in combination with mono-substituted succinic acid, the mono-substituted succinic acid and reaction products thereof are present in an amount of 10 mol% or less based on the sum of the moles of the mono-substituted succinic anhydride and the at least one mono-substituted succinic acid and reaction products thereof. For example, the mono-substituted succinic acid and its reaction products are present in an amount of ≦ 5 mol%, preferably ≦ 2.5 mol% and most preferably ≦ 1 mol%, based on the sum of the moles of the mono-substituted succinic anhydride and the mono-substituted succinic acid and its reaction products.

Aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms

The aliphatic linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and reaction products thereof may comprise one or more aliphatic linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and reaction products thereof. According to one embodiment of the invention, the aliphatic linear and/or branched carboxylic acid having 8 to 24 carbon atoms and reaction products thereof comprise only one aliphatic linear and/or branched carboxylic acid having 8 to 24 carbon atoms and reaction products thereof. According to another embodiment of the invention, the aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof comprise two or more, for example three or four, different aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof.

The term "aliphatic linear and/or branched carboxylic acid" in the meaning of the present invention refers to compounds containing a carboxyl group (C (═ O) OH) and having the general formula R — COOH, wherein R refers to a linear and/or branched hydrocarbon chain.

The term "reaction product" of an aliphatic linear and/or branched carboxylic acid in the meaning of the present invention refers to the product obtained by contacting a calcium carbonate-comprising filler material with a mixture of aliphatic linear and/or branched carboxylic acids. The reaction products are formed between a mixture of aliphatic linear and/or branched carboxylic acids and reactive molecules located at the surface of the calcium carbonate containing filler material.

The aliphatic linear and/or branched carboxylic acids and/or reaction products thereof of the present invention have from 8 to 24 carbon atoms, preferably from 8 to 22, preferably from 10 to 22, more preferably from 12 to 20 and most preferably from 14 to 20 carbon atoms.

Such aliphatic linear and/or branched carboxylic acids having from 8 to 24 carbon atoms are known to the person skilled in the art and are commercially available. For example, the linear and/or branched carboxylic acid having 8 to 24 carbon atoms is selected from the group consisting of octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, stearic acid, and mixtures thereof.

According to one embodiment of the invention, the linear and/or branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof comprise only one linear and/or branched carboxylic acid having 8 to 24 carbon atoms and reaction products thereof. According to one embodiment of the invention, the linear and/or branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof are branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof. According to another embodiment of the present invention, the linear and/or branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof are linear carboxylic acids having 8 to 24 carbon atoms and reaction products thereof, preferably selected from the group consisting of caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid and mixtures thereof, and most preferably selected from the group consisting of stearic acid and palmitic acid.

According to another embodiment of the invention, the linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and reaction products thereof comprise two or more, for example three or four or five, linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and reaction products thereof. According to a preferred embodiment of the present invention, the linear and/or branched carboxylic acid having 8 to 24 carbon atoms and the reaction product thereof comprises two linear and/or branched carboxylic acids having 8 to 24 carbon atoms and the reaction product thereof. For example, one carboxylic acid may be a linear carboxylic acid, while another carboxylic acid may be a branched carboxylic acid. Alternatively, both of the carboxylic acids may be linear carboxylic acids or both may be branched carboxylic acids.

According to a preferred embodiment of the present invention, the linear and/or branched carboxylic acids having 8 to 24 carbon atoms and reaction products thereof comprise two linear carboxylic acids having 8 to 24 carbon atoms and reaction products thereof, preferably selected from the group consisting of caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid and mixtures thereof, and most preferably selected from the group consisting of palmitic acid and stearic acid.

If the linear and/or branched carboxylic acid having from 8 to 24 carbon atoms and reaction products thereof is a mixture of two different linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and reaction products thereof, the weight ratio of the first linear and/or branched carboxylic acid having from 8 to 24 carbon atoms and reaction products thereof to the second linear and/or branched carboxylic acid having from 8 to 24 carbon atoms and reaction products thereof is from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 4:1 to 1:4 and most preferably 1: 1.

According to a preferred embodiment of the invention, the linear and/or branched carboxylic acids having 8 to 24 carbon atoms and the reaction products thereof are 1:1 mixtures of stearic acid and palmitic acid.

The surface-treated filler material product comprises a treatment layer comprising i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent in an amount of from 0.2 to 7% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material. Preferably, the surface-treated filler material product comprises a treatment layer comprising i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent in an amount of from 0.4 to 5% by weight based on the total dry weight of the at least one calcium carbonate containing filler material, more preferably from 0.6 to 4% by weight and most preferably from 0.8 to 3% by weight based on the total dry weight of the at least one calcium carbonate containing filler material.

According to another embodiment of the invention, the treatment layer may be further characterized by: the total weight of the treatment layer on the surface of the surface-treated filler material is 0.2-10mg/m²More preferably 0.4 to 8mg/m²And most preferably 2 to 8mg/m²The at least one calcium carbonate-containing filler material.

According to another embodiment of the invention, the treatment layer may be further characterized by: the total weight of the treatment layer on the surface of the surface-treated filler material is 0.1-4% weight/m²More preferably 0.2 to 2% by weight/m²And most preferably 0.3-0.5% weight/m²The at least one calcium carbonate-containing filler material.

As already stated, the surface-treated filler material product comprises a treatment layer comprising i) a maleic anhydride grafted polyethylene and/or a maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent on the surface of the at least one calcium carbonate containing filler material. According to one embodiment of the invention, the treatment layer comprises the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5 and most preferably from 4:1 to 1:4, for example 1: 1.

According to another embodiment of the invention, the treatment layer may be further characterized by: the total weight of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) on the surface of the surface treated filler material is from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight and most preferably from 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material.

According to another embodiment of the invention, the treatment layer may be further characterized by: the total weight of the at least one hydrophobizing agent of step ii) on the surface of the surface-treated filler material is from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate-containing filler material.

According to one embodiment of the invention, the treatment layer may be further characterized by: the total weight of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) on the surface of the surface treated filler material is from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight and most preferably from 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material, and the total weight of the at least one hydrophobizing agent of step ii) on the surface of the surface treated filler material is from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material.

According to one embodiment, further surface treatment agents are present on the surface of the at least one calcium carbonate-comprising filler material in addition to the maleic anhydride grafted polyethylene, the maleic anhydride grafted polypropylene and the at least one hydrophobizing agent. The other surface treatment agents may be present in an amount of less than 50% by weight, preferably less than 40% by weight, more preferably less than 20% by weight and most preferably less than 10% by weight, based on the total weight of the treatment layer on the surface of the at least one calcium carbonate-comprising filler material.

According to a preferred embodiment, the surface treatment layer consists exclusively of i) maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene and ii) at least one hydrophobicizing agent.

According to a preferred embodiment of the invention, the surface treatment layer comprises i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent, wherein the at least one hydrophobizing agent is at least one of

Monosubstituted succinic anhydrides and/or reaction products thereof, and

aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and/or reaction products thereof.

For example, the surface treatment layer comprises i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent, wherein the at least one hydrophobizing agent is a monosubstituted succinic anhydride and/or a reaction product thereof. According to one embodiment of the invention, the treatment layer comprises the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) in an amount of from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight and most preferably from 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material, and the monosubstituted succinic anhydride of step ii) and/or reaction products thereof in an amount of from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material, on the surface of the surface treated filler material.

Additionally or alternatively, the treatment layer comprises the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the mono-substituted succinic anhydride of step ii) and/or the reaction product thereof in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5 and most preferably from 4:1 to 1:4, e.g. 1: 1.

