HUE034671T2 - Eljárás kalcium-karbonát-töltõanyag elõállítására - Google Patents
Eljárás kalcium-karbonát-töltõanyag elõállítására Download PDFInfo
- Publication number
- HUE034671T2 HUE034671T2 HUE14156165A HUE14156165A HUE034671T2 HU E034671 T2 HUE034671 T2 HU E034671T2 HU E14156165 A HUE14156165 A HU E14156165A HU E14156165 A HUE14156165 A HU E14156165A HU E034671 T2 HUE034671 T2 HU E034671T2
- Authority
- HU
- Hungary
- Prior art keywords
- maleic anhydride
- mineral filler
- styrene
- less
- polymers
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 85
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 79
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 29
- 239000000945 filler Substances 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title description 3
- 239000012764 mineral filler Substances 0.000 claims description 97
- 239000000203 mixture Substances 0.000 claims description 84
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 78
- 238000000227 grinding Methods 0.000 claims description 71
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 51
- 229920001577 copolymer Polymers 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 27
- 238000009837 dry grinding Methods 0.000 claims description 23
- -1 potassium carboxylate Chemical class 0.000 claims description 21
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- 239000011591 potassium Substances 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 17
- 239000011707 mineral Substances 0.000 claims description 17
- 235000010755 mineral Nutrition 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- 239000004579 marble Substances 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 7
- 239000010459 dolomite Substances 0.000 claims description 7
- 229910000514 dolomite Inorganic materials 0.000 claims description 7
- 239000006028 limestone Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- 239000002537 cosmetic Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 210000004556 brain Anatomy 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 239000004927 clay Substances 0.000 claims 2
- 235000016623 Fragaria vesca Nutrition 0.000 claims 1
- 240000009088 Fragaria x ananassa Species 0.000 claims 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 claims 1
- 241000234435 Lilium Species 0.000 claims 1
- 241001465754 Metazoa Species 0.000 claims 1
- 241000282849 Ruminantia Species 0.000 claims 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims 1
- ZSCYJHGJGRSPAB-UHFFFAOYSA-N carbamic acid Chemical compound NC(O)=O.NC(O)=O ZSCYJHGJGRSPAB-UHFFFAOYSA-N 0.000 claims 1
- 239000004568 cement Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 239000003517 fume Substances 0.000 claims 1
- 210000004907 gland Anatomy 0.000 claims 1
- 230000002363 herbicidal effect Effects 0.000 claims 1
- 239000004009 herbicide Substances 0.000 claims 1
- 230000003993 interaction Effects 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 claims 1
- 235000010446 mineral oil Nutrition 0.000 claims 1
- 235000015097 nutrients Nutrition 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 117
- 239000003795 chemical substances by application Substances 0.000 description 61
- 239000000047 product Substances 0.000 description 38
- 235000010216 calcium carbonate Nutrition 0.000 description 29
- 239000000178 monomer Substances 0.000 description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 23
- 239000011575 calcium Substances 0.000 description 22
- 229910052791 calcium Inorganic materials 0.000 description 22
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 239000002952 polymeric resin Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical class OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001190 organyl group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Description
(12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C09C 1102 <2006 01> 05.07.2017 Bulletin 2017/27 (21) Application number: 14156165.4 (22) Date of filing: 21.02.2014 (54) Process for the preparation of a calcium carbonate filler product
Verfahren zur Herstellung eines Kalziumkarbonatfijllprodukts
Procede pour la pr6paration d’un produit de remplissage a base de carboante de calcium (84) Designated Contracting States: · GANE, Patrick A. C. AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 4852 Rothrist (CH)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR (74) Representative: Glas, Holger
Designated Extension States: Maiwald Patentanwalts GmbH BA ME Elisenhof
Elisenstrasse 3 (43) Date of publication of application: 80335 Miinchen (DE) 26.08.2015 Bulletin 2015/35 (56) References cited: (73) Proprietor: Omya International AG WO-A1-2012/055739 US-A- 4 136 830 4665 Oftringen (CH) US-A1- 2010 025 507
(72) Inventors: · GODARD P ET AL: "TENSILE BEHAVIOUR OF
• RENTSCH, Samuel POLYSTYRENE FILLED WITH CALCIUM
3095 Spiegel bei Bern (CH) CARBONATE", THE 5TH INTERNATIONAL • BLUM, Rene Vinzenz FILLERS CONFERENCE FILPLAS, 19-20 4915 St. Urban (CH) MAY1992, MANCHESTER, LONDON, GB, 19 May 1992 (1992-05-19), pages 1-16, XP000372034,
Description [0001] The present invention relates to a mineral filler product which may be used in a multitude of applications, for example in polymer compositions, in paper making, paper coatings, agricultural applications, paints, adhesives, sealants, construction applications, or cosmetic applications.
[0002] Well-known mineral fillers comprise, for example, natural ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC).
[0003] For the preparation of GCC it has been quite common to use polymers such as polyalkylene glycols or polymers based on partially or totally neutralized polyacrylic acids, polymethacrylic acids, their derivatives and salts thereof, as grinding aids and dispersing agents in a grinding process to provide aqueous mineral suspensions.
[0004] In EP 2 029 677, a process for dry grinding a material containing a carbonate ore is described, said process includes the steps of dry grinding said material in at least one grinding unit in the presence of at least one polyalkylene glycol polymer in such manner that the quantity of water in the grinding unit is less than 10 wt.-%, based on the dry material in said grinding unit. The process may further comprise an optional classifying step, wherein both the grinding step and the latter classifying step may be carried out repeatedly with all or part of the material obtained in the dry grinding step and/or in the classifying step.
[0005] EP 2 132 268 provides a method for dry grinding of one or more mineral materials which include at least one calcium carbonate. The method includes the steps of crushing the mineral material(s) in at least one crushing unit, dry grinding the crushed material in at least one grinding unit in the presence of a comb-type hydrophilic polymer containing at least one polyalkylene oxide, wherein the quantity of liquid in the grinding unit is less than 15 wt.-%, based on the dry material crushed in said crushing unit. The process may further comprise an optional classifying step, wherein both the grinding step and the latter classifying step may be carried out repeatedly with all or part of the material obtained in the dry grinding step and/or in the classifying step.
[0006] WO 2011/077232 relates to the use of formulations containing glycerol and/or polyglycerols as an agent during dry grinding to improve the self-dispersing properties of said mineral material in an aqueous composition. The viscosity of the final composition is thus reduced and kept stable over time. Furthermore, the amount of foam formed during the dispersing step is reduced.
[0007] Attempts have also been made to improve the applicability of particulate mineral materials and especially calcium carbonate-containing mineral fillers, e.g., by treating such materials with higher aliphatic carboxylic acids, which in some cases may also be referred to as fatty acids, and aliphatic carboxylic acid salts. For instance, WO 00/20336 relates to an ultrafine natural calcium carbonate which may optionally be treated with one or more several fatty acids or one or more several salts, or mixtures thereof, and which is used as a rheology regulator for polymer compositions.
[0008] Likewise, US 4,407,986 relates to a precipitated calcium carbonate that is surface-treated with a dispersant that may include higher aliphatic acids and their metal salts in order to limit the addition of lubricant additives when kneading this calcium carbonate with crystalline polypropylene and to avoid the formation of calcium carbonate aggregates that limit the impact strength of the polypropylene.
[0009] In EP 0 325 114 relating to non-sagging underseal compositions for motor vehicles based on polyvinyl chloride which has improved rheological and adhesion properties, a mixture of an ammonium salt of 12-hydroxystearic acid in combination with a fatty acid (in a weight ratio of 1:1) is used to treat a mineral filler.
[0010] The article "Tensile behaviour of polystyrene filled with calcium carbonate" by P. Godard and Y. Bomal, The 5th International Fillers Conference Filplas, 19-20 May 1992, Manchester, London, GB, XP000372034, refers to the tensile behavior of polystyrene filled with calcium carbonate. The calcium carbonate may be surface-treated with a statistical styrene-maleic anhydride copolymer.
[0011] US 2010/025507 refers to a method for dry grinding of one or more mineral materials consisting of at least one calcium carbonate. The grinding takes place in the presence of at least one comb-type hydrophilic polymer containing at least one polyalkylene oxide function grafted onto at least one unsaturated ethylene monomer.
[0012] US 4,136,830 refers to an ore grinding process containing copolymer grinding aids. The copolymer grinding aids comprise copolymers of styrene with maleic anhydride, itaconicor citraconic acids dispersible in the liquid medium.
[0013] Moreover, particulate mineral materials may also be treated with other surface-treatment agents, such as silanes, siloxanes, phosphates, phosphonates, oxalates, succinates, fluorides, natural or synthetic polymers, or mixtures thereof in order to hydrophobize the surface of said mineral material.
[0014] However, in many cases, the preparation of calcium carbonate-containing mineral filler products by use of the aforementioned grinding agents and dispersants leads to a poor quality. For example, the use of grinding agents often results in a high water pick up susceptibility of the resulting mineral filler product. Particulate calcium carbonate-containing materials having high moisture pick up susceptibilities may also be disadvantageous when used as filler in polymer compositions. For example, such materials may pick up moisture during storage, transportation, and/or processing which, in turn, may lead to the formation of voids in polymer compositions produced in a melt extrusion process.
[0015] Although related to a wet grinding process, EP 0 998 522 discloses suspensions being ground in the absence of dispersant or in presence of only sub-efficient amounts, which are then dried and used as a filler in polymer products. As a general rule, the prior art teaches to use neither any dispersant nor grinding agent for the either dry or wet grinding of calcium carbonate if intended for the use as a filler in polymer products.
[0016] In view of the foregoing, the expert is still faced with the problem of efficient production of dry ground fillers for the application in plastics, such as polyolefins, without a decrease in quality. Still today, dry grinding processes have several disadvantages. For example, the absence of grinding agents and dispersants results in a low throughput and low grinding efficiency which, in turn, leads to an overall increase in energy consumption.
[0017] There is still a need to provide mineral filler products and processes for their preparation which may reduce or avoid one or more of the aforementioned technical drawbacks.
[0018] It is thus an object of the present invention to provide a process for the preparation of a mineral filler product which may be carried under high throughput and high grinding efficiency. Another object may also be seen in the provision of a more efficient process for the provision of a mineral filler product having a relatively low moisture pick up susceptibility.
[0019] One or more of the foregoing and other problems are solved by the subject-matter as defined herein in the independent claims.
[0020] A first aspect of the present invention relates to a process for the preparation of a mineral filler product, said process comprising the steps of: a) providing a calcium carbonate-containing material; b) providing at least one grinding agent; c) dry grinding the calcium carbonate-containing material in a mixture obtained by contacting: i) the calcium carbonate-containing material provided in step a), with ii) the at least one grinding agent provided in step b) in at least one grinding unit to obtain a dry ground mineral filler; d) classifying the dry ground mineral filler of step c) to obtain a coarse fraction and a fine fraction, wherein the coarse fraction is removed or subjected to dry grinding step c) and the fine fraction represents a fine mineral filler; and e) optionally drying the fine mineral filler of step d) to obtain a dried mineral filler having a total moisture content of less than 1.0 wt.-%, based on the total weight of said dried mineral filler; wherein the total moisture content in the mixture of step c) is less than or equal to 10.0 wt.-%, based on the total weight of said mixture; the amount of the at least one grinding agent provided in step b) ranges from 0.05 to 150 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method; the temperature in step c) ranges from 65 °C to 200 °C; and the at least one grinding agent is selected from the group consisting of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers, and has a monomer unit ratio (styrene units : maleic anhydride units, S:MA) of from 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol.
[0021] According to the process of the present invention, the mineral filler product can be prepared from a calcium carbonate-containing material, for example from marble, limestone, chalk, dolomite, and the like, in a dry grinding process. The present invention makes use of at least one grinding agent selected from the group of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers instead of conventional agents, such as mono-or polyalkylene glycols or polyacrylates. For this purpose, a calcium carbonate-containing material is provided and subjected to a dry grinding step in a grinding unit (e.g., a ball mill) at elevated temperatures ranging from 65 °C to 200 °C. The grinding agent may be contacted with said calcium carbonate-containing material prior to the grinding step or during dry grinding. Upon addition of the grinding agent and during the grinding step, a layer may be formed on at least part of the surface of the dry ground mineral filler. Said layer may comprise the styrene-maleic anhydride co-polymers or derivatives of styrene-maleic anhydride co-polymers. It may also comprise the corresponding reaction products of the grinding agent(s) which may result from the reaction of said agent(s), for example, with the calcium carbonate-containing material. Typically, said reaction products are reaction products resulting from the reaction of the grinding agent(s) with the surface of the calcium carbonate-containing material. Subsequently to the grinding step, the dry ground mineral filler is subjected to a classifying step. In said classifying step, the dry ground mineral filler is divided into a coarse fraction and a fine fraction. Whereas the fine fraction represents the final product which, optionally, may be subjected to a drying step to remove at least part of the moisture (i.e. water) in order to obtain a dried mineral filler having a moisture content of less than 1.0 wt.-%, the coarse fraction may be removed or may be recycled by subjecting same again to dry grinding step c). In order to achieve optimal grinding efficiency and optimal quality of the obtained mineral filler product, the at least one grinding agent has a monomer unit ratio (styrene units : maleic anhydride units, S :MA) of from 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol.
[0022] Another aspect of the present invention relates to a mineral filler product. Said product is obtained by the process according to the present invention and has a volatile onset temperature of at least or equal to 200 °C.
