EP4229125A1 - Compositions polymères à charge minérale résistante aux rayures, procédés de production et utilisations - Google Patents
Compositions polymères à charge minérale résistante aux rayures, procédés de production et utilisationsInfo
- Publication number
- EP4229125A1 EP4229125A1 EP21765875.6A EP21765875A EP4229125A1 EP 4229125 A1 EP4229125 A1 EP 4229125A1 EP 21765875 A EP21765875 A EP 21765875A EP 4229125 A1 EP4229125 A1 EP 4229125A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer composition
- inorganic filler
- load
- polymer
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 225
- 229920000642 polymer Polymers 0.000 title claims abstract description 213
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 title description 7
- 239000011707 mineral Substances 0.000 title description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 97
- 239000011256 inorganic filler Substances 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 82
- 239000004952 Polyamide Substances 0.000 claims abstract description 38
- 229920002647 polyamide Polymers 0.000 claims abstract description 38
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 24
- 239000004417 polycarbonate Substances 0.000 claims abstract description 24
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 24
- 229920000728 polyester Polymers 0.000 claims abstract description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 96
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 150000002484 inorganic compounds Chemical class 0.000 claims description 55
- 229910010272 inorganic material Inorganic materials 0.000 claims description 55
- 239000005909 Kieselgur Substances 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 43
- 238000012360 testing method Methods 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 39
- 239000005995 Aluminium silicate Substances 0.000 claims description 38
- 235000012211 aluminium silicate Nutrition 0.000 claims description 38
- 229910052618 mica group Inorganic materials 0.000 claims description 30
- 239000010445 mica Substances 0.000 claims description 27
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 26
- 239000010456 wollastonite Substances 0.000 claims description 26
- 229910052882 wollastonite Inorganic materials 0.000 claims description 26
- 238000011068 loading method Methods 0.000 claims description 25
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000010451 perlite Substances 0.000 claims description 22
- 235000019362 perlite Nutrition 0.000 claims description 22
- 239000003365 glass fiber Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000011324 bead Substances 0.000 claims description 16
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 16
- 239000004917 carbon fiber Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000454 talc Substances 0.000 claims description 16
- 229910052623 talc Inorganic materials 0.000 claims description 16
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 description 19
- 239000004609 Impact Modifier Substances 0.000 description 9
- 238000013329 compounding Methods 0.000 description 9
- 239000004614 Process Aid Substances 0.000 description 8
- -1 e.g. Substances 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 238000009863 impact test Methods 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical class C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052628 phlogopite Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- QYFRTHZXAGSYGT-UHFFFAOYSA-L hexaaluminum dipotassium dioxosilane oxygen(2-) difluoride hydrate Chemical compound O.[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O QYFRTHZXAGSYGT-UHFFFAOYSA-L 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Chemical group 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006100 Vydyne® Polymers 0.000 description 2
- 238000010960 commercial process Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Chemical group 0.000 description 2
- 239000011572 manganese Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000005335 volcanic glass Substances 0.000 description 2
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- 229920013731 Dowsil Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910017356 Fe2C Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229920003317 Fusabond® Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000005035 Surlyn® Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- IUMKBGOLDBCDFK-UHFFFAOYSA-N dialuminum;dicalcium;iron(2+);trisilicate;hydrate Chemical compound O.[Al+3].[Al+3].[Ca+2].[Ca+2].[Fe+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IUMKBGOLDBCDFK-UHFFFAOYSA-N 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052869 epidote Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052610 inosilicate Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910001737 paragonite Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052889 tremolite Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052875 vesuvianite Inorganic materials 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/04—Polyamides derived from alpha-amino carboxylic acids
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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
Definitions
- the present disclosure relates to the field of polymer compositions comprising an inorganic filler, in particular to the use of inorganic fillers in scratch resistant polymer compositions. Furthermore, polymer compositions comprising an inorganic filler and articles of manufacture comprising the afore- mentioned polymer compositions are further provided by the present disclosure.
- Inorganic fillers e.g., mineral fillers
- improving one property may negatively affect another property.
- improving mechanical properties such as stiffness by addition of mineral fillers to thermoplastic resin, often results in deteriorating the scratch performance of the formulation.
- sacrificing haptic properties such as scratch resistance is not always feasible or desirable, e.g., in case of articles which are visible to the human eye such as casings of electrical devices, automotive interior and exterior parts etc.