Additionally or alternatively, the molar ratio of the at least one monosubstituted succinic anhydride to its salt reaction products in the treatment layer on the surface of the at least one calcium carbonate-comprising filler material is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90: 10. The expression "molar ratio of the at least one monosubstituted succinic anhydride to its salt reaction product" in the meaning of the present invention refers to the sum of the molecular weights of the at least one monosubstituted succinic anhydride to the sum of the molecular weights of the monosubstituted succinic anhydride molecules in its salt reaction product.

Further optionally, the surface treatment layer comprises i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent, wherein the at least one hydrophobizing agent is an aliphatic linear and/or branched carboxylic acid having 8 to 24 carbon atoms and/or a reaction product thereof. According to one embodiment of the invention, the treatment layer comprises on the surface of the surface-treated filler material the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) in an amount of from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight and most preferably from 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material, and the aliphatic linear and/or branched carboxylic acid having from 8 to 24 carbon atoms and/or reaction products thereof of step ii) in an amount of from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material.

Additionally or alternatively, the treatment layer comprises the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the aliphatic linear and/or branched carboxylic acid having 8 to 24 carbon atoms of step ii) and/or the reaction product thereof in a weight ratio of 10:1 to 1:10, preferably 5:1 to 1:5 and most preferably 4:1 to 1:4, e.g. 1: 1.

Additionally or alternatively, the molar ratio of the at least one aliphatic linear and/or branched carboxylic acid to its salt reaction products in the treatment layer on the surface of the at least one calcium carbonate-comprising filler material is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90: 10. The expression "molar ratio of the at least one aliphatic linear and/or branched carboxylic acid to its salt reaction product" in the meaning of the present invention means the sum of the molecular weights of the at least one aliphatic linear and/or branched carboxylic acid to the sum of the molecular weights of the aliphatic linear and/or branched carboxylic acid molecules in its salt reaction product.

According to another embodiment of the invention, the surface treatment layer comprises i) maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and ii) at least one hydrophobizing agent, wherein the at least one hydrophobizing agent is a mixture of monosubstituted succinic anhydride and/or reaction products thereof and aliphatic linear and/or branched carboxylic acids having 8 to 24 carbon atoms and/or reaction products thereof.

For example, the treatment layer comprises on the surface of the surface-treated filler material a maleic anhydride grafted polyethylene and/or a maleic anhydride grafted polypropylene of step i) in an amount of from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight and most preferably from 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material, and a mixture of the monosubstituted succinic anhydride and/or reaction products thereof of step ii) and aliphatic linear and/or branched carboxylic acids having from 8 to 24 carbon atoms and/or reaction products thereof in an amount of from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material.

Additionally or alternatively, the treatment layer comprises a mixture of the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene of step i) and the monosubstituted succinic anhydride and/or reaction products thereof of step ii) and the aliphatic linear and/or branched carboxylic acid having 8-24 carbon atoms and/or reaction products thereof in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5 and most preferably from 4:1 to 1:4, e.g. 1: 1.

The surface treated filler material product of the present invention may be in the form of a slurry or a powder, preferably in the form of a powder.

The present inventors have surprisingly found that the surface treated filler material products described above have good powder flow and low moisture pick-up sensitivity.

In particular, when powder flow is measured on a FT4 powder rheometer (ASTM D7891-15), the surface treated filler material product of the invention has a Basic Flow Energy (BFE) and a conditioned (conditioned) bulk density (CBD) comparable to the Basic Flow Energy (BFE) and Conditioned Bulk Density (CBD) of a surface treated filler material surface treated with only the same hydrophobizing agent but without maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene.

Additionally or alternatively, the surface treated filler material product of the present invention has a moisture pickup sensitivity preferably below 1.0mg/g and which is comparable to the moisture pickup sensitivity of a surface treated filler material surface treated with only the same hydrophobizing agent but without maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene.

Method for preparing surface treated filler material

Furthermore, a method for preparing a surface treated filler material product is provided, the method comprising at least the steps of:

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

b) provide for

i. Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and

at least one hydrophobizing agent, and

According to step a), at least one calcium carbonate-comprising filler material is provided. The calcium carbonate-containing filler material has been described above.

According to step b), maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobicizing agent are provided. The maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and the at least one hydrophobizing agent have been described above.

Step c) characterization of the formation of a treatment layer on the surface of the at least one calcium carbonate-comprising filler material

According to step c), a treatment layer is formed on the surface of the at least one calcium carbonate-comprising filler material by contacting the surface of the at least one calcium carbonate-comprising filler material of step a) with 0.2 to 7% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material, of the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in any order in one or more steps under mixing, wherein the treatment layer comprises the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least hydrophobizing agent of step ii).

Contacting the at least one calcium carbonate-comprising filler material with the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) under mixing conditions. Those skilled in the art will adapt these mixing conditions (e.g., the configuration of the mixing tray and the mixing speed) according to their process equipment.

According to one embodiment of the invention, the contacting step c) is carried out by adding the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) simultaneously or sequentially, preferably simultaneously, with the proviso that if the compounds are added sequentially, the addition of the first compound does not lead to complete coverage of the surface of the at least one calcium carbonate containing filler material.

In a preferred embodiment of the present invention, the process of the present invention may be a continuous process. In this case, the at least one calcium carbonate-comprising filler material may be contacted with the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) at a constant flow rate such that a constant concentration of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) is provided during step c).

Further optionally, the at least one calcium carbonate-comprising filler material is contacted in one step with the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii), wherein said maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) are preferably added in one portion.

In another embodiment of the present invention, the inventive process may be a batch process, i.e. contacting the at least one calcium carbonate-comprising filler material with the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in more than one step, wherein said maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) are preferably added in approximately equal parts. Alternatively, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) may also be added in unequal parts (i.e. in larger and smaller parts).

According to one embodiment of the invention, the contacting in step c) is carried out in a batch or in a connection process for a period of time of 0.1 to 1000 seconds. For example, the contacting in step c) is a continuous process and comprises one or more contacting steps and the total contacting time is from 0.1 to 20 seconds, preferably from 0.5 to 15 seconds and most preferably from 1 to 10 seconds.

It is to be understood that the contacting in step c) can be performed in any order. For example, the contacting in step c) is performed by simultaneously adding the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) to the at least one calcium carbonate containing filler material. In this embodiment, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) are preferably added as a blend to the at least one calcium carbonate containing filler material.

Further optionally, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is added before or after the at least one hydrophobizing agent of step ii). According to a preferred embodiment of the present invention, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is added before the at least one hydrophobizing agent of step ii). When the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) are added sequentially, the addition of the first compound does not result in complete coverage of the surface of the at least one calcium carbonate containing filler material.

For example, if the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is added after the at least one hydrophobizing agent of step ii), the addition of the at least one hydrophobizing agent of step ii) does not result in complete coverage of the surface of the at least one calcium carbonate containing filler material. For example, only 10-90%, preferably 20-80% and most preferably 30-70% of the surface of the calcium carbonate-comprising filler material is coated with the at least one hydrophobizing agent of step ii). The theoretical value of the coated surface can be calculated based on the amount of the at least one hydrophobizing agent and the specific surface area (BET) value of the calcium carbonate-comprising filler material. In a second step, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) is added to cover the remaining surface not covered by the at least one hydrophobizing agent of step ii). The inventors have found that an additional treatment of the calcium carbonate-comprising material with a second compound (e.g. maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) will be less efficient if the addition of the first compound (e.g. the at least one hydrophobizing agent of step ii) already results in a complete surface coverage of the calcium carbonate-comprising filler material.

It is to be understood that the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) should exhibit a workable viscosity, i.e. the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) should be in a molten state or a liquid state during contacting.

It is therefore necessary to adjust the temperature before and/or during the contacting step c) so that the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) are in a molten or liquid state.