[0023] Still another aspect of the present invention relates to the use of the inventive mineral filler product in a polymer composition, in paper making, paper coatings, agricultural applications, paints, adhesives, sealants, construction applications, and/or cosmetic applications.
[0024] Advantageous embodiments of the process according to the present invention and embodiments of the mineral filler product obtained by the process according to the present invention are defined in the corresponding subclaims.
[0025] According to one embodiment, the calcium carbonate-containing material provided in step a) is selected from natural calcium carbonate sources and preferably is selected from the group consisting of marble, limestone, chalk, dolomite, and mixtures thereof.
[0026] According to another embodiment, the amount of said at least one grinding agent provided in step b) ranges from 0.01 to 10.0 wt.-%, preferably from 0.05 to 5.0 wt.-%, more preferably from 0.1 to 3.0 wt.-%, and most preferably from 0.15 to 2.0 wt.-%, based on the total dry weight of the calcium carbonate-containing material.
[0027] According to another embodiment, the at least one grinding agent provided in step b) has a monomer unit ratio (S :MA) of from 1:1 to 5:1, preferably from 1:1 to 4:1, and more preferably from 1:1 to 3:1.
[0028] According to another embodiment, the at least one grinding agent provided in step b) has a molecular weight Mw of from 2Ό00 to 30Ό00 g/mol and preferably from 3Ό00 to 25Ό00 g/mol.
[0029] According to still another embodiment, the at least one grinding agent provided in step b) is partially or fully neutralized with cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0030] According to another embodiment, the total moisture content in the mixture of step c) is less than or equal to 5.0 wt.-%, preferably less than or equal to 2.0 wt.-%, and more preferably less than or equal to 1.0 wt.-%, based on the total weight of said mixture.
[0031] According to still another embodiment, the temperature in step c) ranges from 70 °C to 180 °C, preferably from 75 °C to 160 °C, and more preferably from 80 °C to 150 °C.
[0032] According to still another embodiment, the fine mineral filler of step d) has a weight median particle size d50 ranging from 0.4 to 40.0 μηι, preferably from 0.6 to 20.0 μηι, and more preferably from 0.7 to 10.0 μηι.
[0033] According to another embodiment, the process comprises a further step of treating the fine mineral filler of step d) and/or the dried mineral filler of step e) with a hydrophobizing agent to obtain a surface-treated product having a treatment layer on at least part of the surface of said product.
[0034] According to another embodiment, the product obtained after treating the fine mineral filler of step d) and/or the dried mineral filler of step e) has a moisture pick up susceptibility of less than or equal to 0.9 mg/g, preferably less than or equal to 0.8 mg/g, more preferably less than or equal to 0.7 mg/g, and most preferably from 0.2 to 0.6 mg/g.
[0035] According to another embodiment, said product has a volatile onset temperature of at least or equal to 230 °C, preferably at least or equal to 250 °C.
[0036] According to another embodiment, the mineral filler product is used in a polymer composition, said polymer composition comprises: a) at least one polymeric resin; and b) from 0.1 to 90.0 wt.-%, preferably from 1.0 to 85.0 wt.-%, and more preferably from 2.0 to 45.0 wt.-%, based on the total weight of said polymer composition, of the mineral filler product obtained by the process according to the present invention.
[0037] It should be understood that for the purposes of the present invention, the following terms have the following meanings:
The term "filler" in the meaning of the present invention refers to substances which may be added to materials, such as polymers, elastomers, paints, or adhesives, e.g. to lower the consumption of more expensive materials or to improve material or mechanical properties of the resulting products. The person skilled in the art very well knows the fillers, typically mineral fillers, used in the respective field.
[0038] The term "dry ground" or "dry grinding" in the meaning of the present invention refers to the comminution of a solid material by using a mill (e.g., by means of a ball mill), wherein said material to be ground has a total moisture content of less than or equal to 10 wt.-%, based on the total weight of said material.
[0039] The terms "coarse" and "fine" as used herein describe the particle size of two fractions of a particulate material relative to each other and, thus, do not imply a specific particle size or size range. Unless indicated otherwise, both terms refer to the relative weight median particle sizes d50. In this respect, the term "fine fraction" indicates that the weight median particle size d50 of said fraction is smaller than the weight median particle size d50 of the corresponding "coarse fraction".
[0040] Unless specified otherwise, the terms "drying" refers to a process according to which at least a portion of water is removed from a material to be dried such that a constant weight of the obtained "dried" material at 120 °C is reached. Moreover, a "dried" material may be further defined by its total moisture content which, unless specified otherwise, is less than or equal to 1.0 wt.-%, preferably less than or equal to 0.5 wt.-%, more preferably less than or equal to 0.2 wt.-%, and most preferably between 0.03 and 0.07 wt.-%, based on the total weight of the dried material.
[0041] The "total moisture content" of a material refers to the percentage of moisture (i.e. water) which may be desorbed from a sample upon heating to 220 °C.
[0042] A "natural calcium carbonate source" may beany natural material comprising calcium carbonate. Such materials comprise, for example, marble, limestone, chalk, dolomite, and the like.
[0043] The "moisture pick up susceptibility" of a material refers to the amount of moisture absorbed on the surface of said material within a certain time upon exposure to a defined humid atmosphere and is expressed in mg/g. The "normalized moisture pick up susceptibility" of a material refers to the amount of moisture absorbed on the surface of said material within a certain time upon exposure to a defined humid atmosphere and is expressed in mg/m2.
[0044] The term "volatile onset temperature" in the meaning of the present application refers to a temperature at which volatiles - including volatiles introduced as a result of the present process - begin to evolve, as observed on a thermo-gravimetric (TGA) curve, plotting the mass of remaining sample (y-axis) as a function of temperature (x-axis), the preparation and interpretation of such a curve being defined hereafter in the experimental part.
[0045] Throughout the present application, the particle size of a fraction of a particulate material is described by its particle size distribution. The value dx represents the diameter relative to which x% by weight of the particles have diameters less than dx. This means, for example, that the d98 value (also referred to as the "topcut") is the particle size at which 98 wt.-% of all particles of a fraction are smaller than the indicated value. The d50 value is thus the "weight median particle size" at which 50 wt.-% of all particles are smaller than the indicated particle size.
[0046] Unless stated otherwise, the "molecular weight" or "Mw" of a polymer as used herein refers to the weight average molecular weight as measured according to the method described hereinafter.
[0047] 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 anything else is specifically stated.
[0048] Where the term "comprising" is used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term "consisting of is considered to be a preferred embodiment of the term "comprising". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is also to be understood to disclose a group, which preferably consists only of these embodiments.
[0049] Terms like "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. This, e.g., means that, unless the context clearly dictates otherwise, the term "obtained" does not mean to indicate that, e.g., an embodiment must be obtained by, e.g., the sequence of steps following the term "obtained" though such a limited understanding is always included by the terms "obtained" or "defined" as a preferred embodiment.
[0050] According to the process of the present invention, a mineral filler product may be prepared from a calcium carbonate-containing material. Said process comprises a dry grinding step which is carried out in the presence of at least one grinding agent selected from styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers. The presence of said at least one grinding agent during dry grinding leads to a dry ground mineral filler which may provide a layer on at least a part of the surface of the dry ground mineral filler, wherein said layer may comprise said at least one grinding agent. As will be discussed herein later in more detail, the presence of said at least one grinding agent during the dry grinding step may also lead to the formation of reaction products resulting from the reaction of the calcium carbonate-containing material provided in step a) with said at least one grinding agent provided in step b). Said reaction product may also form part of the layer being present on at least a part of the surface of the dry ground mineral filler.
[0051] The inventors surprisingly found that the mineral filler product obtained by the process according to the present invention provides several advantages. For example, the at least one styrene-maleic anhydride co-polymer and/or at least one derivative of a styrene-maleic anhydride co-polymer may be used as a substitute for conventional grinding agents and dispersing agents, such as mono- or polyalkylene glycols or polyacrylates.
[0052] The problems described hereinabove with respect to the prior art may be solved by the process according to the present invention using efficient amounts of specific styrene-maleic anhydride co-polymers or derivatives thereof. The use of the grinding agents as described herein may result in higher mill capacities and a higher throughput. In turn, lower investments and smaller plant footprints for equal production capacities are required.
[0053] In the following, preferred embodiments of the process according to the present invention for the preparation of a mineral filler product will be discussed in more detail. It is to be understood that these details and embodiments also apply to the mineral filler product itself as well as to the use of said product in any of the disclosed applications.
Process step a) [0054] According to step a) of the process according to the present invention, a calcium carbonate-containing material is provided. In general, said calcium carbonate-containing material may be any calcium carbonate source and may be of natural or synthetic origin.
[0055] In some embodiments of the process according to the present invention, the calcium carbonate-containing material provided in step a) is selected from natural calcium carbonate sources, preferably containing from 50 to 98 wt.-% of calcium carbonate, based on the total weight of said calcium carbonate-containing material.
[0056] According to one embodiment, the calcium carbonate-containing material contains at least 50 wt.-%, preferably at least 70 wt.-%, more preferably at least 80 wt.-%, even more preferably at least 90 wt.-%, and most preferably from 90 to 98 wt.-% of calcium carbonate, based on the total weight of said calcium carbonate-containing material.
[0057] According to another embodiment, the calcium carbonate-containing material provided in step a) is selected from the group consisting of marble, limestone, chalk, dolomite, and mixtures thereof.
[0058] According to a preferred embodiment, the calcium carbonate-containing material provided in step a) is selected from the group consisting of marble, limestone, chalk, and mixtures thereof.
[0059] In cases where the calcium carbonate is of synthetic origin, the calcium carbonate-containing may be precipitated calcium carbonate (PCC). A PCC in the meaning of the present invention is a synthesized material, generally obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment or by precipitation of a calcium- and a carbonate source in water. Additionally, precipitated calcium carbonate can also be the product of introducing calcium and carbonate salts, calcium chloride and sodium carbonate, for example, in an aqueous environment. PCC may be vaterite, calcite or aragonite. PCCs are described, for example, in EP 2 447 213, EP 2 524 898, EP 2 371 766, or unpublished European patent application No. 12 164 041.1.
[0060] Suitably, the calcium carbonate-containing material of step a) is provided as a solid material being in particulate form. In this respect, the calcium carbonate-containing material provided in step a) may have any particle size distribution allowing the material to be subjected to a dry grinding step. Therefore, the calcium carbonate-containing material may be provided as a comminuted material, for example, in crushed or preground form.
[0061] According to one embodiment, the calcium carbonate-containing material provided in step a) has a weight median particle size d50 ranging from 5.0 to 600.0 μ(η and preferably from 50.0 to 300.0 μ(η.
Process step b) [0062] According to step b) of the process according to the present invention, at least one grinding agent is provided. A "grinding agent" in the meaning of the present invention may be any compound which may be added prior to and/or during a grinding step (e.g., dry grinding) in order to enhance the grinding performance.
[0063] The inventors surprisingly found that it is of particular advantage to use at least one grinding agent selected from the group consisting of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride copolymers, wherein said grinding agent has a monomer unit ratio (styrene units : maleic anhydride units, S:MA) of from 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol.
[0064] For the purpose of the present invention, styrene-maleic anhydride co-polymers (SMAs) may be defined by their "monomer unit ratio" of the polymer chain, i.e. by the monomer unit ratio (S:MA) of styrene units (S) to maleic anhydride (MA) units.
[0065] Unless indicated otherwise, the ratio (S:MA) is used likewise to define the monomer unit ratio of: " derivatives of styrene-maleic anhydride co-polymers (SMA derivatives); * reaction products of styrene-maleic anhydride co-polymers (reaction products of SMAs); and * reaction products of derivates of styrene-maleic anhydride co-polymers (reaction products of SMA derivatives).
[0066] Said reaction products typically result from the reaction of the calcium carbonate-containing material provided in step a) with said at least one grinding agent provided in step b).
[0067] As will become more apparent from the embodiments herein below, the monomer unit ratio (S:MA) thus, on the one hand, includes styrene units, modified styrene units (present in SMA derivatives) and reaction products of both and, on the other hand, includes maleic anhydride units, modified maleic anhydride units (present in SMA derivatives) and reaction products of both.
[0068] Styrene-maleic anhydride co-polymers in the meaning of the present invention may be any polymers obtainable by co-polymerizing styrene and maleic anhydride, e.g., linear or branched random co-polymers, linear or branched block co-polymers, ora mixture thereof.
[0069] Therefore, according to one embodiment, the at least one grinding agent is selected from virgin styrene-maleic anhydride co-polymers, i.e. from unmodified styrene-maleic anhydride co-polymers (in the art also referred to as SMA or SMAnh).
[0070] According to a preferred embodiment, the at least one grinding agent is selected from derivatives of styrene-maleic anhydride co-polymers (SMA derivatives), preferably said at least one grinding agent is selected from derivatives of styrene-maleic anhydride co-polymers having partially or fully hydrolyzed maleic anhydride units and/or partially or fully esterified maleic anhydride units and/or partially or fully amidized maleic anhydride units and/or partially or fully imidized maleic anhydride units.
[0071] Derivatives of styrene-maleic anhydride co-polymers (SMA derivatives) may be any polymers obtainable by: a) co-polymerizing styrene and maleic anhydride to obtain co-polymers and further subjecting said co-polymers to a modification step; or b) co-polymerizing a mixture comprising a styrene monomer and a maleic anhydride monomer to obtain co-polymers, wherein at least a part of one or both of the two monomers is a modified monomer and, optionally, subjecting said co-polymers to a modification step.