For example, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) are in powder form and are heated before or during the contacting step c) so that they are in a molten or liquid state.

Generally, the contacting step c) is carried out at a treatment temperature of 20 to 250 ℃, preferably 60 to 180 ℃ and most preferably 80 to 150 ℃.

Preferably, if the at least one hydrophobizing agent is provided in liquid form, i.e. at Standard Ambient Temperature and Pressure (SATP), which means a temperature of 298.15K (25 ℃) and an absolute pressure of exactly 100000Pa (1 bar, 14.5psi, 0.98692atm), it is to be understood that the contacting step c) can be carried out at room temperature or at a temperature above room temperature, i.e. at 20 to 250 ℃, preferably 20 to 180 ℃ and most preferably 20 to 150 ℃.

If the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) is provided in the molten state, it is understood that the temperature before and/or during the contacting step c) is adjusted such that the temperature is at least 2 ℃ higher than the melting point of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii). For example, the temperature before the contacting step c) is adjusted such that the temperature is at least 2 ℃ higher than the melting point of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i). Further optionally, the temperature before and during the contacting step c) is adjusted such that the temperature is at least 2 ℃ above the melting point of the at least one hydrophobizing agent.

It is to be understood that the term "melting point" refers to the solid-liquid phase transition of the corresponding compound. In the case where the compound is a polymer, the term "melting point" refers to the transition temperature from crystalline to solid amorphous phase.

In one embodiment of the invention, the temperature before and/or during the contacting step c) is adjusted such that the temperature is at least 5 ℃, preferably at least 8 ℃ and most preferably at least 10 ℃ higher than the melting point of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii).

The treatment time for carrying out the contacting of the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) is carried out for a period of time of 1000 seconds or less, preferably 500 seconds or less, more preferably 250 seconds or less and most preferably 0.1 to 1000 seconds. For example, the contacting step c) is carried out for a period of time of 0.1 to 20 seconds, preferably 0.5 to 15 seconds and most preferably 1 to 10 seconds. Generally, the length of time the at least one calcium carbonate-comprising filler material is contacted with the maleic anhydride-grafted polyethylene and/or the maleic anhydride-grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) is determined by the treatment temperature applied during said contacting. For example, in the case of applying a treatment temperature of about 250 ℃, the treatment time is as short as, for example, about 0.1 second. If a treatment temperature of about 90 deg.C is applied, the treatment time may be as long as, for example, about 1000 seconds.

It is understood that the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) is added in the contacting step c) in a total amount of from 0.2 to 7% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material of step a). For example, the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) is added in contacting step c) in an amount of from 0.3 to 4.0% by weight or from 0.6 to 3.0% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material of step a).

According to another embodiment of the present invention, the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene of step i) is added in contacting step c) in a total amount of 0.1 to 4% by weight, preferably 0.2 to 3% by weight and most preferably 0.5 to 2% by weight based on the total dry weight of the at least one calcium carbonate containing filler material.

Additionally or alternatively, the at least one hydrophobizing agent of step ii) is added in the contacting step c) in a total amount of from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight and most preferably from 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate-comprising filler material.

According to one embodiment of the invention, the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene of step i) is added in the contacting step c) in a total amount of 0.1 to 4% by weight, preferably 0.2 to 3% by weight and most preferably 0.5 to 2% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material, and the at least one hydrophobizing agent of step ii) is added in the contacting step c) in a total amount of 0.1 to 3% by weight, preferably 0.2 to 2% by weight and most preferably 0.3 to 1% by weight, based on the total dry weight of the at least one calcium carbonate containing filler material.

The ratio of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) to the at least one hydrophobizing agent of step ii) can vary within a wide range. Preferably, however, the contacting step c) is carried out by adding the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in a weight ratio of from 10:1 to 1: 10. Preferably, the contacting step c) is performed by adding the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii) in an amount of from 5:1 to 1:5 and most preferably from 4:1 to 1:4, e.g. 1: 1.

In one embodiment of the present invention, the at least one calcium carbonate-comprising filler material is preheated, i.e. activated, before carrying out the contacting step c). That is, the at least one calcium carbonate-comprising filler material is treated at a temperature of from 20 to 250 ℃, preferably from 40 to 200 ℃, more preferably from 50 to 150 ℃ and most preferably from 60 to 140 ℃ before the contacting step c) is performed.

The treatment time for carrying out the preheating of the at least one calcium carbonate-comprising filler material is carried out for a period of 30 minutes or less, preferably for a period of 20 minutes or less and more preferably for a period of 15 minutes or less.

In one embodiment of the present invention, the preheating of the at least one calcium carbonate-comprising filler material is carried out at a temperature approximately equal to the temperature carried out during the contacting step c).

The term "equal" temperature in the meaning of the present invention refers to a preheating temperature which is lower or higher by at most 20 ℃, preferably at most 15 ℃, more preferably 10 ℃ and most preferably at most 5 ℃ than the temperature carried out during the contacting step c).

It is therefore understood that the treatment layer formed on the surface of the at least one calcium carbonate-comprising filler material comprises the maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii). During the contacting of step c), the salted reaction product of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and/or the at least one hydrophobizing agent of step ii) may be obtained as a reaction product of contacting the calcium carbonate containing filler material with the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii). In this case, the treated layer of the surface-treated filler material product preferably further comprises the salt reaction products formed on the surface of the at least one calcium carbonate-containing filler material in step c). For example, a salt reaction product of the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene of step i) and the at least one hydrophobizing agent of step ii), such as one or more calcium and/or magnesium salts.

In one embodiment, the surface treated filler material product obtained in step c) is dried. This optional step is preferably performed to reduce the moisture content of the resulting surface treated filler material product. Thus, the dried surface-treated filler material product obtained in step d) has a moisture content that is lower than the moisture content of the surface-treated filler material product obtained before the drying step, i.e. after step c).

According to one embodiment of the invention, the method therefore comprises a further step d): drying the surface-treated filler material product obtained in step c).

For example, the optional drying step d) is carried out at a temperature of 60-180 ℃, preferably 50-150 ℃, more preferably 60-120 ℃ and most preferably 80-120 ℃ under ambient or reduced pressure until the moisture content of the obtained surface treated filler material product is reduced.

In one embodiment, the optional drying step d) is carried out until the moisture content of the obtained surface-treated filler material product is from 0.001 to 2% by weight, preferably from 0.005 to 1.5% by weight, more preferably from 0.01 to 1.0% by weight and most preferably from 0.05 to 0.5% by weight, based on the total weight of the surface-reacted calcium carbonate.

It will be appreciated that the optional drying step d) may be carried out at ambient or reduced pressure. Preferably, the drying is carried out at ambient pressure.

Thus, the optional drying step d) is preferably carried out at a temperature of 60 to 180 ℃ at ambient pressure. For example, the optional drying step e) is carried out at a temperature of 50 to 150 ℃, preferably 60 to 120 ℃ and more preferably 80 to 120 ℃ at ambient pressure.

According to one embodiment, the present invention therefore relates to a process for preparing a surface-treated filler material product, the process comprising at least the steps of:

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

b) provide for

i. Maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene, and

at least one hydrophobicizing agent

d) drying the surface-treated filler material product obtained in step c).

By the process of the present invention, it is possible to provide surface-treated filler material products having good powder flow properties but also having low moisture pick-up sensitivity. Furthermore, a surface treated filler material product may be provided having both maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobizing agent present in the surface treatment layer on the at least one calcium carbonate-comprising filler material.

The surface-treated filler material product thus obtained is advantageously implemented in a polymer composition comprising at least one polymer resin and from 1 to 95% by weight of the surface-treated filler material product of the invention.

In another aspect, the present invention therefore relates to a polymer composition comprising at least one polymer resin and from 1 to 95% by weight, based on the total weight of the polymer composition, of the surface-treated filler material product of the present invention.