[0072] In a preferred embodiment, SMA derivatives may be any polymers obtainable by co-polymerizing styrene and maleic anhydride to obtain co-polymers and further subjecting said co-polymers to a modification step.
[0073] Said modification of the co-polymers typically leads to a partial orfull modification of the styrene-maleic anhydride co-polymers, i.e. to styrene-maleic anhydride co-polymers having partially or fully modified monomer units. Accordingly, the derivatives of styrene-maleic anhydride co-polymers in the meaning of the present invention may have partially or fully modified styrene units and/or partially or fully modified maleic anhydride units, preferably partially modified styrene units and/or partially modified maleic anhydride units, and more preferably fully modified styrene units and/orfully modified maleic anhydride units.
[0074] Unless dictated otherwise, the term "partially modified" as used herein indicates that SMA derivatives still comprise unmodified monomer unit(s), e.g., unmodified styrene units or unmodified maleic anhydride units. In contrast thereto, the term "fully modified" indicates that any monomer unit present in an SMA derivative is modified, e.g., any styrene unit or any maleic anhydride unit. The same meaning also applies to more specific modifications: In this respect, the term "partially hydrolyzed maleic anhydride units", for example, means that a derivative of a styrene-maleic anhydride co-polymer may still comprise non-hydrolyzed maleic anhydride units, whereas the term "fully hydrolyzed maleic anhydride units" means that all maleic anhydride units of the SMA derivative are in a hydrolyzed form.
[0075] According to one embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully modified maleic anhydride units, preferably having partially modified maleic anhydride units, and more preferably having fully modified maleic anhydride units.
[0076] According to another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers obtainable by co-polymerizing styrene and maleic anhydride to obtain co-polymers and further subjecting said co-polymers to a modification step, said derivatives having partially or fully modified maleic anhydride units, preferably having partially modified maleic anhydride units, and more preferably having fully modified maleic anhydride units.
[0077] According to one embodiment, the modification step comprises the reaction with metal hydroxides, ammonia, amines, imines, alcohols, carboxylic acids, mineral acids, and mixtures thereof.
[0078] According to a preferred embodiment, the modification step comprises the reaction with metal hydroxides, preferably alkali metal hydroxides, and more preferably sodium hydroxide, potassium hydroxide, and mixtures thereof.
[0079] Therefore, the derivatives of styrene-maleic anhydride co-polymers may be selected from styrene-maleic anhydride co-polymers obtainable by co-polymerizing styrene and maleic anhydride to obtain co-polymers and further subjecting said co-polymers to a modification step comprising the reaction with metal hydroxides, ammonia, amines, imines, alcohols, carboxylic acids, mineral acids, and mixtures thereof, said derivatives having partially or fully modified maleic anhydride units, preferably having partially modified maleic anhydride units, and more preferably having fully modified maleic anhydride units.
[0080] According to another embodiment, the modification step comprises the reaction with alkali metal hydroxides, ammonia, primary amines, C1-C10 alcohols, C1-C10 carboxylic acids, hydrochloric acid, phosphoric acid, sulfuric acid, and mixtures thereof.
[0081] According to another embodiment, the derivatives of styrene-maleic anhydride co-polymers thus are selected from styrene-maleic anhydride co-polymers obtainable by co-polymerizing styrene and maleic anhydride to obtain copolymers and further subjecting said co-polymers to a modification step comprising the reaction with alkali metal hydroxides, ammonia, primary amines, C1-C10 alcohols, C1-C10 carboxylic acids, hydrochloric acid, phosphoric acid, sulfuric acid, and mixtures thereof, said derivatives having partially or fully modified maleic anhydride units, preferably having partially modified maleic anhydride units, and more preferably having fully modified maleic anhydride units.
[0082] According to another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers obtainable by co-polymerizing styrene and maleic anhydride to obtain co-polymers and further subjecting said co-polymers to a modification step comprising the reaction with sodium hydroxide, potassium hydroxide, and mixtures thereof, said derivatives having partially or fully modified maleic anhydride units, preferably having partially modified maleic anhydride units, and more preferably having fully modified maleic anhydride units.
[0083] As disclosed hereinabove, the derivatives of styrene-maleic anhydride co-polymers may be styrene-maleic anhydride co-polymers having partially or fully modified styrene units and/or partially or fully modified maleic anhydride units, and preferably said SMA derivatives may be styrene-maleic anhydride co-polymers having partially or fully modified maleic anhydride units. The term "modified" as used herein indicates that a polymer comprises monomer units which may be obtainable from modifications steps, for example, by the formation of hydrolysates (e.g., hydrolyzed maleic anhydride units), esters (e.g., esterified maleic anhydride units), amides (e.g., amidized maleic anhydride units), and imides (e.g., imidized maleic anhydride units).
[0084] In this respect, styrene-maleic anhydride co-polymers having hydrolyzed maleic anhydride units, for example, may comprise carboxyl groups [-C(=0)0H] and/or carboxylate groups [-C(=0)0-]. Accordingly, styrene-maleic anhydride co-polymers having esterified maleic anhydride units may comprise estergroups [-C(=0)0R] resulting from a modification step using alcohols, such as methanol, ethanol, and the like, whereas styrene-maleic anhydride co-polymers having amidized maleic anhydride units may comprise amide moieties [-C(=0)NHR] resulting from a modification step using amines, such as ammonia, primary amines (e.g., methylamine, dimethylaminopropylamine), and secondary amines (e.g., dimethylamine). Imide moieties [-C(=0)NHC(=0)-] as present in styrene-maleic anhydride co-polymers having imidized maleic anhydride units may also result from modifications using amines such as ammonia or primary amines (e.g., methylamine, dimethylaminopropylamine) but, however, require a nucleophilic substitution with a single amine moiety on both carbonyl groups of the maleic anhydride unit.
[0085] In general, a modification of the maleic anhydride unit - from a chemical point of view - may comprise at least one modification at the first carbonyl group and, alternatively, another nucleophilic substitution at the second carbonyl group of the maleic anhydride unit. In particular, this applies to styrene-maleic anhydride co-polymers having partially or fully esterified maleic anhydride units as well as to styrene-maleic anhydride co-polymers having partially or fully amidized maleic anhydride units which thus may comprise mono- and/or diester units (i.e. "monoesterified" and/or "diesterified" maleic anhydride units) as well as mono- and diamide monomer units (i.e. "monoamidized" and/or "dia-midized" maleic anhydride units).
[0086] If not indicated otherwise, the terms "esterified maleic anhydride units" and "amidized maleic anhydride units" encompasses both mono- and dimodified maleic anhydride units.
[0087] As already outlined above, imidized styrene-maleic anhydride co-polymers are formed by a substitution at both carbonyl groups of a maleic anhydride unit which, in turn, renders a further specification redundant. In case of hydrolytic modifications, e.g., in a modification step using a metal hydroxide, a dicarboxylic acid or dicarboxylate unit is already obtained after nucleophilic substitution at the first carbonyl group. Consequently the term "hydrolyzed" implies the presence of two carboxylic groups [-C(=0)OH or -C(=0)0‘ or both] and does also not require any specification whether the maleic anhydride group is monohydrolyzed or dihydrolyzed.
[0088] According to one embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully hydrolyzed maleic anhydride units and/or partially or fully esterified maleic anhydride units and/or partially or fully amidized maleic anhydride units and/or partially or fully imidized maleic anhydride units.
[0089] According to one embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully hydrolyzed maleic anhydride units, preferably having partially hydrolyzed maleic anhydride units, and more preferably having fully hydrolyzed maleic anhydride units.
[0090] According to one embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially orfully esterified maleic anhydride units, preferably having partially esterified maleic anhydride units, and more preferably having fully esterified maleic anhydride units.
[0091] According to one embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially orfully amidized maleic anhydride units, preferably having partially amidized maleic anhydride units, and more preferably having fully amidized maleic anhydride units.
[0092] According to one embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially orfully imidized maleic anhydride units, preferably having partially imidized maleic anhydride units, and more preferably having fully imidized maleic anhydride units.
[0093] According to a preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having: a) partially orfully hydrolyzed maleic anhydride units; and/or b) partially or fully mono- and/or diesterified maleic anhydride units; and/or c) partially or fully mono- and/or diamidized maleic anhydride units; and/or d) partially or fully imidized maleic anhydride units.
[0094] According to another preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having: a) partially hydrolyzed maleic anhydride units; and/or b) partially mono- and/or diesterified maleic anhydride units; and/or c) partially mono- and/or diamidized maleic anhydride units; and/or d) partially imidized maleic anhydride units.
[0095] According to still another preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having: a) fully hydrolyzed maleic anhydride units; and/or b) fully mono- and/or diesterified maleic anhydride units; and/or c) fully mono- and/or diamidized maleic anhydride units; and/or d) fully imidized maleic anhydride units.
[0096] According to another embodiment of the present invention, the derivatives of styrene-maleic anhydride copolymers may be partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof, meaning that protons present in the derivatives of styrene-maleic anhydride co-polymers may be partially or fully replaced by any of the aforementioned cations. Said neutralization may be achieved, for exam pie, by adjustment to a specific pH value using reagents such as metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), amines (e.g., ammonia, polyethylenimine), or imines. Typical protons that may be replaced are those found in carboxylic acids [-C(=0)OH], sulfonic acids [-S(=0)2OH], and/or imides [-C(=0)NHC(=0)-]. The skilled person knows how to partially or fully replace protons by mono- or divalent cations and also knows how to determine whether a derivative is partially or fully neutralized.
[0097] However, in cases where the derivatives of styrene-maleic anhydride co-polymers comprise basic groups (e.g., amines), the derivatives of a styrene-maleic anhydride co-polymers may also be neutralized by the addition of C1-C10 carboxylic acids (e.g., acetic acid), mineral acids (e.g., hydrochloric acid, phosphoric acid, or sulfuric acid), and mixtures thereof.
[0098] Accordingly, the derivatives of styrene-maleic anhydride co-polymers may be selected from styrene-maleic anhydride co-polymers having partially or fully modified styrene units and/or partially or fully modified maleic anhydride units, wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0099] According to another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully hydrolyzed maleic anhydride units and/or partially or fully esterified maleic anhydride units and/or partially or fully amidized maleic anhydride units and/or partially or fully imidized maleic anhydride units, wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0100] According to a preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having: a) partially or fully hydrolyzed maleic anhydride units; and/or b) partially or fully mono- and/or diesterified maleic anhydride units; and/or c) partially or fully mono- and/or diamidized maleic anhydride units; and/or d) partially or fully imidized maleic anhydride units; wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0101] According to still another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully hydrolyzed maleic anhydride units, preferably having partially hydrolyzed maleic anhydride units, and more preferably having fully hydrolyzed maleic anhydride units, wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0102] According to still another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully esterified maleic anhydride units, preferably having partially esterified maleic anhydride units, and more preferably having fully esterified maleic anhydride units, wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0103] According to still another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully amidized maleic anhydride units, preferably having partially amidized maleic anhydride units, and more preferably having fully amidized maleic anhydride units, wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0104] According to still another embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having partially or fully imidized maleic anhydride units, preferably having partially imidized maleic anhydride units, and more preferably having fully imidized maleic anhydride units, wherein said derivatives are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0105] In another embodiment of the present invention, the derivatives of styrene-maleic anhydride co-polymers further comprise partially or fully modified styrene units, preferably the partially or fully modified styrene units are fully or partially sulfonated styrene units, more preferably the partially or fully modified styrene units are partially sulfonated styrene units, and most preferably the partially or fully modified styrene units are fully sulfonated styrene units.
[0106] According to a preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers thus are selected from styrene-maleic anhydride co-polymers having: a) maleic anhydride units being i) partially or fully hydrolyzed; and/or ii) partially or fully mono- and/or diesterified; and/or iii) partially or fully mono- and/or diamidized; and/or iv) partially or fully imidized; and/or b) styrene units being partially or fully sulfonated; wherein said derivatives of styrene-maleic anhydride co-polymers are partially or fully neutralized with mono-or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0107] According to another preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers thus are selected from styrene-maleic anhydride co-polymers having: a) maleic anhydride units being i) partially hydrolyzed; and/or ii) partially mono- and/or diesterified; and/or iii) partially mono- and/or diamidized; and/or iv) partially imidized; and/or b) styrene units being partially or fully sulfonated; wherein said derivatives of styrene-maleic anhydride co-polymers are partially or fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0108] According to still another preferred embodiment, the derivatives of styrene-maleic anhydride co-polymers are selected from styrene-maleic anhydride co-polymers having: a) maleic anhydride units being i) fully hydrolyzed; or ii) fully mono- and/or diesterified; or iii) fully mono- and/or diamidized; or iv) fully imidized; and/or b) styrene units being partially or fully sulfonated; wherein said derivatives of styrene-maleic anhydride co-polymers are fully neutralized with mono- or divalent cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof.
[0109] The styrene-maleic anhydride co-polymers having partially or fully esterified (mono- and/or diesterified) maleic anhydride units and/or partially or fully amidized (mono- and/or diamidized) maleic anhydride units and/or partially or fully imidized maleic anhydride units, may be substituted with linear, branched, aliphatic, cyclic, saturated and unsaturated organyl groups, preferably said organyl groups have a total amount of carbon atoms from C1 to C10, more preferably from C1 to C5, and most preferably from C1 to C3.
[0110] For the purposes of the present invention, the at least one grinding agent (i.e. both the styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers) provided in step b) may have a monomer unit ratio (styrene units : maleic anhydride units, S:MA) of from 1:2 to 15:1.
[0111] According to one embodiment, the at least one grinding agent provided in step b) has a monomer unit ratio (S:MA) of from 1:1 to 5:1, preferably from 1:1 to 4:1, and more preferably from 1:1 to 3:1.
[0112] Additionally or alternatively, the at least one grinding agent may also be defined by its molecular weight Mw which may be in the range from 500 to 40Ό00 g/mol.
[0113] According to another embodiment, the at least one grinding agent provided in step b) has a molecular weight Mw of from T000 to 40Ό00 g/mol, preferably from 2Ό00 to 30Ό00 g/mol, and more preferably from 3Ό00 to 25Ό00 g/mol.
[0114] According to still another embodiment, the at least one grinding agent provided in step b) has a molecular weight Mw of from T000 to 40Ό00 g/mol and a monomer unit ratio (S:MA) of from 1:1 to 5:1, preferably from 1:1 to 4:1, and more preferably from 1:1 to 3:1.
[0115] According to still another embodiment, the at least one grinding agent provided in step b) has a molecular weight Mw of from 2Ό00 to 30Ό00 g/mol and a monomer unit ratio (S:MA) of from 1:1 to 5:1, preferably from 1:1 to 4:1, and more preferably from 1:1 to 3:1.
[0116] According to still another embodiment, the at least one grinding agent provided in step b) has a molecular weight Mw of from 3Ό00 to 25Ό00 g/mol and a monomer unit ratio (S:MA) of from 1:1 to 5:1, preferably from 1:1 to 4:1, and more preferably from 1:1 to 3:1.
[0117] The at least grinding may be provided in undiluted form or in form of an aqueous solution. The undiluted form may comprise, for example, powders or flakes, being essentially free of water.
[0118] According to one embodiment of the present invention, the at least one grinding agent is thus provided in undiluted form, preferably containing less than or equal to 5.0 wt.-%, more preferably less than or equal to 2.0 wt.-%, even more preferably less than or equal to 1.5 wt.-%, and most preferably from 0.01 to 1.2 wt.-% of water, based on the total weight of said at least one grinding agent.
[0119] According to a preferred embodiment, the at least one grinding agent provided in step b) is provided in form of an aqueous solution.
[0120] In cases where the at least one grinding agent is provided as an aqueous solution, said solution may comprise a defined amount of said at least one grinding agent, wherein highly concentrated solutions may be preferred in order to keep the total moisture content in the mixture of grinding step c) at 10.0 wt.-% or below.
[0121] According to one embodiment, the at least one grinding agent provided in step b) is provided in form of an aqueous solution comprising from 5.0 to 50.0 wt.-%, preferably from 10.0 to 45.0 wt.-%, and more preferably from 20.0 to 40.0 wt.-%, based on the total weight of the solution, of said at least one grinding agent.
[0122] According to another embodiment, said aqueous solution has a pH value ranging from pH 4.0 to 12.0, preferably from pH 6.0 to 11.0, and more from pH 7.5 to 10.5.
[0123] The amount of the at least one grinding agent may be adjusted to the specific needs. In many cases, the amount of grinding agent may be based on the specific surface area of the carbonate-containing material provided in step a). According to the present invention, the amount of said at least one grinding agent provided in step b) ranges from 0.05 to 150 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method. Unless specifically stated, the amount of the at least one grinding agent is to be understood as a total amount. In cases where said grinding agent is added in one portion, the indicated amount thus refers to the amount of said one portion. Accordingly, in cases where the grinding agent is added in more than one portions, the indicated amount thus refers to the total amount of said portions.
[0124] In one embodiment of the process according to the present invention, the amount of said at least one grinding agent provided in step b) ranges from 0.1 to 100.0 mg/m2, preferably from 0.2 to 75.0 mg/m2, and more preferably from 0.2 to 50.0 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method.
[0125] According to another embodiment, the amount of said at least one grinding agent provided in step b) ranges from 0.1 to 25.0 mg/m2, preferably from 0.2 to 15.0mg/m2.
[0126] However, the amount of said at least one grinding agent provided in step b) may also be based on the total dry weight of the calcium carbonate-containing material provided in step a).
[0127] According to one embodiment, the amount of said at least one grinding agent provided in step b) thus ranges from 0.05 to 5.0 wt.-%, preferably from 0.1 to 3.0 wt.-%, and more preferably from 0.15 to 2.0 wt.-%, based on the total dry weight of the calcium carbonate-containing material.
[0128] According to another embodiment, the amount of said at least one grinding agent provided in step b) ranges from 0.01 to 1.0 wt.-%, preferably from 0.05 to 0.75 wt.-%, and more preferably from 0.1 to 0.5 wt.-%, based on the total dry weight of the calcium carbonate-containing material.
Process step c) [0129] According to step c) of the process according to the present invention, a mixture obtained by contacting the calcium carbonate-containing material provided in step a) with the at least one grinding agent provided in step b) is dry ground in at least one grinding unit to obtain a dry ground mineral filler.
[0130] The term "dry ground" or "dry grinding" in the meaning of the present invention refers to the comminution of a solid material by using a mill (e.g., by means of a ball mill), wherein said material to be ground has a total moisture content of less than or equal to 10 wt.-%, based on the total weight of said material.
[0131] For the purposes of the present invention, any suitable mill known in the art may be used. However, said at least one grinding unit preferably is a ball mill. It has to be noted that step c) is carried out by using at least one grinding unit, i.e. it is also possible to use a series of grinding units which may, for example, be selected from ball mills, semi-autogenous mills, or autogenous mills.
[0132] The amount of water being present in the mixture to be ground may be expressed by the total moisture content which is based on the total weight of said mixture. Typically, dry grinding processes are carried using mixtures having a total moisture of less than or equal to 10.0 wt.-%, based on the total weight of said mixture.
[0133] According to one embodiment, the total moisture content in the mixture of step c) is less than or equal to 5.0 wt.-%, preferably less than or equal to 2.0 wt.-%, and more preferably less than or equal to 1.0 wt.-%, based on the total weight of said mixture.
[0134] According to another embodiment, the total moisture content in the mixture of step c) is less than or equal to 5.0 wt.-%, preferably less than or equal to 2.0 wt.-%, and more preferably less than or equal to 1.0 wt.-%, based on the total weight of said mixture, wherein the total moisture content in the mixture of step c) preferably has a lower limit of 0.03 wt.-%, based on the total weight of said mixture.
[0135] According to still another embodiment of the process according to the present invention, the total moisture content in the mixture of step c) is less than or equal to 0.2 wt.-%, preferably less than or equal to 0.1 wt.-%, and more preferably between 0.03 and 0.07 wt.-%, based on the total weight of said mixture.
[0136] The calcium carbonate-containing material provided in step a) may undergo reactions with said at least one grinding agent provided in step b) upon contacting with each other said components to form a mixture. Said reaction products(s) may thus be present in the mixture of step c) but also may be present in any of the following process steps. Such reaction products(s) may be formed on the surface of the calcium carbonate-containing material which may result in one or more reaction product(s) being bound to the surface of the calcium carbonate-containing material. However, said reaction product(s) may also be present in the mixture without being bound to any other component present in said mixture of step c) or in any of the following process steps.
[0137] Therefore, in one embodiment of the process according to the present invention, the mixture of step c) may be obtained by contacting: i) the calcium carbonate-containing material provided in step a), with ii) the at least one grinding agent provided in step b), wherein at least a part of one or both components may be present in said mixture in form of one or more reaction products resulting from the reaction of the calcium carbonate-containing material provided in step a) with said at least one grinding agent provided in step b).
[0138] According to another embodiment, said mixture of step c) comprises one or more lithium, sodium, potassium, strontium, calcium, magnesium and/or aluminum salts of the at least one grinding agent provided in step b).
[0139] According to step c) of the process according to the present invention, a mixture obtained by contacting a calcium carbonate-containing material with at least one grinding agent is dry ground in at least one grinding unit to obtain a dry ground mineral filler.
[0140] In this respect, it is possible to obtain the mixture to be ground in step c) of the process according to the present invention by contacting with each other the components provided in steps a) and b) prior to or during grinding step c). In addition, it is also possible to obtain said mixture by contacting with each other the components in one or more portions prior to or during grinding.
[0141] According to one embodiment, the mixture of grinding step c) is obtained prior to said grinding step by simultaneously contacting the calcium carbonate-containing material provided in step a) with the at least one grinding agent provided in step b).
[0142] According to another embodiment, the mixture of grinding step c) is obtained prior to said grinding step by simultaneously contacting the calcium carbonate-containing material provided in step a) with a first portion of the at least one grinding agent provided in step b), wherein a second portion of the at least one grinding agent is added during grinding step c).
[0143] It has further been found by the inventors that grinding step c) is preferably carried out at elevated temperatures. For the purposes of the process according to the present invention, a temperature ranging from 65 °C to 200 °C is particularly suitable.
[0144] According to another embodiment, the temperature in step d) ranges from 70 °C to 180 °C, preferably from 75 °C to 160 °C, and more preferably from 80 °C to 150 °C.
[0145] Process step c) involves the dry grinding of a mixture obtained by contacting a calcium carbonate-containing material and at least one grinding agent in at least one grinding unit to obtain a dry ground mineral filler.
[0146] In one embodiment, the dry ground mineral filler obtained after grinding step c) has a weight median particle d50 ranging from 0.5 to 100.0 μηι and preferably from 1.0 to 30.0 μηι.
Process step d) [0147] The dry ground mineral filler obtained in process step c) is subsequently subjected to classifying step d).
[0148] In said classifying step, the dry ground mineral filler of step c) is divided into at least two fractions, i.e. into a coarse fraction and a fine fraction.
[0149] A classifying step in general serves to divide a feed fraction having a certain particle size into a coarse fraction and a fine fraction each having different particle sizes. Typically, the coarse fraction has a d50 value being higher than that of the feed fraction, whereas the fine fraction has a d50 value being smaller than that of the feed fraction. For this purpose, screening devices as well as gravity-based devices, such as centrifuges or cyclones and any combination of the aforementioned devices may be used.
[0150] According to one embodiment, the dry ground mineral filler of step c) is classified using a cyclone.
[0151] According to another embodiment, the fine mineral filler of step d) has a weight median particle size d50 ranging from 0.4 to 40.0 μηι, preferably from 0.6 to 20.0 μ(η, and more preferably from 0.7 to 10.0 μην [0152] As already described above, the dry ground mineral filler of step c) is classified in step d) to obtain a coarse fraction and a fine fraction, wherein the coarse fraction is removed or subjected to dry grinding step c) and the fine fraction represents a fine mineral filler which may represent the final product or may be used in one or more following optional process step.
[0153] To also use the coarse fraction obtained in classifying step d), said coarse material may be recycled. Therefore, in a preferred embodiment, the coarse fraction of step d) is subjected to dry grinding step c).
Process step e) [0154] The process according to the present invention further comprises optional drying step e). In said drying step, the fine mineral filler obtained in classifying step d) is dried to obtain a dried mineral filler.
[0155] In some cases, the total moisture content in the mixture of dry grinding step c) may be very low. In these cases, for example, where the total moisture content in the mixture of step c) is less than or equal to 0.2 wt.-%, preferably less than or equal to 0.1 wt.-%, and more preferably between 0.03 and 0.07 wt.-%, based on the total weight of said mixture, the process according to the present invention does not comprise any drying step after classifying step d).
[0156] Therefore, according to one embodiment, the process for the preparation of a mineral filler product comprises the steps of: a) providing a calcium carbonate-containing material; b) providing at least one grinding agent; c) dry grinding the calcium carbonate-containing material in a mixture obtained by contacting: i) the calcium carbonate-containing material provided in step a), with ii) the at least one grinding agent provided in step b) in at least one grinding unit to obtain a dry ground mineral filler; and d) classifying the dry ground mineral filler of step c) to obtain a coarse fraction and a fine fraction, wherein the coarse fraction is removed or subjected to dry grinding step c) and the fine fraction represents a fine mineral filler; wherein the total moisture content in the mixture of step c) is less than or equal to 10.0 wt.-%, based on the total weight of said mixture; the amount of the at least one grinding agent provided in step b) ranges from 0.05 to 150 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method; the temperature in step c) ranges from 65 °C to 200 °C; and the at least one grinding agent is selected from the group consisting of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers, and has a monomer unit ratio (styrene units : maleic anhydride units, S:MA) of from 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol.
[0157] The mixture of step c) may also have a higher total moisture content but still being less than or equal to 10.0 wt.-%, based on the total weight of said mixture. For example, the total moisture content of said mixture may be less than or equal to 5.0 wt.-%, preferably less than or equal to 2.0 wt.-%, and more preferably less than or equal to 1.0 wt.-%, based on the total weight of said mixture. In these cases, a drying step following step c) may be mandatory in order to obtain a dried mineral filler having a total moisture content of less than 1.0 wt.-%, based on the total weight of said dried mineral filler.
[0158] According to another embodiment, the process for the preparation of a mineral filler product thus comprises the steps of: a) providing a calcium carbonate-containing material; b) providing at least one grinding agent; c) dry grinding the calcium carbonate-containing material in a mixture obtained by contacting: i) the calcium carbonate-containing material provided in step a), with ii) the at least one grinding agent provided in step b) in at least one grinding unit to obtain a dry ground mineral filler; d) classifying the dry ground mineral filler of step c) to obtain a coarse fraction and a fine fraction, wherein the coarse fraction is removed or subjected to dry grinding step c) and the fine fraction represents a fine mineral filler; and e) drying the fine mineral filler of step d) to obtain a dried mineral filler having a total moisture content of less than 1.0 wt.-%, based on the total weight of said dried mineral filler; wherein the total moisture content in the mixture of step c) is less than or equal to 10.0 wt.-%, based on the total weight of said mixture; the amount of the at least one grinding agent provided in step b) ranges from 0.05 to 150 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method; the temperature in step c) ranges from 65 °C to 200 °C; and the at least one grinding agent is selected from the group consisting of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers, and has a monomer unit ratio (styrene units : maleic anhydride units, S:MA)offrom 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol.