Thus, the polymer composition comprises at least one polymer resin. The polymer resin represents the backbone of the composition and provides strength, flexibility, toughness and durability to the final fiber and/or filament and/or film and/or filament and/or sheet and/or pipe and/or profile and/or mold and/or injection molding compound and/or blow molding compound.

It is to be understood that the at least one polymer resin according to the present invention is not limited to a specific resin material as long as the polymer composition is suitable for the production of fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds.

In one embodiment of the present invention, the at least one polymer resin is at least one thermoplastic polymer. Preferably, therefore, the at least one polymer resin is a thermoplastic polymer chosen from homopolymers and/or copolymers of: polyolefins, polyamides, halogen-containing polymers and/or polyesters.

Additionally or alternatively, the at least one polymer resin is a homopolymer and/or a copolymer of a polyolefin. For example, the at least one polymer resin is a homopolymer and a copolymer of a polyolefin. Alternatively, the at least one polymer resin is a homopolymer or a copolymer of a polyolefin.

It is to be understood that the at least one polymer resin is preferably a homopolymer of a polyolefin.

For example, the polyolefin may be polyethylene and/or polypropylene and/or polybutylene. Thus, if the polyolefin is a polyethylene, the polyolefin is selected from homopolymers and/or copolymers of polyethylene, such as High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Very Low Density Polyethylene (VLDPE), Linear Low Density Polyethylene (LLDPE).

For example, the polyolefin is a homopolymer and/or copolymer of polyethylene.

The expression homopolymer of polyethylene as used in the present invention refers to the following polyethylenes: the polyethylene comprises a polyethylene consisting essentially of (i.e., greater than 99.7 weight percent, and more preferably at least 99.8 weight percent, based on the total weight of the polyethylene) ethylene units. For example, only ethylene units are detectable in a homopolymer of polyethylene.

In the case where the at least one polymer resin of the polymer composition comprises a copolymer of polyethylene, it is understood that the polyethylene comprises units derived from ethylene as a major component. Thus, the copolymer of polyethylene comprises at least 55% by weight of units derived from ethylene, more preferably at least 60% by weight of units derived from ethylene, based on the total weight of the polyethylene. For example, the copolymer of polyethylene comprises from 60 to 99.5% by weight, more preferably from 90 to 99% by weight, of units derived from ethylene, based on the total weight of the polyethylene. The comonomer present in the copolymer of this polyethylene is C₃-C₁₀Preferably 1-butene, 1-hexene and 1-octene, the latter being particularly preferred.

Additionally or alternatively, the polyolefin is a homopolymer and/or copolymer of polypropylene.

The expression homopolymer of polypropylene as used throughout the present invention refers to such polypropylene as follows: the polypropylene consists essentially of (i.e., greater than 99 wt%, still more preferably at least 99.5 wt%, e.g., 99.8 wt%, based on the total weight of the polypropylene) propylene units. For example, only propylene units are detectable in a homopolymer of polypropylene.

In case the at least one polymer resin of the polymer composition comprises a copolymer of polypropylene, the polypropylene preferably comprises units derived from propylene as main component. The copolymer of polypropylene preferably comprises, preferably consists of: derived from propylene and C₂And/or at least one C₄-C₁₀Units of alpha-olefins of (a). In one embodiment of the invention, the copolymer of polypropylene comprises, preferably consists of: units derived from propylene and at least one alpha-olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene. For example, the copolymer of polypropylene comprises, preferably consists of: units derived from propylene and ethylene. In one embodiment of the invention, the units derived from propylene constitute the major part of the polypropylene, i.e. at least 60 wt. -%, preferably at least 70 wt. -%, more preferably at least 80 wt. -%, still more preferably from 60 to 99 wt. -%, yet more preferably from 70 to 99 wt. -% and most preferably from 80 to 99 wt. -%, based on the total weight of the polypropylene. Derived from C in the copolymer of the polypropylene₂And/or at least one C₄-C₁₀The amount of units of alpha-olefin(s) of (a) is from 1 to 40% by weight, more preferably from 1 to 30% by weight and most preferably from 1 to 20% by weight, based on the total weight of the copolymer of polypropylene.

If the copolymer of polypropylene comprises only units derived from propylene and ethylene, the amount of ethylene is preferably from 1 to 20% by weight, preferably from 1 to 15% by weight and most preferably from 1 to 10% by weight, based on the total weight of the copolymer of polypropylene. Thus, the amount of propylene is preferably from 80 to 99% by weight, preferably from 85 to 99% by weight and most preferably from 90 to 99% by weight, based on the total weight of the copolymer of polypropylene.

Additionally or alternatively, the polyolefin is a homopolymer and/or copolymer of polybutene.

The expression homopolymer of polybutene used throughout the present invention refers to the following such polybutenes: the polybutene consists essentially of (i.e., greater than 99 wt%, still more preferably at least 99.5 wt%, e.g., 99.8 wt%, based on the total weight of the polybutene) butene units. In a preferred embodiment, only the butene units are detectable in the homopolymer of polybutene.

In case the at least one polymer resin of the polymer composition comprises a copolymer of polybutene, the polybutene preferably comprises units derived from butene as main component. The copolymer of polybutene preferably comprises, preferably consists of: derived from butene and C₂And/or C₃And/or at least one C₅-C₁₀Units of alpha-olefins of (a). In one embodiment of the invention, the copolymer of polybutene comprises, preferably consists of: units derived from butene and at least one alpha-olefin selected from ethylene, 1-propene, 1-pentene, 1-hexene and 1-octene. For example, the copolymer of polybutene comprises, preferably consists of: units derived from butene and ethylene. In one embodiment of the invention, the units derived from butene constitute the major part of the polybutene, i.e. at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, even more preferably from 60 to 99% by weight, still more preferably from 70 to 99% by weight and most preferably from 80 to 99% by weight, based on the total weight of the polybutene. Derived from C in the copolymer of polybutene₂And/or C₃And/or at least one C₅-C₁₀The amount of units of alpha-olefin(s) is from 1 to 40% by weight, more preferably from 1 to 30% by weight and most preferably from 1 to 20% by weight, based on the total weight of the copolymer of polybutene.

If the at least one polymer is a homopolymer and/or copolymer of polyamide, the at least one polymer resin is preferably selected from the group consisting of berlon (PA6), nylon (PA6.6), nylon 11(PA11), nylon 12(PA12), poly (p-phenylene terephthalamide) (PPTA) and poly (m-phenylene isophthalamide) (PMPI).

If the at least one polymer resin is a homopolymer and/or copolymer of a halogen-containing polymer, the at least one polymer resin is preferably selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE).

If the at least one polymer resin is a homopolymer and/or copolymer of a polyester, the at least one polymer resin is preferably selected from the group consisting of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and also degradable polyesters such as polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), Polyhydroxyalkanoates (PHA).

In one embodiment of the invention, the at least one polymer resin is a homopolymer of polyethylene and/or polypropylene and/or polybutylene. For example, the at least one polymer resin is a homopolymer of polyethylene and polypropylene. Alternatively, the at least one polymer resin is a homopolymer of polyethylene or polypropylene. In one embodiment of the present invention, the at least one polymer resin is a homopolymer of polypropylene.

The expression "at least one" polymer resin refers to one or more types of polymer resins that may be present in the polymer composition of the present invention.

It is therefore to be understood that the at least one polymer resin may be a mixture of two or more types of polymer resins. For example, if the at least one polymer resin is a mixture of two or more types of polymer resins, one polymer resin is a homopolymer or copolymer of polypropylene and the second or further polymer resin is selected from homopolymers and/or copolymers of: polyethylene, polybutylene, polyamide, polyester, halogen-containing polymers, and mixtures thereof.

In one embodiment of the present invention, the at least one polymer resin is one type of polymer resin. Preferably, the at least one polymer resin is a homopolymer of polyethylene or polypropylene, and more preferably a homopolymer of polyethylene, such as Linear Low Density Polyethylene (LLDPE).

In one embodiment of the invention, theAt least one polymer resin having a melting temperature T_mAbove 80 deg.C, more preferably above 100 deg.C. For example, the melting temperature of the at least one polymer resin is in the range of 80 to 350 ℃, more preferably in the range of 100 to 300 ℃ and most preferably in the range of 100 to 250 ℃.

It is further understood that the at least one polymer resin may be selected from polymer resins having a wide range of melt flow rates. Generally, it is preferred that the at least one polymer resin has a melt flow rate MFR (190 ℃) of 0.1 to 3000g/10min, more preferably 0.2 to 2500g/10 min. For example, the at least one polymer resin has a melt flow rate MFR (190 ℃) of 0.3 to 2000g/10min or 0.3 to 1600g/10 min. Additionally or alternatively, the at least one polymer resin has a melt flow rate MFR (230 ℃) of from 0.1 to 3000g/10min, more preferably from 0.2 to 2500g/10 min. For example, the at least one polymer resin has a melt flow rate MFR (230 ℃) of 0.3 to 2000g/10min or 0.3 to 1600g/10 min.

If the at least one polymer resin is a polyolefin, which is a homopolymer and/or copolymer of polyethylene, it is understood that the at least one polymer resin has a relatively low melt flow rate. Thus, preferably the at least one polymer resin as a homopolymer and/or copolymer of polyethylene has a melt flow rate MFR (190 ℃) of 0.5-20g/10min, more preferably 0.7-15g/10 min. For example, the at least one polymer resin has a melt flow rate MFR (190 ℃) of 0.9 to 10g/10min or 0.9 to 5g/10 min. Additionally or alternatively, the at least one polymer resin as a homopolymer and/or copolymer of polyethylene has a melt flow rate MFR (230 ℃) of from 0.1 to 3000g/10min, more preferably from 0.2 to 2500g/10 min. For example, the at least one polymer resin as a homopolymer and/or copolymer of polyethylene has a melt flow rate MFR (230 ℃) of 0.3 to 2000g/10min or 0.3 to 1600g/10 min.

"natural fibers" according to the invention are fibers which occur naturally, for example in wood, cellulose, hemp or agricultural waste products such as sugar cane, bananas, corn stalks or straw. "synthetic fibers" are fibers produced, for example, from glass, carbon or aramid syntheses. Such fibers are commercially available and known to those skilled in the art. The person skilled in the art is able to select suitable fibers based on the respective application of the polymer composition.

According to a preferred embodiment of the present invention, the polymer composition comprises at least one polymer resin, 1-95% by weight, based on the total weight of the polymer composition, of the surface-treated filler material product according to the present invention and natural and/or synthetic fibers.

According to another preferred embodiment of the present invention, the polymer composition comprises at least one polymer resin, from 1 to 95% by weight, based on the total weight of the polymer composition, of the surface-treated filler material product according to the present invention and natural and/or synthetic fibers, wherein the at least one polymer resin is a thermoplastic polymer selected from homopolymers and/or copolymers of: polyolefins, polyamides, halogen-containing polymers and/or polyesters, and are preferably selected from the group consisting of polyethylene, polypropylene and mixtures thereof.

Another essential component of the present polymer composition is the surface treated filler material product. With regard to the definition of the surface-treated filler material product and its preferred embodiments, reference is made to the comments provided above.

One requirement of the present invention is: the polymer composition comprises the surface treated filler material product in an amount of 1 to 95 wt% based on the total weight of the polymer composition.

In one embodiment of the invention, the polymer composition comprises the surface treated filler material product in an amount of 5 to 95% by weight and preferably 10 to 85% by weight, based on the total weight of the polymer composition. For example, the polymer composition comprises the surface treated filler material product in an amount of 15 to 80% by weight based on the total weight of the polymer composition.

In one embodiment of the invention, the polymer composition is a masterbatch.

The term "masterbatch" refers to such a composition as follows: the composition has a concentration of the surface treated filler material product that is higher than the concentration of the polymer composition used to prepare the end-use product, such as a fiber and/or filament and/or film and/or thread and/or sheet and/or pipe and/or profile and/or mold and/or injection molding compound and/or blow molding compound. That is, the masterbatch is further diluted to obtain a polymer composition suitable for the preparation of end-use products such as fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds.

For example, the masterbatch comprises the surface treated filler material product in an amount of 20 to 95% by weight, preferably 30 to 85% by weight and more preferably 35 to 80% by weight, based on the total weight of the masterbatch.

According to one embodiment of the invention, the masterbatch is used for producing fibers and/or filaments and/or films and/or threads.

In another embodiment of the present invention, the polymer composition used for the production of end-use products such as fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds comprises the surface treated filler material product in an amount of 1 to 70% by weight, preferably 5 to 55% by weight and most preferably 10 to 50% by weight, based on the total weight of the polymer composition. For example, a polymer composition used to prepare end-use products such as fibers and/or filaments and/or films includes the surface treated filler material product in an amount of 20 to 50 weight percent based on the total weight of the polymer composition.

If the masterbatch is used to produce fibers and/or filaments and/or films and/or strands and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds, preferably the masterbatch is diluted to obtain a polymer composition suitable for the preparation of end-use products such as fibers and/or filaments and/or films and/or strands and/or sheets and/or pipes and/or profiles and/or molding compounds and/or injection molding compounds and/or blow molding compounds. That is, the masterbatch is diluted to comprise the surface treated filler material product in an amount of 1 to 70% by weight, preferably 5 to 55% by weight and most preferably 10 to 50% by weight, based on the total weight of the polymer composition.

According to another embodiment of the invention, the polymer composition is a fiber and/or filament and/or film and/or filament and/or sheet and/or pipe and/or profile and/or mold and/or injection molding compound and/or blow molding compound. For example, the fibers and/or filaments and/or films and/or wires and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds comprise the surface treated filler material product in an amount of 1 to 70% by weight, preferably 5 to 55% by weight, more preferably 10 to 50% by weight and most preferably 15 to 30% by weight, based on the total weight of the fibers and/or filaments and/or films and/or wires and/or sheets and/or pipes and/or profiles and/or molds and/or injection molding compounds and/or blow molding compounds.

In view of the good flowability characteristics of the surface-treated filler material product and its good dispersibility in polymer compositions, the surface-treated filler material product according to the invention can advantageously be used in end-use products such as fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or moulds and/or injection-moulding compounds and/or blow-moulding compounds. In view of this, when the surface-treated filler material product is provided in the form of the polymer composition of the present invention, the surface-treated filler material product imparts excellent mechanical and/or rheological properties to the end-use product, such as fibers and/or filaments and/or films and/or threads and/or sheets and/or pipes and/or profiles and/or moulds and/or injection compounds and/or blow compounds.

The term "fiber" in the meaning of the present invention refers to a linear structure forming a textile fabric, such as a nonwoven, which is typically composed of a web of fibers bonded together by, for example, mechanical means. Thus, the term "fiber" is understood to mean a finite structure.

The term "thread" in the meaning of the present invention refers to a linear structure forming a textile fabric, such as a nonwoven, which is typically composed of a network of threads bonded together by, for example, mechanical means. Thus, the term "thread" is understood to mean a finite structure.

The term "filament" in the meaning of the present invention refers to a structure that differs from a fiber in its structural length. Thus, the term "filament" refers to an infinite fiber. It is further understood that the filaments may be configured as monofilaments, monofilaments or multifilaments.