[0159] In particular, such a drying step may be mandatory in cases where the at least one grinding agent provided in step b) is provided in form of an aqueous solution as has been described herein above. However, it has to be noted that the provision of said grinding agent in form an aqueous solution does not in any case require a mandatory drying step since the total amount of said at least one grinding agent is generally low.
[0160] Typically, the drying step according to the process of the present invention may be carried out by any drying method known to the skilled person.
[0161] According to one embodiment, drying step e) is a spray drying step, preferably said spray drying step is carried out at a tower temperature ranging from 90 °C to 130 °C and preferably from 100 °C to 120 °C.
[0162] By means of drying step e), a dried mineral filler is obtained having a low total moisture content which is less than or equal to 1.0 wt.-%, based on the total weight of said dried mineral filler.
[0163] According to another embodiment, the dried mineral filler of step e) has a total moisture content of less than or equal to 0.5 wt.-% and preferably less than or equal to 0.2 wt.-%, based on the total weight of said dried mineral filler.
[0164] According to still another embodiment, the dried mineral filler of step e) has a total moisture content of between 0.01 and 0.15 wt.-%, preferably between 0.02 and 0.10 wt.-%, and more preferably between 0.03 and 0.07 wt.-%, based on the total weight of said dried mineral filler.
Optional treatment step [0165] Independently from whether the process according to the present invention comprises an optional drying step or not, the process may further comprise an optional step of treating (also referred to as "treatment step") the fine mineral filler obtained in step d) and/or the dried mineral filler obtained in step e) with at least one hydrophobizing agent. By means of said treatment step, a treatment layer is formed on at least part of the surface of the obtained mineral filler product.
[0166] Therefore, according to one embodiment, the process for the preparation of a mineral filler product comprises the steps of: a) providing a calcium carbonate-containing material; b) providing at least one grinding agent; c) dry grinding the calcium carbonate-containing material in a mixture obtained by contacting: i) the calcium carbonate-containing material provided in step a), with ii) the at least one grinding agent provided in step b) in at least one grinding unit to obtain a dry ground mineral filler; d) classifying the dry ground mineral filler of step c) to obtain a coarse fraction and a fine fraction, wherein the coarse fraction is removed or subjected to dry grinding step c) and the fine fraction represents a fine mineral filler; e) optionally drying the fine mineral filler of step d) to obtain a dried mineral filler having a total moisture content of less than 1.0 wt.-%, based on the total weight of said dried mineral filler; and f) optionally treating the fine mineral filler of step d) and/or the dried mineral filler of step e) with a hydrophobizing agent to obtain a surface-treated product having a treatment layer on at least part of the surface of said product; wherein the total moisture content in the mixture of step c) is less than or equal to 10.0 wt.-%, based on the total weight of said mixture; the amount of the at least one grinding agent provided in step b) ranges from 0.05 to 150 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method; the temperature in step c) ranges from 65 °C to 200 °C; and the at least one grinding agent is selected from the group consisting of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers, and has a monomer unit ratio (styrene units : maleic anhydride units, S:MA) of from 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol.
[0167] Said hydrophobizing agent used in the optional treatment step may be any agent known to the skilled person which is capable to form a hydrophobic treatment layer on at least part of the surface of a mineral filler product.
[0168] In one embodiment, the hydrophobizing agent is selected from the group consisting of fatty acids having from 6 to 24 chain carbon atoms, mono-substituted succinic anhydrides, alkyl phosphoric acid esters, polyhydrogensiloxane, polydimethylsiloxane, and mixtures thereof.
[0169] According to another embodiment, the hydrophobizing agent is a fatty acid having from 6 to 24 chain carbon atoms, preferably selected from the group consisting of stearic acid, behenic acid, palmitic acid, isostearic acid, montanic acid, capric acid, lauric acid, myristic acid, salts thereof, and mixtures thereof, and more preferably is stearic acid and/or a salt thereof.
[0170] According to another embodiment, the hydrophobizing agent is an alkenyl succinic anhydride.
[0171] According to still another embodiment, the hydrophobizing agent is an alkyl phosphoric acid ester.
[0172] According to still another embodiment, the hydrophobizing agent is selected from polyhydrogensiloxane, polydimethylsiloxane, and mixtures thereof.
[0173] In some embodiments of the process according to the present invention, the temperature in the treatment step ranges from 70 °C to 140 °C, preferably from 75 °C to 130 °C, and more preferably from 80 °C to 125 °C.
[0174] In some cases, the treatment step may be carried out directly at the end of the drying step. In one embodiment, drying step e) is thus carried out in a drying unit comprising a drying chamber and the hydrophobizing agent of step f) is contacted with the dried mineral filler by direct injection of said agent into the drying chamber.
The mineral filler product [0175] As already described above, the moisture pick up susceptibility of a material refers to the amount of moisture absorbed on the surface of said material and is expressed in mg moisture/g absorbed on a sample upon exposure to a defined humid atmosphere.
[0176] In this respect, the fine mineral filler obtained after classifying step d) and/or optional drying step e) may have a moisture pick up susceptibility of less than or equal to 12.0 mg/g, preferably of less than or equal to 10.0 mg/g, and most preferably less than or equal to 8.0 mg/g.
[0177] In another embodiment, the mineral filler product obtained by the optional treatment step may have a moisture pick up susceptibility of less than or equal to 3.0 mg/g, preferably of less than or equal to 2.5 mg/g, and most preferably less than or equal to 2.0 mg/g.
[0178] In another embodiment, the mineral filler product obtained by the optional treatment step has a moisture pick up susceptibility of less than or equal to 0.9 mg/g, preferably less than or equal to 0.8 mg/g, more preferably less than or equal to 0.7 mg/g, and most preferably less than or equal to 0.6 mg/g.
[0179] In another embodiment, the mineral filler product obtained by the optional treatment step has a moisture pick up susceptibility of from 0.1 to 0.9 mg/g, preferably from 0.2 to 0.8 mg/g, and most preferably from 0.2 to 0.6 mg/g.
[0180] In some particular cases as, for example in case of high specific surface areas of the mineral filler product, the moisture pick up susceptibility is suitably defined based on the specific surface area of said product (referred to as the normalized moisture pick up susceptibility).
[0181] According to one embodiment, the mineral filler product obtained by the optional treatment step has a normalized moisture pick up susceptibility of less than or equal to 0.18 mg/m2, preferably less than or equal to 0.17 mg/m2, more preferably less than or equal to 0.16 mg/m2, and most preferably less than or equal to 0.15 mg/m2, based on the specific surface area of said product as measured by the BET nitrogen method.
[0182] According to one embodiment, the mineral filler product obtained by the optional treatment step has a normalized moisture pick up susceptibility of from 0.10 to 0.18 mg/m2, preferably from 0.11 to 0.17 mg/m2, and most preferably from 0.12 to 0.16 mg/m2, based on the specific surface area of said product as measured by the BET nitrogen method.
[0183] According to another embodiment, the mineral filler product obtained after classifying step d) and/or optional drying step e) has a specific surface area ranging from 0.1 to 20.0 m2/g and more preferably from 3.0 to 14.0 m2/g as measured by the BET nitrogen method.
[0184] According to still another embodiment, also the mineral filler product obtained by the optional treatment step has a specific surface area ranging from 0.1 to 20.0 m2/g and more preferably from 3.0 to 14.0 m2/g as measured by the BET nitrogen method.
[0185] By means of the process according to the present invention, a low total volatiles content and, in particular, a high volatile onset temperature may be achieved.
[0186] In one embodiment, the mineral filler product according to the present invention may have a volatile onset temperature of at least or equal to 230 °C, preferably at least or equal to 250 °C. These values likewise refer to the fine mineral filler of step d) of the process according to the present invention, to the dried mineral filler of drying step e) and to the product obtained by the optional treatment step.
[0187] The inventive mineral filler product may be used in a polymer composition, in paper making, paper coatings, agricultural applications, paints, adhesives, sealants, construction applications, and/or cosmetic applications, preferably said mineral filler product is used in a polymer composition.
[0188] As the mineral filler product has a low moisture pick up susceptibility, it may advantageously be used in paper coatings in order to adjust the printing properties of a coated paper. Furthermore, the mineral filler product may also be used in exterior paints and bathroom paints which may lead to a reduction in mildew growth on surfaces being treated with such paints.
[0189] A number of the aforementioned applications (e.g., for coatings or paints) involve the preparation of an aqueous slurry comprising the mineral filler product obtained by the process according to the present invention. Such aqueous slurries may be easily prepared from the inventive mineral filler product by the addition of water to obtain slurries having a solids content of, for example, from 10.0 to 85.0 wt.-%, based on the total weight of said slurry.
[0190] The use of the mineral filler product according to the present invention as a filler material in polymer applications may also be of particular advantage. For example, said filler may be used in thermoplastic polymers, such as polyvinyl chloride, polyolefins, and polystyrene which may allow an increased filler load as compared to conventional calcium carbonate fillers.
[0191] Moreover, the mineral filler product may also be used in polymer coatings which may be applied on the surface of polymer articles, such as foils, in order to increase the hydrophobicity (e.g., reflected by an increased contact angle measured against water) of said surface.
[0192] According to one embodiment, the mineral filler product is used in a polymer composition, wherein said polymer composition comprises: a) at least one polymeric resin; and b) from 0.1 to 90.0 wt.-%, preferably from 1.0 to 85.0 wt.-%, and more preferably from 2.0 to 45.0 wt.-%, based on the total weight of said polymer composition, of the mineral filler product obtained by the process according to the present invention.
[0193] According to another embodiment, said at least one polymeric resin is a thermoplastic resin and preferably is a polyolefin, polyvinylchloride, or polystyrene.
[0194] According to another embodiment, said at least one polymeric resin is a polyolefin and preferably polyethylene or polypropylene.
[0195] According to still another embodiment, said at least one polymeric resin is polyvinylchloride.
[0196] According to still another embodiment, said at least one polymeric resin is polystyrene.
[0197] The polymer composition of the present invention may be used in a number of processes including the man- ufacture of blown films, sheets, or pipe profiles, in processes such as extrusion of pipes, profiles, cables, fibres or the like, and in compression molding, injection molding, thermoforming, blow molding, rotational molding, etc.
[0198] In this respect, said polymer com position may be directly used in the manufacture of polymer articles. Therefore, in one embodiment of the present invention, the polymer composition comprises the mineral filler product in an amount of from 1 to 50 wt.-%, preferably of from 5 to 45 wt.-% and most preferably from 10 to 40 wt.-%, based on the total weight of the polymer composition.
[0199] In an alternative embodiment, the polymer composition may be used as a masterbatch.
[0200] The term "masterbatch" refers to a composition having a concentration of the mineral filler product that is higher than the concentration in the polymer composition used for preparing the final application product. That is to say, the masterbatch is further diluted such as to obtain a polymer composition which is suitable for preparing the final application product.
[0201] For example, a polymer composition according to the present invention suitable to be used as a masterbatch comprises the mineral filler product in an amount of from 50 to 95 wt.-%, preferably from 60 to 95 wt.-%, and more preferably from 70 to 95 wt.-%, based on the total weight of the polymer composition.
Examples [0202] The scope and interest of the invention may be better understood on basis of the following examples which are intended to illustrate embodiments of the present invention. However, they are not to be construed to limit the scope of the claims in any manner whatsoever.
Weight average molecular weight Mw [0203] The weight average molecular weight Mw as used herein may be determined using GPC (SEC) as follows: A sample corresponding to 90 mg of dry polymer is introduced into a 10 ml flask and at least 1 ml of 5 M aqueous NaOH is added until the pH value does change by not more than 0.3 pH units within 48 hours. Mobile phase with an additional 0.04 wt.-% of dimethylformamide is added until a total mass of 10 g is reached. The composition of the mobile phase at pH 9 is as follows: 0.05 M NaHCOs, 0.1 M NaNOs, 0.02 M triethanolamine, 0.03 wt.-% of NaN3.
[0204] The SEC equipment is consisting of an isocratic Waters™ 515 type pump, the flow rate of which is set to 0.8 ml/min, a Waters™ 717+ sample changer, a kiln containing a precolumn type Guard Column Ultrahydrogel Waters™ which is 6 cm in length and has an internal diameter of 40 mm, followed by a linear column type Ultrahydrogel Waters™ which is 30 cm in length and has an internal diameter of 7.8 mm.
[0205] Detection is accomplished by means of a Waters™ 410 differential refractometer. The kiln is heated to a temperature of 60 °C and the refractometer is heated to a temperature of 45 °C.
[0206] The SEC is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standard Service having maximum molecular weight of between 2Ό00 and T106g/mol and a polydispersity index of between 1.4 and 1.7 and further with a sodium polyacrylate of average weight molecular weight of 5’600 g/mol and a polydispersity index equal to 2.4.
[0207] The calibration graph is of the linear type and takes account of the correction obtained using the flow rate marker (dimethylformamide).
Measurement of volatiles [0208] For the purpose of the present application, the "total volatiles" associated with mineral fillers and evolved over a temperature range of 25 °C to 350 °C is characterized by % of mass loss of a mineral filler sample over a temperature range as read on a thermogravimetric (TGA) curve.