The cross-section of the filaments and/or fibers and/or threads may have a variety of shapes. Preferably, the shape of the cross-section of the filaments and/or fibres and/or threads may be circular, elliptical or n-sided, where n ≧ 3, for example n is 3. For example, the cross-section of the filaments and/or fibres and/or threads is circular or trilobal, e.g. circular. Additionally or alternatively, the cross-sectional shape of the filaments and/or fibers and/or threads may be hollow.

It is to be understood that the filaments and/or fibers and/or threads may be prepared by all methods known in the art for preparing such filaments and/or fibers and/or threads. For example, the filaments and/or fibers and/or threads of the present invention may be prepared by well-known melt blowing processes, extrusion molding processes, compression molding processes, injection molding processes, spunbonding processes, or staple fiber production.

The term "film" in the meaning of the present invention refers to a structure which differs from filaments and/or fibers in its dimensional structure. Thus, the term "film" is understood to mean a sheet.

It is understood that the films may be prepared by all techniques known in the art for preparing such films. For example, the films of the present invention can be prepared by well-known techniques for preparing stretched or oriented films, preferably extrusion coated films, blown films, industrial blown films, monotapes, cast films, and the like.

According to another embodiment of the invention, the surface treated filler material product of the invention treated as defined above is used in a polymer composition, preferably a polyethylene or polypropylene composition, for improving the mechanical and/or rheological properties of the polymer composition compared to the same polymer composition treated in the same way, wherein the surface treated mineral filler product is treated with at least one hydrophobizing agent only. The present inventors have surprisingly found that when the surface treated filler material products of the present invention are used in polymer compositions, they maintain or improve the mechanical and/or rheological properties of the polymer composition and/or end-use product, especially as compared to surface treated filler material products that are surface treated with only the same hydrophobizing agent. Even though surface treated filler material products treated with hydrophobizing agents alone have shown good powder flow and low moisture pick-up sensitivity, the mechanical and/or rheological properties of polymer compositions comprising such products are weak. However, the present inventors have found that the polymer compositions and/or end-use products of the present invention have maintained or improved mechanical and/or rheological properties when used in a polymer composition, wherein the surface treated filler material product of the present invention comprises a treatment layer comprising maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobizing agent on the surface of the at least one calcium carbonate containing filler material. In particular, they have a retained or lower melt flow rate and/or a retained or higher maximum load performance, a retained or higher impact strength and/or a retained or higher flexural modulus and/or a retained or higher tensile properties such as yield strength-in particular compared to polymer compositions and/or end-use products comprising surface-treated filler material products which have been surface-treated with the same hydrophobizing agent only.

The expression "treated with at least one hydrophobizing agent only" compared to the same polymer composition treated in the same way "according to the present invention refers to a comparative polymer composition wherein the surface-treated mineral filler material product is treated with at least one hydrophobizing agent only according to the present invention and not with the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene according to the present invention. Apart from this, the polymer composition according to the invention and the comparative polymer composition are identical, which means that they comprise the same compound. Furthermore, both polymer compositions are treated in the same way, which means that the compounding and storage treatments are the same.

Detailed Description

The following examples may additionally illustrate the invention, but are not intended to limit the invention to the illustrated embodiments.

Experiment of

I. Analytical method

Powder flow-stability and variable flow method

The Basic Flow Energy (BFE), Stability Index (SI), Specific Energy (SE), Flow Rate Index (FRI) and Conditioned Bulk Density (CBD) were measured using the stability and variable flow rate methods on a FT4 powder rheometer (Freeman Technology, UK) equipped with powder rheometer software (v5.000.00012) and Freeman Technology data analysis software version 4.0.17.

This method consists in filling cylindrical containers (25mm x 25mL glass containers).

The first stage of the testing process is to obtain a uniform, conditioned powder state for highly repeatable measurements. The conditioning cycle involved a dynamic test blade cutting down into the powder and then moving 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 the 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. Thereafter, 8 repeated cycles of conditioning and measurement were performed using 23.5mm blades. For each test cycle, the blade was inserted down into the powder bed (counter clockwise, tip speed-100 mm/s, helix angle 5 °/target height 5mm) and up. For the conditioning step, the blade was inserted down into the powder bed (tip speed 40 mm/s/helix angle 5 °, target height 5mm) and up.

After these 8 tests, 3 more cycles (conditioning + test) were performed at variable flow rate, i.e. blade tip speed 70mm/s (test 9), 40mm/s (test 10) and finally 10mm/s (test 11). Recording energy and torque and allowing various flow parameters to be calculated, is defined as follows:

-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 split mass)

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

Conditioned bulk density (CBD, g/mL): (cleavage Mass)/(cleavage volume)

Melt flow rate

Melt flow index was measured according to ISO 1133-1:2011 on a CEAST instrument equipped with Ceast View 6.154C software. The die length was 8mm and its diameter was 2.095 mm. The measurement was carried out at 190 ℃ with no load preheating for 300 seconds, and then the melt flow was measured along 20mm using a nominal load of 2.16 kg.

Tensile Properties

Tensile properties were measured according to ISO527-1:2012 type BA (1:2) on an Allround Z020 traction device from Zwick Roell. The measurement was carried out at an initial load of 0.1 MPa. For the measurement of the E-modulus, a speed of 1mm/min was used, which was then increased to 500 mm/min. Tensile strain at break was obtained under standard conditions. All measurements were made on samples that had been stored under similar conditions after preparation.

Flexural Properties

Flexural properties were measured according to ISO 178:2013-09 on an Allround Z020 traction device from Zwick Roell. Measurements were made using a 2N pre-applied force. For the flexural modulus measurement, a speed of 1.72mm/min was used, which was then increased to 10 mm/min. The test was stopped after 3.5% deformation.

All measurements were made on samples that had been stored under similar conditions after preparation.

Impact performance

Impact properties were measured according to ISO179-1 eU:2010-11 on an HIT5.5P apparatus from Zwick Roell. The unnotched samples were measured with a 5J hammer. All measurements were made on samples that had been stored under similar conditions after preparation.

Maximum load performance

The maximum load performance was measured on a Hounsfield H10 KM instrument on a handled bottle with a nominal volume of 1.5L. The measurement was carried out at 10mm/min with a load measuring range of 2000N.

All measurements were made on samples that had been stored under similar conditions after preparation.

Sensitivity to moisture uptake

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

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, "d₅₀"values are based on a Sedigraph by using Micromeritics Instrument Corporation^TM5100 and are defined as the following such dimensions: at this size 50% (median point) of the mass of the particles is constituted by particles having a diameter equal to the specified value.

Methods and apparatus are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. At 0.1% by weight of Na₄P₂O₇Is measured in an aqueous solution of (a). A high speed stirrer and ultrasound were used to disperse the samples.

BET specific surface area of the Material

Throughout this document, mineSpecific surface area (m) of the filler²Per g) was determined using the BET method (using nitrogen as adsorption gas) well known to the person skilled in the art (ISO9277: 2010). Total surface area of mineral filler (m)²) It is obtained by multiplying the specific surface area by the mass (g) of the mineral filler before treatment.

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 maleic anhydride-grafted polyethylene and/or maleic anhydride-grafted polypropylene and the at least one hydrophobicizing agent used for the surface treatment. It is assumed that the maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene added to 100% of the calcium carbonate containing filler material and the at least one hydrophobizing agent are present as a surface treatment layer on the surface of the calcium carbonate containing filler material.

Experimental part

Part 1: preparation of surface-treated calcium carbonate

Materials used in the examples：

1. Hydrophobizing agent 01: ASA 1

Monosubstituted alkenyl succinic anhydrides (2, 5-furandiones, dihydro-, mono-C)_15-20-alkenyl derivative, CAS number: 68784-12-3) was a blend of predominantly branched octadecenyl succinic anhydride (CAS #28777-98-2) and predominantly branched hexadecenyl succinic anhydride (CAS # 32072-96-1). More than 80% of the blend was branched octadecenyl succinic anhydride. Purity of the blend>95% by weight. The residual olefin content is less than 3% by weight.