[0209] TGA analytical methods provide information regarding losses of mass and volatile onset temperatures with great accuracy. The methods are well-known to the skilled person and described in, for example, "Principles of Instrumental analysis", 5th edition, Skoog Holler Nieman, 1998, chapter 31, pp. 798 - 800. In the present invention, thermogravimetric analysis (TGA) is performed using a Mettler Toledo TGA 851 based on a sample of 500 ± 50 mg and scanning temperatures of from 25 °C to 350 °C at a rate of 20 °C/min under an airflow of 70 ml/min.
[0210] The "volatile onset temperature" can be determined as follows by analysis of the TGA curve: The first derivative of the TGA curve is obtained and the inflection points thereon between 150 °C and 350 °C are identified. Among these inflection points having a tangential slope value of greater than 45° relative to a horizontal line, the one having the lowest associated temperature above 200 °C is identified. The temperature associated with this lowest inflection point of the first derivative curve is the "volatile onset temperature".
Particle size distribution [0211] For the purpose of the present application, particle sizes being lower than 100 μηι, the weight median particle size d50 and further granulometric characteristics are determined based on measurements made by using a Sedigraph™ 5100 instrument of Micromeritics Instrument Corporation. The method and the instrument are known to the skilled person and are commonly used to determine the particle size of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt.-% Na4P207. The samples are dispersed using a high speed stirrer and supersonics. In case of surface-treated products, additional 0.5 g of a surfactant (Photo-Flo 200® from Kodak) were added to 50 ml of the solution of 0.1 wt.-% Na4P207 before dispersing the treated carbonate sample.
[0212] In case of particle sizes being greater than 100 μηι, fractional sieving is used to determine granulometric characteristics. BET specific surface area of a material [0213] Throughout the present document, the specific surface area (expressed in m2/g) of a mineral filler is determined using the BET method (using nitrogen as adsorbing gas), which is well known to the skilled person (ISO 9277:1995). The total surface area (in m2) of the mineral filler can be obtained by multiplication of the specific surface area (in m2/g) and the mass (in g) of the mineral filler.
Moisture pick up susceptibility [0214] The moisture pick up susceptibility of a material as referred to herein is determined in mg moisture/g after exposure to an atmosphere of 10 and 85% relative humidity, respectively, for 2.5 hours at a temperature of +23 °C (± 2 °C). For this purpose, the sample is first kept at 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 another 2.5 hours. The weight increase between 10 and 85% relative humidity is then used to calculate the moisture pick-up in mg moisture/g of sample.
[0215] The moisture pick up susceptibility in mg/g divided by the specific surface area in m2 (BET method) corresponds to the "normalized moisture pick up susceptibility" expressed in mg/m2 of sample.
Total moisture content [0216] The total moisture content as used herein is measured according to the Karl Fischer coulometric titration method, desorbing the moisture in an oven at 220 °C for 10 min and passing it continuously into a KF coulometer (Mettler Toledo coulometric KF Titrator C30, combined with Mettler oven DO 0337) using dry nitrogen at 100 ml/min for 10 min. A calibration curve using water has to be recorded and a blank of 10 min nitrogen flow without a sample has to be taken into account.
Materials
* Grinding agent A
[0217] MPG = monopropylene glycol.
* Grinding agent B
[0218] Cray Valley SMA 1000HNa = aqueous solution of hydrolyzed styrene-maleic anhydride co-polymer, 100% sodium neutralized, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw, = 5Ό00 g/mol; monomer unit ratio (S:MA) = 1:1; 40.4 wt.-% grinding agent content; phi = 8.5.
" Grinding agent C
[0219] Cray Valley SMA 1000 = powdered styrene-maleic anhydride co-polymer, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw= 5Ό00 g/mol; monomer unit ratio (S:MA) = 1:1.
* Grinding agent D
[0220] Cray Valley SMA 3000HNa = aqueous solution of hydrolyzed styrene-maleic anhydride co-polymer, 100% sodium neutralized, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw = 9’500 g/mol; monomer unit ratio (S:MA) = 3:1; 24.4 wt.-% grinding agent content; pH = 8.6.
* Grinding agent E
[0221] Cray Valley SMA EF-30 = powdered styrene-maleic anhydride co-polymer, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw = 9’500 g/mol; monomer unit ratio (S:MA) = 3:1.
« Grinding agent F
[0222] Cray Valley SMA EF-40 = solution in acetone prepared from styrene-maleic anhydride co-polymer, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw = 11Ό00 g/mol; monomer unit ratio (S:MA) = 4:1; 33.0 wt.-% grinding agent content.
* Grinding agent G
[0223] Cray Valley SMA 17352 = partially esterified styrene-maleic anhydride co-polymer in powdered form, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw = 7Ό00 g/mol; acid value: 270 mg KOH/g.
* Grinding agent H
[0224] Cray Valley SMA 1440 = partially esterified styrene-maleic anhydride co-polymer in powdered form, commercially available from Cray Valley LLC, USA; approx, molecular weight Mw = 7Ό00 g/mol; acid value: 185 mg KOH/g.
General procedure [0225] Italian marble having an average diameterof approx. 5 cm was crushed using a hammer mill. The size distribution of the crushed material was determined by sieving and is given in Table 1 herein below.
[0226] The crushed material was contacted with one of the grinding agents summarized above immediately before grinding and mixed in a concrete mixer for at least 10 min.
[0227] The obtained material was then transferred into a ball mill (Hosokawa™ Ball Mill S.O. 80/32) using 100 kg of cylindrically shaped iron grinding balls, having an average diameterof 16 mm in order to obtain a ground material having a weight median particle size d50 of less than or equal to 1.0 μηι.
[0228] The outlet of the grinding chamber was equipped with an opening of 20 X 5 mm discharging to an Alpine Turboplex™ 100 ATP classifier. The classifier was adjusted in order to recover the fine fraction having a desired weight median particle size d50. The remaining coarse material having a weight median particle size d50 being higher than said desired value is sent back to the mill feed.
[0229] The dry grinding was performed in a continuous fashion, wherein approx. 15 kg of material were constantly present in the system. Thus, the mill feed was continuously fed with a quantity of crushed material and/or coarse fraction material resulting from the classifying step material which was equal to the quantity of the fine fraction leaving the system.
[0230] The system was operated until constant amounts of material having a suitable quality could be recovered by monitoring the grinding capacity and the grinding energy. The grinding chamber is heated to a constant temperature of 80 °C.
Table 1: Particle size distribution of crushed marble.
Table 2: Process throughput and particle sizes after grinding.
Table 3: Volatile onset temperatures.
[0231] These examples illustrate the improved grinding capacities (i.e. an increased throughput) in a process according to the present invention as compared to a process carried out in the absence of grinding agent or using a conventional grinding agent.
Claims 1. A process for the preparation of a mineral filler product, the process comprising the steps of: a) providing a calcium carbonate-containing material; b) providing at least one grinding agent; c) dry grinding the calcium carbonate-containing material in a mixture obtained by contacting: i) the calcium carbonate-containing material provided in step a), with ii) the at least one grinding agent provided in step b) in at least one grinding unit to obtain a dry ground mineral filler; d) classifying the dry ground mineral filler of step c) to obtain a coarse fraction and a fine fraction, wherein the coarse fraction is removed or subjected to dry grinding step c) and the fine fraction represents a fine mineral filler; and e) optionally drying the fine mineral filler of step d) to obtain a dried mineral filler having a total moisture content of less than 1.0wt.-%, based on the total weight of said dried mineral filler; wherein the total moisture content in the mixture of step c) is less than or equal to 10.0 wt.-%, based on the total weight of said mixture; the amount of the at least one grinding agent provided in step b) ranges from 0.05 to 150 mg/m2, based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method; the temperature in step c) ranges from 65 °C to 200 °C; and the at least one grinding agent is selected from the group consisting of styrene-maleic anhydride co-polymers and derivatives of styrene-maleic anhydride co-polymers, and has a monomer unit ratio (styrene units : maleic anhydride units, S:MA) of from 1:2 to 15:1 and a molecular weight Mw of from 500 to 40Ό00 g/mol. 2. The process according to claim 1, wherein the calcium carbonate-containing material provided in step a) is selected from natural calcium carbonate sources and preferably is selected from the group consisting of marble, limestone, chalk, dolomite, and mixtures thereof. 3. The process according to any of claims 1 or 2, wherein the amount of said at least one grinding agent provided in step b) ranges from 0.1 to 100.0 mg/m2, preferably from 0.2 to 75.0 mg/m2, and more preferably 0.2 to 50.0 mg/m2 from based on the specific surface area of the calcium carbonate-containing material as measured by the BET nitrogen method. 4. The process according to any of claims 1 to 3, wherein the at least one grinding agent provided in step b) has a monomer unit ratio (S:MA) of from 1:1 to 5:1, preferably from 1:1 to 4:1, and more preferably from 1:1 to 3:1. 5. The process according to any of claims 1 to 4, wherein the at least one grinding agent provided in step b) has a molecular weight Mw of from 2Ό00 to 30Ό00 g/mol and preferably from 3Ό00 to 25Ό00 g/mol. 6. The process according to any of claims 1 to 5, wherein the at least one grinding agent provided in step b) is partially or fully neutralized with cations selected from lithium, sodium, potassium, calcium, magnesium, ammonium, iminium, and mixtures thereof. 7. The process according to any of claims 1 to 6, wherein the total moisture content in the mixture of step c) is less than or equal to 5.0 wt.-%, preferably less than or equal to 2.0 wt.-%, and more preferably less than or equal to 1.0 wt.-%, based on the total weight of said mixture. 8. The process according to any of claims 1 to 7, wherein the temperature in step c) ranges from 70 °C to 180 °C, preferably from 75 °C to 160 °C, and more preferably from 80 °C to 150 °C. 9. The process according to any of claims 1 to 8, wherein the fine mineral filler of step d) has a weight median particle size d50 ranging from 0.4 to 40.0 μίτι, preferably from 0.6 to 20.0 μίτι, and more preferably from 0.7 to 10.0 μ(η. 10. The process according to any of claims 1 to 9, wherein the process comprises a further step of treating the fine mineral filler of step d) and/or the dried mineral filler of step e) with a hydrophobizing agent to obtain a surface-treated product having a treatment layer on at least part of the surface of said product. 11. A mineral filler product obtained by a process according to any of claims 1 to 10, wherein said product has a volatile onset temperature of at least or equal to 200 °C. 12. The mineral filler product obtained by the process according to claim 10, wherein said product has a moisture pick up susceptibility of less than or equal to 0.9 mg/g, preferably less than or equal to 0.8 mg/g, more preferably less than or equal to 0.7 mg/g, and most preferably from 0.2 to 0.6 mg/g. 13. The mineral filler product according to any of claims 11 or 12, wherein said product has a volatile onset temperature of at least or equal to 230 °C, preferably at least or equal to 250 °C. 14. Use of a mineral filler product according to any of claims 11 to 13 in a polymer composition, in paper making, paper coatings, agricultural applications, paints, adhesives, sealants, construction applications, and/or cosmetic applications, preferably said mineral filler product is used in a polymer composition. 15. The use according to claim 14, wherein said polymer composition comprises: a) at least one polymeric resin; and b) from 0.1 to 90.0 wt.-%, preferably from 1.0 to 85.0 wt.-%, and more preferably from 2.0 to 45.0 wt.-%, based on the total weight of said polymer composition, of the mineral filler product according to claims 11 to 13.
Patentansprüche 1. Verfahren zur Herstellung eines Mineralfüllstoffprodukts, wobei das Verfahren die Schritte umfasst: a) Bereitstellen von einem Calciumcarbonat enthaltenden Material; b) Bereitstellen von wenigstens einem Mahlmittel; c) Trockenvermahlen des Calciumcarbonat enthaltenden Materials in einem Gemisch, erhalten durch Inkontaktbringen von: i) dem im Schritt a) bereitgestellten Calciumcarbonat enthaltenden Material mit ii) dem in Schritt b) bereitgestellten wenigstens einen Mahlmittel in wenigstens einer Mahleinheit, um einen trockenvermahlenen Mineralfüllstoff zu erhalten; d) Klassieren des trockenvermahlenen Mineralfüllstoffs aus Schritt c), um eine grobe Fraktion und eine feine Fraktion zu erhalten, wobei die grobe Fraktion entfernt oder dem Trockenvermahlungsschritt c) unterzogen wird, und die feine Fraktion stellt einen feinen Mineralfüllstoff dar; und e) gegebenenfalls Trocknen des feinen Mineralfüllstoffs aus Schritt d), um einen getrockneten Mineralfüllstoff mit einem Gesamtfeuchtigkeitsgehalt von kleiner 1,0 Gew.-%, bezogen auf das Gesamtgewicht des getrockneten Mineralfüllstoffs, zu erhalten; wobei der Gesamtfeuchtigkeitsgehalt in dem Gemisch von Schritt c) kleiner oder gleich 10,0 Gew.-% ist, bezogen auf das Gesamtgewicht des Gemischs; die Menge des in Schritt b) bereitgestellten wenigstens einen Mahlmittels reicht von 0,05 bis 150 mg/m2, bezogen auf die spezifische Oberfläche des Calciumcarbonat enthaltenden Materials, wie durch das BET-Stickstoffverfahren gemessen; die Temperatur in Schritt c) reicht von 65 °C bis 200 °C; und das wenigstens eine Mahlmittel ist ausgewählt aus der Gruppe bestehend aus Styrol-Maleinsäureanhydrid-Copo-lymeren sowie Derivaten von Styrol-Maleinsäureanhydrid-Copolymeren, und weist ein Monomereinheitsverhältnis (Styrol-Einheiten : Maleinsäureanhydrid-Einheiten, S:MA) von 1:2 bis 15:1 und ein Molekulargewicht Mw von 500 bis 40 000 g/mol auf. 2. Verfahren nach Anspruch 1, bei dem das in Schritt a) bereitgestellte Calciumcarbonat enthaltende Material ausgewählt ist aus natürlichen Calciumcarbonat-Quellen, und ist bevorzugt ausgewählt aus der Gruppe bestehend aus Marmor, Kalkstein, Kreide, Dolomit, sowie Gemischen davon. 3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem die Menge des in Schritt b) bereitgestellten wenigstens einen Mahlmittels von 0,1 bis 100,0 mg/m2 reicht, bevorzugt von 0,2 bis 75,0 mg/m2, und bevorzugter von 0,2 bis 50,0 mg/m2, bezogen auf die spezifische Oberfläche des Calciumcarbonat enthaltenden Materials, wie durch das BET-Stickstoffverfahren gemessen. 4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem das in Schritt b) bereitgestellte wenigstens eine Mahlmittel ein Monomereinheitsverhältnis (S:MA) von 1:1 bis 5:1 aufweist, bevorzugt von 1:1 bis 4:1, und bevorzugter von 1:1 bis 3:1. 5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem das in Schritt b) bereitgestellte wenigstens eine Mahlmittel ein Molekulargewicht Mw von 2 000 bis 30 000 g/mol aufweist, und bevorzugt von 3 000 bis 25 000 g/mol. 6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem das in Schritt b) bereitgestellte wenigstens eine Mahlmittel teilweise oder vollständig mit Kationen, ausgewähltaus Lithium, Natrium, Kalium, Calcium, Magnesium, Ammonium, Iminium, sowie Gemischen davon, neutralisiert ist. 7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem der Gesamtfeuchtigkeitsgehalt in dem Gemisch von Schritt c) kleiner oder gleich 5,0 Gew.-% ist, bevorzugt kleiner oder gleich 2,0 Gew.-%, und bevorzugter kleiner oder gleich 1,0 Gew.-%, bezogen auf das Gesamtgewicht des Gemischs. 8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem die Temperatur in Schritt c) von 70 °C bis 180 °C reicht, bevorzugt von 75 °C bis 160 °C, und bevorzugter von 80 °C bis 150 °C. 9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem der feine Mineralfüllstoff aus Schritt d) eine gewichtsgemittelte Partikelgrösse d50 aufweist, die von 0,4 bis 40,0 μ(η reicht, bevorzugt von 0,6 bis 20,0 μ(η, und bevorzugter von 0,7 bis 10,0 μηι. 10. Verfahren nach einem der Ansprüche 1 bis 9, bei dem das Verfahren einen weiteren Schritt umfasst, bei dem der feine Mineralfüllstoff aus Schritt d) und/oder der getrocknete Mineralfüllstoff aus Schritt e) mit einem Hydrophobierungsmittel behandelt wird, um ein oberflächenbehandeltes Produkt mit einer Behandlungsschicht auf wenigstens einem Teil der Oberfläche des Produkts zu erhalten. 11. Mineralfüllstoffprodukt, erhalten durch ein Verfahren gemäss einem der Ansprüche 1 bis 10, bei dem das Produkt eine Onsettemperatur der flüchtigen Bestandteile von wenigstens oder gleich 200 °C aufweist. 12. Mineralfüllstoffprodukt, erhalten durch das Verfahren gemäss Anspruch 10, bei dem das Produkt eine Anfälligkeit für Feuchtigkeitsaufnahme von kleiner oder gleich 0,9 mg/g aufweist, bevorzugt von kleiner oder gleich 0,8 mg/g, bevorzugter von kleiner oder gleich 0,7 mg/g, und am meisten bevorzugt von 0,2 bis 0,6 mg/g. 13. Mineralfüllstoffprodukt nach einem der Ansprüche 11 oder 12, bei dem das Produkt eine Onsettemperatur der flüchtigen Bestandteile von wenigstens oder gleich 230 °C aufweist, bevorzugt wenigstens oder gleich 250 °C. 14. Verwendung eines Mineralfüllstoffprodukts gemäss einem der Ansprüche 11 bis 13 in einer Polymerzusammensetzung, bei der Papierherstellung, in Papierstrichen, in Agraranwendungen, in Farben, Klebstoffen, Dichtmitteln, in Baugewerbeanwendungen und/oder in Kosmetikanwendungen, bevorzugt wird das Mineralfüllstoffprodukt in einer Polymerzusammensetzung verwendet. 15. Verwendung nach Anspruch 14, bei der die Polymerzusammensetzung umfasst: a) wenigstens ein Polymerharz; und b) von 0,1 bis 90,0 Gew.-%, bevorzugt von 1,0 bis 85,0 Gew.-%, und bevorzugter von 2,0 bis 45 Gew.-%, bezogen auf das Gesamtgewicht der Polymerzusammensetzung, des Mineralfüllstoffprodukts gemäss einem der Ansprüche 11 bis 13.
Revendications 1. Procédé de préparation d’un produit de charge minérale, le procédé comprenant les étapes suivantes: a) fournir un matériau contenant du carbonate de calcium ; b) fournir au moins un agent de broyage ; c) broyer à sec le matériau contenant du carbonate de calcium dans un mélange obtenu par la mise en contact : i) du matériau contenant du carbonate de calcium fourni à l’étape a), avec ii) l’au moins un agent de broyage fourni à l’étape b) dans au moins une unité de broyage pour obtenir une charge minérale broyée sèche ; d) classifier la charge minérale broyée sèche de l’étape c) pour obtenir une fraction grossière et une fraction fine, dans laquelle la fraction grossière étant éliminée ou soumise à l’étape de broyage à sec c) et la fraction fine représentant une charge minérale fine ; et e) sécher facultativement la charge minérale fine de l’étape d) pour obtenir une charge minérale séchée ayant une teneur totale en humidité inférieure à 1.0 % en poids, par rapport au poids total de ladite charge minérale séchée ; dans lequel la teneur totale en humidité dans le mélange de l’étape c) est inférieure ou égale à 10.0 % en poids, par rapport au poids total dudit mélange ; la quantité de Γ agent de broyage utilisé dans l’étape b) est comprise dans la plage allant de 0.05 à 150 mg/m2, en se basant sur la surface spécifique du matériau contenant du carbonate de calcium, comme mesurée parla méthode BET à l’azote ; la température de l’étape c) est comprise dans la plage allant de 65 °C à 200 °C ; et le dit agent de broyage est choisi dans le groupe constitué par des copolymères de styrène-anhydride maléique et des dérivés de copolymères de styrène-anhydride maléique, et a un rapport de motifs monomères (motifs de styrène:motifs d’anhydride maléique, S:AM) de 1:2 à 15:1 et un poids moléculaire Mm de 500 à 40 000 g/mol. 2. Procédé selon la revendication 1, dans lequel le matériau contenant du carbonate de calcium utilisé dans l’étape a) est choisi parmi des sources de carbonate de calcium naturelles et de préférence est choisi dans le groupe constitué par le marbre, le calcaire, la craie, la dolomie et des mélanges de ceux-ci. 3. Procédé selon la revendication 1 ou 2, dans lequel la quantité dudit agent de broyage utilisé dans l’étape b) est comprise dans la plage allant de 0.1 à 100.0 mg/m2, de préférence de 0.2 à 75.0 mg/m2, et plus préférablement de 0.2 à 50.0 mg/m2, en se basant sur la surface spécifique du matériau contenant du carbonate de calcium, comme mesurée par la méthode BET à l’azote. 4. Procédé selon l’une quelconque des revendications 1 à 3, dans lequel ledit agent de broyage utilisé dans l’étape b) a un rapport de motifs monomères (S:AM) de 1:1 à 5:1, de préférence de 1:1 à 4:1, et plus préférablement de 1:1 à 3:1. 5. Procédé selon l’une quelconque des revendications 1 à 4, dans lequel ledit agent de broyage utilisé dans l’étape b) a un poids moléculaire Mm de 2000 à 30 000 g/mol, et de préférence de 3000 à 25 000 g/mol. 6. Procédé selon l’une quelconque des revendications 1 à 5, dans lequel ledit agent de broyage utilisé dans l’étape b) est partiellement ou totalement neutralisé avec des cations choisis parmi le lithium, le sodium, le potassium, le calcium, le magnésium, l’ammonium, l’iminium et des mélanges de ceux-ci. 7. Procédé selon l’une quelconque des revendications 1 à 6, dans lequel la teneur totale en humidité dans le mélange de l’étape c) est inférieure ou égale à 5.0 % en poids, de préférence inférieure ou égale à 2.0 % en poids et plus préférablement inférieure ou égale à 1.0 % en poids, par rapport au poids total dudit mélange. 8. Procédé selon l’une quelconque des revendications 1 à 7, dans lequel la température de l’étape c) est comprise dans la plage allant de 70 °C à 180 °C, de préférence de 75 °C à 160 °C et plus préférablement de 80 °C à 150 °C. 9. Procédé selon l’une quelconque des revendications 1 à 8, dans lequel la charge minérale fine de l’étape d) a une taille de particule médiane en poids d50 comprise dans la plage allant de 0.4 à 40.0 μηι, de préférence de 0.6 à 20.0 μίτι et plus préférablement de 0.7 à 10.0 μηι. 10. Procédé selon l’une quelconque des revendications 1 à 9, dans lequel le procédé comprend une étape supplémentaire de traitement de la charge minérale fine de l’étape d) et/ou de la charge minérale séchée de l’étape e) avec un agent hydrophobisant pour obtenir un produit traité en surface ayant une couche de traitement sur au moins une partie de la surface dudit produit. 11. Produit de charge minérale obtenu par un procédé selon l’une quelconque des revendications 1 à 10, dans lequel ledit produit a une température de départ volatile d’au moins ou égale à 200 °C. 12. Produit de charge minérale obtenu par le procédé selon la revendication 10, dans lequel ledit produit a une susceptibilité d’absorption d’humidité inférieure ou égale à 0.9 mg/g, de préférence inférieure ou égale à 0.8 mg/g, plus préférablement inférieure ou égale à 0.7 mg/g, et de manière préférée entre toutes de 0.2 à 0.6 mg/g. 13. Produit de charge minérale obtenu parun procédé selon l’une quelconque des revendications 11 ou 12, dans lequel ledit produit aune température de départ volatile d’au moins ou égale à 230 °C, de préférence d’au moins ou égale à 250 °C. 14. Utilisation d’un produit de charge minérale obtenu selon l’une quelconque des revendications 11 à 13 dans une composition polymere, dans la fabrication de papier, les revetements de papier, les applications agricoles, les peintures, les adhesifs, les agents d’etancheite, les applications de construction et/ou les applications cosmetiques, de preference ledit produitde charge minerale est utilise dans une composition polymere. 15. Utilisation selon la revendication 14, dans laquelle ladite composition polymere comprend : a) au moins une resine polymere ; et b) de 0.1 a 90.0 % en poids, de preference de 1.0 a 85.0 % en poids et plus preferablement de 2.0 a 45.0 % en poids, par rapport au poids total de ladite composition polymere, du produit de charge minerale selon I’une quelconque des revendications 11 a 13.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description • EP 2029677 A [0004] · US 4136830 A [0012] • EP 2132268 A [0005] · EP 0998522 A [0015] • WO 2011077232 A [0006] · EP 2447213 A [0059] • WO 0020336 A [0007] · EP 2524898 A [0059] • US 4407986 A [0008] · EP 2371766 A [0059] • EP 0325114 A [0009] · EP 12164041 A [0059] • US 2010025507 A[0011]
Non-patent literature cited in the description • P. GODARD ; Y. BOMAL. Tensile behaviour of pol- · SKOOG HOLLER NIEMAN. Principles of Instrumen- ystyrene filled with calcium carbonate. The 5th Inter- tal analysis. 1998, 798-800 [0209] national Fillers Conference Filplas, 19 May 1992 [0010]
Claims (15)
- SZABADALMI IGÉNYPONTOK 1 < Eljárás •ás^á^irMlti^nyag oiiáfltására, amely eljárás a I<övaík8zö iépésak- bő! áll: a) kalcium-karbonátot tartalmazó anyag biztosítása; b) legalább agy örlöanyag biztosítása; c) a kaíoium^karbouátöt tarmlmazo anyag száraz őrlése egy keverékben; amelyet: í) az aj lépésben biztosított kalcium-karbonátot tartalmazó anyagnak ii) a b) lépésben biztosított legalább agy öriöanyaggal való érintkezietéssel kapunk, legalább agy örlöegységben, amellyel egy szárazon őrölt ásványi töltőanyagot kapunk; d) a c) lépés szerinti szárazon őröli ásványi töltőanyag osztályozása., amellyel egy durva frakciót és égy finom frakciót kapunk, ahol a durva frakciót eltávolítjuk vagy c) lépés szerinti száraz őrlésnek vetjük alá, és a finom frakció egy finom ásványiioitö-anyagot képvisel; és e) a d) lépés szerinti finom ásványi töltőanyag adott esetben történő szárítása, amellyel egy oíyan szárított ásványi töltőanyagot kapunk, amelynek teljes nedvességtartalma, a szárított ásványi töltőanyag teljes tömegére vonatkoztatva, 1 :ö tömegig -nál kisebb; ahol a c) lépés szerinti keverék teljes nedvességtartalma, a keverék teljés tömegére vonatkoztatva, 10 tőmeg% -nál kisebb vagy ezzel egyenlő; a b) lépésben biztosított légilbb egy örlöanyag mennyisége, a kalcium-karbonátot tartalmazó anyag fajlagos felületet véve alapúi, amilyet a BET nitrogén módszer szerint mérőnk, O.öö-lii mg/m2; a c) lépésbe!! hőmérséklet 65 X és 20Ö,:'C között van; és a legalább egy őrlőanyag a sztíroi-maleinsav-anhkirid kopolimerek és szirokmaléln-savanhidrid kopofímer-származékok által alkotott csoportból van kiválasztva, és ennek monomeregpig-hányadosa (szflrolegységek: maieínsav-anhidrid egységek, |:ÜA) 1:2-től IS: 1-ig terjed, és Mw molekulatömege 500 és 40 OÖÖ g/rnol között van.