2. Hydrophobizing agent 02: fatty acid mixture 2

Fatty acid mixture 2 is a 1:1 mixture of stearic and palmitic acids.

3. Maleic anhydride grafted polyethylene/polypropylene: maleic anhydride grafted PE3

MA-grafted PE3 is a functionalized metallocene catalyst-based polyethylene wax (grafted with maleic anhydride) produced by Clariant corporation (fine Licocene PEMA 4351 particles) having an acid value of 42 to 49mgKOH/g and a viscosity of 200-500 mPas at 140 ℃.

4. Calcium carbonate containing filler material CC1

Calcium carbonate CC1 is a wet-milled and spray-dried calcium carbonate (d) from Italy₅₀＝1.9μm，d₉₈＝5.8μm)。

5. Calcium carbonate containing filler material CC2

Calcium carbonate CC2 is dry-milled calcium carbonate (marble, d) from Italy₅₀＝3.3μm，d₉₈＝13.8μm，BET SSA＝2.6m²/g)。

6. Polymer resin 1

Polymer resin 1 is Resinex PE RXP 1303 Natural commercially available from Resinex.

7. Polymer resin 2

Polymer resin 2 is HDPE luplen 5021DX commercially available from LyondellBasell Industries.

8. Polymer resin 3

Polymer resin 3 is PLA Ingeo 2003D, commercially available from NatureWorks LLC.

Surface treatment process

The surface treatment was carried out in a high-speed Mixer (Somakon MP-LB Mixer, Somakon Verfahrenstechnik, Germany) and conditioned by stirring at the treatment temperature for 10 minutes (600-. Thereafter, the additives were added to the mixture, and then stirring and heating were continued for an additional 15 minutes (for each step) (600-. Thereafter, the mixture was allowed to cool and the powder was collected.

Table 1: and (3) preparing a filler material product subjected to surface treatment.

Section 2: effect of the surface treated filler material on the melt flow rate of the polymer composition:

the masterbatches MB-1 to MB-7 were produced on a 25:1 twin-screw extruder from Three Tec (extruder model No. ZE12, die: 0.5mm) with the following line settings:

extruder temperature: 20 deg.C (feed) -190 deg.C/210 deg.C/190 deg.C

-feed rate: 7 percent of

-screw speed: 20rpm

-conveyor speed: 1.4rpm

-cutting speed: 21rpm

The polymer used was a Linear Low Density Polyethylene (LLDPE) available from Resinex under the trade name RXP Natural 1303 (polymer resin 1).

The masterbatches MB-8 to MB-13 were produced on a 25:1 twin-screw extruder from Three Tec (extruder model No. ZE12, die: 0.5mm) with the following line settings:

extruder temperature: 20 deg.C (feed) -180 deg.C/190 deg.C/180 deg.C

-feed rate: 10 percent of

-screw speed: 30rpm

-conveyor speed: 1.5rpm

-cutting speed: 21rpm

The polymer used is polylactic acid (PLA), which is available from Natureworks LLC under the trade name PLA Ingeo 2003D (polymer resin 3).

Table 2: preparation and composition of masterbatches MB-1 to MB-13

Sample (I)	Polymer (% by weight)	Surface treated filler material (% by weight)	Additional additives (% by weight)Measuring)
				MB-1	Polymer resin 1 (60%)	Powder 1 (40%)	/
MB-2	Polymer resin 1 (60%)	Powder 2 (40%)	/
				MB-3	Polymer resin 1 (60%)	Powder 3 (40%)	/
MB-4	Polymer resin 1 (60%)	Powder 1 (39.2%)	MA-grafted PE3 (0.8%)
				MB-5	Polymer resin 1 (60%)	Powder 4 (40%)	/
MB-6	Polymer resin 1 (60%)	Powder 5 (40%)	/
				MB-7	Polymer resin 1 (60%)	Powder 6 (40%)	/
MB-8	Polymer resin 3 (100%)	/	/
				MB-9	Polymer resin 3 (70%)	Powder 1 (30%)	/
MB-10	Polymer resin 3 (70%)	Powder 2 (30%)	/
				MB-11	Polymer resin 3 (70%)	Powder 10 (30%)	/
MB-12	Polymer resin 3 (70%)	Powder 11 (30%)	/
				MB-13	Polymer resin 3 (70%)	Powder 3 (30%)	/

Table 3: melt flow rates of MB-1 to MB-7

	MB-1	MB-2	MB-3	MB-5	MB-6	MB-7
							MFI(g/10min)	4.60	4.87	3.68	4.31	4.53	4.49

It can be seen from table 3 that the treatment of the calcium carbonate-comprising filler material (MB-3) with maleic anhydride grafted polyethylene/polypropylene results only in a lower MFI-which makes the processing more complicated. This reduction in MFI (due to MA grafted PE) can be mitigated by appropriate co-treatment with at least one hydrophobizing agent (MB-5 to MB-7) and almost match the melt rheology obtained with standard fatty acid treated calcium carbonate (MB-1).

Table 4: melt flow rates of MB-8 to MB-12

	MB-8	MB-9	MB-11	MB-12
					MFI(g/10min)	8.1	9.7	6.1	4.7

The polymer resin 3 is susceptible to hydrolysis. As can be seen from table 4, treatment of the calcium carbonate-containing filler material (MB-9) with the fatty acid mixture resulted in only a higher MFI-which may be attributed to some degradation. This increase in MFI (due to the presence of MA-grafted PE) can be moderated by appropriate co-treatment with MA-grafted and at least one hydrophobicizing agent (MB-11 to MB-12).

Section 3: impact on impact and flexural Properties

Plaques were made in Dr Collin P300 Press with the pellets (MB-1 to MB-7) produced as described in Table 2, with the settings as shown in Table 5:

table 5: pressing conditions

Temperature of	190℃	190℃	20℃
				Pressure of	20 bar	200 bar	120 bar
Time	60s	120s	120s

The dimensions of the produced panels were 170mm x 170mm x 4 mm. The impact bar test was cut to the dimensions required for Charpy test ISO179-1eU and flexural test ISO 178. Impact testing was performed according to ISO179-1eU (unnotched) using a 5J hammer.

Table 6: impact Properties according to ISO179-1eU

	MB-1	MB-2	MB-5	MB-6	MB-7
						Rebound resilience (kJ/m)²)	69.8	65.7	81.4	78.2	76.5

As can be seen from Table 6, the impact strength/resilience can be improved by the co-treatment (MB-5, MB-6 and MB-7) when compared with the surface-treated calcium carbonate (MB-1 and MB-2) comprising only the hydrophobizing agent without the maleic anhydride-grafted polyethylene/polypropylene.

Flexural testing was performed according to ISO 178.

Table 7: flexural Properties according to ISO178

	MB-1	MB-2	MB-5	MB-6	MB-7
						Flexural modulus (MPa)	369	292	399	412	419
Flexural Strain (N/mm) at 3.5%²)	10.2	9.5	11.6	12	12.1

As can be seen from Table 7, the flexural properties can be improved by the co-treatment (MB-5, MB-6 and MB-7) as compared to the surface-treated calcium carbonate (MB-1 and MB-2) comprising only the hydrophobizing agent without the maleic anhydride grafted polyethylene/polypropylene.

Ballistic bars comprising polymer resin 3 were made from pellets (MB-8 to MB-13) produced as described in Table 2 in a laboratory injection molding machine Xplore IM12 from Xplore Instruments BV, with the settings as shown in Table 8.