- 2. ám. 1;> igénypont szarint! eljárás, amelyben az a) lépésben biztosított kaid-pra-kartenátpt tartaímazé anyagot természetes kaieiu?rT-karbonát-fosTások közűi vá-íasztjük kL és előnyösen a márvány, mészkő, kréta, dolomit is ezek keverékei közül válaszunk ki.
- 3. Az 1 , vagy 2, igénypont szerinti eljárás, amelyben a 0} lépisben biztosított legáíibb égy Ődöanyag mennyiiga, a kÉieinm-karbönátof tartalmazó anyag fajlagos felületét véve alapot, amelyet a BET nitrogén módszer szerint mérünk, 0,1-180,0 mgrm2, előnyösen 3,2-73,0 mgán^, még előnyösebben 0,2 - 50J rogfr#,
- 4. Az 1"3. Igénypontok bármelyike szerinti eprás, amelyben a b) lépisben biztöiloi legalább egy Őrlési anyag rnonomeregység-hányadesa r$:fvlA) 1:1-5:1, előnyösén: 1:1-4:1, még előnyösebben; 1::¾ 1 közötti,
- 5. Az: 1 -4. Igénypontok bármelyike szerinti éljárás, amelyben a b) lépésben biztosított legalább egy örlöanyag Mw molekulatömege 2'00Ö és 3(7000 g/niol, előnyösen 3*008*25' 000 g/meí:
- 6. Az 1-5, igénypontok bármelyike izérí π ti eljárás, amelyben a b) lépésben biztosított legalább egy örlöanyag részlegesen vagy teljesen semlegesitve van a lítium, nátrium, kálium, kalblum, magnézium, ammóníum, imlíiium és az ezek keverékéi közül kiválasztott kationokkal
- 7. Az 1-6. igénypontok bármelyike szerinti eprás, amelyben: a o) lépés szerinti keverék tépi nedvességtafia Írna, az emlltii keverék teljes tömegére vonatkoztatva ő;0 I5rneg% vagy ennél kevesebb, előnyösen kisebb vagy egyenlő 2,0 tömeg%-nái, és még előnyösebben 1,0 íömeg%-ná! kisebb vagy azzal: egyenlő,
- 8. Az 1 -7, Igénypontok bármelyike szerinti eljárás, amelyben a e) lépésben a bÖmérsékiet 70¾ is 180X közötti, előnyösen 75CC és 180¾ közötti, előnyösebben 80¾ is 150¾ közötti,
- 9. Az 1 -8. igénypontok bármelyike szerint! eprás, amelyben; a d) lépés finom ásványi töltőanyagának timeiitlagolt részeeskemérete 0,4-40,0 pm, előnyösen 0,8-20,0 μην, előnyösebben 0:7-1 ÖSÖ pm.
- 10. Az 1-9. igénypontök bármelyike szerinti eprás, amelyben az. eljárás egy további a i| lépes szerinti finom ásványi töltőanyag és/vagy az e) lépés szerinti szári-főtt ásványi töltőanyag hlőroföbizáló-szerrel velő kezelési lépést tartalmaz, amellyel egy olyan Miletkezelf termékot kapunk, amely kezelt réteggel rendelkezik a lermék felületének léiálibb egy résiin,
- 11, Az feárnialyiká sáriití a|SrAtsaÍ előállított ásványi töltő anyag.. amelyben a termék illékony kezdeti hőmérséklete
- 12, A 10. Igénypont szerin! eptássai előáílttötf ásványi töltőanyag:, amelyben a tennék iedyeeségtartairnának érzékelési értéke kisebb, mint ö,§ mg/g vagy ezzel egyenlő, előnyösen kílibb, mint 0,1 m||g vagy ezzel egyenlő, előnyösebben kisebb, mint 0,7 mg/g vagy ezzel egyenlő, és legelőnyösebben ΒΜΦΜ mg/g.
- 13, A 11. vagy 12. Igénypont szerinti ásványi töltőanyag, amelyben a termék Illékony keidet! hőmérséklete legalább 23CFfD, előnyösen legalább 2¾¾.
- 14, A 11-13. igénypontok bármelyike szerinti ásványi töltőanyag alkalmazása polimer készítményben, papírgyártásban, papIrbevonatokha n, mezőgazdasági alkalmazásokban, festékekben, ragasztökban, tömkőanyagokban. építési alkalmazásokban és/vagy kozmetikai alkalmazásokban, előnyösen pedig az ásványi töltőanyag terméket polimer összefiteíben alkalmazzuk,
- 15, A 14, igénypont szerinti ilkalmazls, ahol a polimer készítmény tartalmaz: a) legalább egy pőiirnergyántáltlt b) e polimef ikészífmlny teips tömegére vonatkoztatva 0,1-90,0 tömeg%, előnyösen 1,0-85,0 tömeg%, még előnyösebben 1,0-40,0 tőmeg% 11-13. Igénypontok szerinti ásványi töltőanyagot. A meghataírnazoít:
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| EP3133127B1 (en) | 2015-08-21 | 2018-08-08 | Omya International AG | Process for the preparation of a mineral filler product |
| EP3156369B1 (en) * | 2015-10-16 | 2018-07-11 | Omya International AG | High solids pcc with copolymeric additive |
| EP3192838A1 (en) * | 2016-01-14 | 2017-07-19 | Omya International AG | Treatment of surface-reacted calcium carbonate |
| ES2702459T3 (es) | 2016-01-14 | 2019-03-01 | Omya Int Ag | Uso de un carbonato de calcio tratado en superficie como secuestrante de oxígeno |
| EP3467050A1 (en) * | 2017-10-04 | 2019-04-10 | Omya International AG | Coating compositions comprising ground natural calcium carbonate (gcc) |
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| US4136830A (en) * | 1976-05-19 | 1979-01-30 | The Dow Chemical Company | Ore grinding process containing copolymer grinding aids |
| JPS532557A (en) * | 1976-06-28 | 1978-01-11 | Shiraishi Chuo Kenkiyuushiyo K | Calcium carbonateewater dispersion substance |
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| SU854940A1 (ru) * | 1978-11-20 | 1981-08-15 | Ордена Трудового Красного Знамени Институт Физической Химии Ан Ссср | Способ получени привитых сополимеров |
| JPS56120742A (en) | 1980-02-29 | 1981-09-22 | Idemitsu Petrochem Co Ltd | Polypropylene composition |
| JPS6272762A (ja) * | 1985-09-26 | 1987-04-03 | Idemitsu Petrochem Co Ltd | 無機顔料スラリ−用添加剤 |
| JPS62132730A (ja) * | 1985-12-02 | 1987-06-16 | Kuraray Co Ltd | 炭酸カルシウム用分散剤 |
| DE3801649C2 (de) | 1988-01-21 | 1996-09-19 | Solvay Werke Gmbh | Unterbodenschutzmasse, Verfahren zu deren Herstellung sowie Verwendung eines gegebenenfalls synthetischen Calciumcarbonats zur Rheologiesteuerung von Unterbodenschutzmassen |
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| FR2784371B1 (fr) | 1998-10-07 | 2000-12-15 | Pluss Stauffer Ag | Nouveaux carbonates de calcium naturels broyes, eventuellement traites avec un acide gras ou son sel, leur application comme regulateur de rheologie dans des compositions polymeriques |
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| GB2383046A (en) * | 2001-12-12 | 2003-06-18 | Imerys Minerals Ltd | Calcium carbonate filler in stretched polyolefin film |
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| FR2901491B1 (fr) * | 2006-05-24 | 2009-03-20 | Coatex Sas | Procede de broyage a sec de materiaux contenant un minerai carbonate |
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| FR2913427B1 (fr) | 2007-03-05 | 2011-10-07 | Omya Development Ag | Procede de broyage a sec d'un ou plusieurs materiaux comprenant au moins un carbonate de calcium |
| CN100436530C (zh) * | 2007-03-15 | 2008-11-26 | 上海交通大学 | 聚乙烯-醋酸乙烯酯基热可塑性木塑复合材料的制备方法 |
| FR2954715B1 (fr) | 2009-12-24 | 2014-12-26 | Coatex Sas | Utilisation de glycerol comme agent ameliorant le caractere autodispersant d'une matiere minerale destinee a une composition aqueuse |
| PT2371766E (pt) | 2010-04-01 | 2013-05-22 | Omya Development Ag | Processo para preparar um produto de carbonato de cálcio precipitado, material e uso do produto de carbonato de cálcio precipitado |
| AU2011240071B2 (en) * | 2010-04-12 | 2015-01-22 | Omya International Ag | Composition for blow molding |
| DK2447213T3 (en) | 2010-10-26 | 2015-07-27 | Omya Int Ag | Preparation of precipitated calcium carbonate with high purity |
| PL2447328T3 (pl) * | 2010-10-29 | 2015-05-29 | Omya Int Ag | Sposób polepszania właściwości materiałów zawierających węglan wapnia związanych z manipulowaniem |
| PT2524898E (pt) | 2011-05-16 | 2015-11-03 | Omya Int Ag | Método para a produção de carbonato de cálcio precipitado a partir de refugos de fábricas de pasta de papel |
| EP2626388B1 (en) * | 2012-02-09 | 2016-05-04 | Omya International AG | A composition and method for controlling the wettability of surfaces |
-
2014
- 2014-02-21 ES ES14156165.4T patent/ES2640099T3/es active Active
- 2014-02-21 PL PL14156165T patent/PL2910610T3/pl unknown
- 2014-02-21 SI SI201430363T patent/SI2910610T1/sl unknown
- 2014-02-21 DK DK14156165.4T patent/DK2910610T3/en active
- 2014-02-21 HU HUE14156165A patent/HUE034671T2/hu unknown
- 2014-02-21 PT PT141561654T patent/PT2910610T/pt unknown
- 2014-02-21 EP EP14156165.4A patent/EP2910610B1/en active Active
-
2015
- 2015-02-12 CN CN201580009616.8A patent/CN106029792B/zh not_active Expired - Fee Related
- 2015-02-12 US US15/116,480 patent/US10316193B2/en not_active Expired - Fee Related
- 2015-02-12 WO PCT/EP2015/053000 patent/WO2015124494A1/en active Application Filing
- 2015-02-12 MX MX2016010842A patent/MX2016010842A/es unknown
- 2015-02-12 CA CA2939144A patent/CA2939144A1/en not_active Abandoned
- 2015-02-12 AU AU2015220955A patent/AU2015220955B2/en not_active Ceased
- 2015-02-12 RU RU2016137487A patent/RU2647026C1/ru not_active IP Right Cessation
- 2015-02-12 KR KR1020167025858A patent/KR20160124202A/ko active IP Right Grant
- 2015-02-12 TW TW104104698A patent/TWI530536B/zh not_active IP Right Cessation
- 2015-02-12 JP JP2016553323A patent/JP6310089B2/ja not_active Expired - Fee Related
- 2015-02-12 EP EP15705568.2A patent/EP3107967A1/en not_active Withdrawn
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2016
- 2016-08-19 CL CL2016002095A patent/CL2016002095A1/es unknown
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2017
- 2017-09-12 HR HRP20171368TT patent/HRP20171368T1/hr unknown
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- 2019-01-04 US US16/240,338 patent/US10619051B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES2640099T3 (es) | 2017-10-31 |
| CN106029792A (zh) | 2016-10-12 |
| PT2910610T (pt) | 2017-09-15 |
| CN106029792B (zh) | 2018-09-11 |
| EP2910610A1 (en) | 2015-08-26 |
| TWI530536B (zh) | 2016-04-21 |
| MX2016010842A (es) | 2016-11-17 |
| CL2016002095A1 (es) | 2017-02-24 |
| HRP20171368T1 (hr) | 2017-11-03 |
| RU2647026C1 (ru) | 2018-03-13 |
| SI2910610T1 (sl) | 2017-10-30 |
| DK2910610T3 (en) | 2017-09-25 |
| EP3107967A1 (en) | 2016-12-28 |
| US20190136066A1 (en) | 2019-05-09 |
| EP2910610B1 (en) | 2017-07-05 |
| US10316193B2 (en) | 2019-06-11 |
| AU2015220955A1 (en) | 2016-08-25 |
| US10619051B2 (en) | 2020-04-14 |
| AU2015220955B2 (en) | 2017-04-13 |
| WO2015124494A1 (en) | 2015-08-27 |
| KR20160124202A (ko) | 2016-10-26 |
| TW201544555A (zh) | 2015-12-01 |
| CA2939144A1 (en) | 2015-08-27 |
| US20170009076A1 (en) | 2017-01-12 |
| PL2910610T3 (pl) | 2017-12-29 |
| JP6310089B2 (ja) | 2018-04-11 |
| JP2017512849A (ja) | 2017-05-25 |
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