Table 8: conditions for the laboratory injection Molding machine Xploore IM12

Temperature of the barrel	210℃	Pressure 1	7 bar, 1 second
				Temperature of the mold	65℃	Pressure 1 to 2	7-8 bar, 2 seconds
Time of fusion	3min	Pressure 2	8 bar, 12 seconds

The ballistic bar test was molded and then notched with an automatic notching machine from CEAST NotchvisPlus to the dimensions required for Charpy test ISO179-1 eA. Impact testing was performed according to ISO179-1eA using a 0.5J hammer.

Table 9: impact Properties according to ISO179-1eA

	MB-8	MB-9	MB-10	MB-12	MB-13
						Rebound resilience (kJ/m)²)	2.9	5.7	6.1	6.4	3.1

As can be seen from Table 9, the impact strength/resilience was improved by the co-treatment (MB-12) as compared to the surface-treated calcium carbonate (MB-9, MB-10) comprising only the hydrophobizing agent without the maleic anhydride-grafted polyethylene/polypropylene.

Section 4: influence on tensile Properties

Films with polymer resin 1 for tensile testing were produced on a 25:1 twin-screw extruder from Three Tec (extruder model No. ZE12, die: 20 × 0.5mm), following the same amounts for masterbatch production (see table 10) and with the following line settings:

extruder temperature: 20 deg.C (feed) -190 deg.C/210 deg.C/190 deg.C

-feed rate: 17 percent of

-screw speed: 60rpm

-conveyor speed: 1

Table 10: film preparation and composition

The effect of the treated minerals on yield strength is shown in table 11.

Table 11: tensile Properties of films-Effect on yield Strength

	F-1	F-2	F-4	F-5	F-6	F-7
							Yield strength (N/mm)²)	9.7	10.4	12.2	12.8	13.1	14.1
Standard deviation of	0.2	0.2	0.2	0.2	0.2	0.2

As can be seen from Table 11, the yield strength can be surprisingly improved by the co-treatment (F-5 to F-7) both compared to the surface treated calcium carbonate (F-1 and F-2) comprising only the hydrophobizing agent without the maleic anhydride grafted polyethylene/polypropylene and also compared to the surface treated calcium carbonate (F-4) comprising the hydrophobizing agent in combination with the same amount of MA-grafted PE as additive during compounding.

Tensile bars comprising polymer resin 3 were made from the pellets produced as described in Table 2 (MB-8 to MB-13) in a laboratory injection molding machine Xplore IM12 from Xplore Instruments BV, with the settings as shown in Table 12.

Table 12: condition of laboratory injection molding machine XploreIM12

Temperature of the barrel	210℃	Pressure 1	7 bar, 1 second
				Temperature of the mold	65℃	Pressure 1 to 2	7-8 bar, 2 seconds
Time of fusion	3min	Pressure 2	8 bar, 12 seconds

The tensile bar test was moulded to the required dimensions according to ISO 5271-BA.

The effect of the treated minerals on the E-modulus is shown in table 13.

Table 13: effect of tensile Properties-on E-modulus

	MB-9	MB-10	MB-11	MB-12
					E-modulus (N/mm)²)	2030	2000	2150	2060

The effect of the treated minerals on yield strength is shown in table 14.

Table 14: tensile Property-Effect on yield Strength

	MB-9	MB-10	MB-11	MB-12
					Yield strength (N/mm)²)	42.3	42.5	44.6	43.6

As can be seen from tables 13 and 14, the E-modulus and yield strength can be improved by co-treatment (MB-11 and MB-12) when compared to the surface-treated calcium carbonate (MB-9 and MB-10) both comprising only the hydrophobizing agent and no maleic anhydride grafted polyethylene/polypropylene.

The effect of the treated minerals on elongation at break is shown in table 15.

Table 15: effect of tensile Properties on elongation at Break

	MB-8	MB-9	MB-10	MB-11	MB-12	MB-13
							Elongation at Break (%)	3.4	7	12.9	9.1	16.3	3.6

As can be seen from Table 15, the elongation at break can be surprisingly improved by co-treatment (MB-11 and MB-12) when compared to surface-treated calcium carbonates (MB-8 and MB-9) both comprising only the hydrophobizing agent without the maleic anhydride grafted polyethylene/polypropylene and also when compared to the use of MA-grafted PE without the hydrophobizing agent.

Section 5: effect of this treatment on powder rheology

Table 16: flowability of powder

Powder of	BFE，mJ	CBD，g/ml
			Powder 1	52.76	0.79
Powder 3	208.43	0.66
			Powder 4	64.94	0.80
Powder 5	55.96	0.72

From table 16 it can be seen that the treatment of pure MA-grafted PE (powder 3) has a drastic effect on the powder flowability compared to the standard fatty acid treated calcium carbonate (powder 1), resulting in a large increase in the BFE value. The co-treated filler material powders (powder 4 and powder 5) had better flow properties (BFE values) than the powder treated with only MA-grafted PE (powder 3). They almost match the flow behaviour of the powder treated with fatty acid only as hydrophobicizing agent (powder 1). This is an important parameter, since the poor flowability of the powder 3 can be a drawback for processing.

Furthermore, the bulk density (CBD) of powders 4 and 5 was also surprisingly higher than the bulk density (CBD) of powder 3. Higher bulk density can be an advantage for storage and transport of materials.

Section 6: influence on moisture uptake sensitivity

Table 17: sensitivity to moisture uptake

Powder of	Sensitivity to moisture uptake (mg/g)
		Powder 1	0.2
Powder 2	0.4
		Powder 3	1.2
Powder 4	0.7
		Powder 5	0.6
Powder 6	0.8

As can be seen from table 17, the moisture pick-up sensitivity of the calcium carbonate treated with MA-grafted PE only (powder 3) is relatively high (much higher than the standard fatty acid or ASA-treated calcium carbonate, powder 1 and powder 2). The co-processed samples (powders 4 to 6) have a much lower moisture pick-up sensitivity than powder 3, an important parameter in polyolefin applications.

Section 7: effect of this treatment on the maximum load of blow-molded HDPE bottles

Masterbatches MB-14 to MB-16 were produced on a Buss Co-Kneader 46mm, set up as follows:

temperature profile of the extruder: 170 ℃/190 ℃/190 ℃/235 DEG C

-screw speed: 200rpm

Table 18: preparation and composition of masterbatches MB-14 to MB-16

Sample (I)	Polymer (% by weight)	Surface treated filler material (% by weight)
			MB-14	Polymer resin 2 (60%)	Powder 7 (40%)
MB-15	Polymer resin 2 (60%)	Powder 8 (40%)
			MB-16	Polymer resin 2 (60%)	Powder 9 (40%)

Blown bottles containing 7.5% by weight or 15% by weight filler content were then continuously extruded on a blow moulding machine Krupp Kautex KEB 4 using the following parameters:

temperature profile of the extruder: 190-200 deg.C

-head temperature: 210 deg.C

-screw speed: 16rpm

-cycle time: 16s

-a nozzle opening: 1.85mm

The composition of the bottles produced is summarized in table 19:

the maximum load performance was evaluated on a Hounsfield H10 KM instrument using the following parameters:

-test speed: 10mm/min

-sampling rate: 10 measurements/second

-load measurement range: 2000N

Table 19: preparation and composition of bottles B-1 to B-6

As can be seen from Table 19, the maximum loads (first failure and maximum) of B-3 and B-6 comprising the surface-treated filler material products according to the invention are higher than the maximum loads (first failure and maximum) of B-1 and B-2 or B-4 and B-5 comprising the comparative surface-treated filler material products.

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Ca coated with maleic anhydride grafted polyethylene and/or maleic anhydride grafted polypropylene and at least one hydrophobicizing agentCO3

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