- the present disclosure provides a scratch-resistant polymer composition that contains an inorganic filler and, optionally, further components, the polymer composition comprising a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, wherein the scratch resistance AL* of the polymer composition, as measured by the Erichsen scratch test, according to GMW 14688 Method A, fulfils one or more of the following conditions: i) a AL* of 2.0 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 20 N; iii) a AL* of 0.5 or less measured at a load of 10 N and the polymer composition further fulfils one or more of the following conditions the tensile modulus of the polymer composition is improved by at least about 1.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined
- the present disclosure provides a method for improving one or more of the following properties: a) tensile modulus; b) flexural modulus; c) tensile strength; d) flexural strength; of a polymer composition or an article formed from the polymer composition, the polymer composition comprising a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, wherein the method comprises adding an inorganic filler and, optionally, further components to the polymer or the mixture thereof, while concomitantly achieving one or more of the following scratch resistances AL*, determined by the Erichsen scratch test according to GMW 14688 Method A, i) a AL* of 2.0 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 20 N; iii) a AL* of 0.5 or less measured at a
- the present disclosure provides a use of an inorganic filler in a polymer composition to improve one or more of the following properties: a) tensile modulus; b) flexural modulus; c) tensile strength; d) flexural strength; of the polymer composition or an article formed from the polymer composition, wherein the polymer composition comprises a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof and, optionally, further components, while concomitantly achieving one or more of the following scratch resistances AL*, determined by the Erichsen scratch test according to GMW 14688 Method A, i) a AL* of 2.0 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 20 N; iii) a AL* of 0.5 or less measured at a load of 10 N.
- the polymer composition comprises a polymer
- the present disclosure provides an article of manufacture, for example automotive, electrical & electronics, packaging, sporting, safety, household, load bearing, structural or heat resistant goods/components, comprising the polymer composition according to the first aspect.
- Fig. 1 shows the KraussMaffei Berstorff co-rotating intermeshing twin-screw extruder used in the experimental part
- Fig. 2 shows the screw design of the KraussMaffei Berstorff co-rotating intermeshing twin-screw extruder used in the experimental part;
- Fig. 3 shows the notched Izod impact test results of the examples
- Fig. 4 shows the notched Charpy impact test results of the examples
- Fig. 5 shows the unnotched Charpy impact test results of the examples
- Fig. 6 shows the flexural modulus test results of the examples
- Fig. 7 shows the flexural strength test results of the examples
- Fig. 8 shows the tensile modulus test results of the examples
- Fig. 9 shows the tensile strength test results of the examples
- Fig. 10 shows the tensile elongation (elongation at break) test results of the examples
- Fig. 11 shows the test results of the Erichsen scratch test conducted with a load of 40 N;
- Fig. 12 shows the test results of the Erichsen scratch test conducted with a load of 20 N.
- the expression “article formed from the polymer composition” denotes that the polymer composition and, optionally, further components are used to prepare an article, usually by methods known in the art such as compounding extrusion and injection molding etc.
- the polymer composition as such is formed into an article, i.e., without the addition of further components.
- an inorganic filler in a polymer composition comprising a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof not only improves one or more physical properties but concomitantly achieves a good scratch resistance. It has further been found that a polymer composition having a scratch resistance AL*, determined by the Erichsen scratch test according to GMW 14688 Method A with a load of 40 N of 2.0 or less may be provided.
- the polymer composition comprises an inorganic filler.
- the inorganic filler comprises an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- the inorganic filler comprises an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica or mixtures thereof and the polymer composition is free of talc.
- an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica or mixtures thereof and the polymer composition is free of talc.
- the inorganic compound may be selected from glass fiber, wollastonite, kaolin, metakaolin, graphite, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), perlite, diatomaceous earth (DE), and mica, for example, the inorganic compound may be selected from glass fiber, wollastonite, kaolin, metakaolin, graphite, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), perlite, and diatomaceous earth (DE) and for example, the inorganic compound may be selected from glass fiber, wollastonite, kaolin, metakaolin, and graphite.
- the total amount of inorganic filler is from about 2.0 wt.-% to about 50 wt.-%, or from about 5.0 to about 40 wt.-% or from about 7.5 to 35 wt.-%.
- the total amount of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica and talc, if present, the total amount of inorganic filler may be from about 2.0 wt.-% to about 50 wt.-%, or from about 5.0 wt.-% to about 40 wt.-% or from about 7.5 wt.-% to about 35 wt.-%, based on the total weight of the polymer composition.
- the inorganic filler comprises, based on the total weight of the inorganic filler, at least about 80 wt.-%, or at least 95 wt.-% or essentially consists of the inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc, if present, or mixtures thereof.
- GCC grounded calcium carbonate
- PCC precipitated calcium carbonate
- DE diatomaceous earth
- mica talc
- the inorganic compound and/or the inorganic filler has a dso particle size, determined by sedigraph, of from about 0.1 to about 75 pm or from about 0.1 to about 65 pm or from about 0.1 to 50 pm. In a specific embodiment, the inorganic inorganic compound and/or the inorganic filler has a dso particle size, determined by sedigraph of from about 0.1 pm to about 10 pm, or from about 0.5 pm to about 7.5 pm, or from about 0.5 pm to about 6.0 pm.
- the inorganic compound may be essentially dry.
- the inorganic compound comprises no greater than about 1.0 wt.-% of water, based on the total weight of the inorganic compound.
- the inorganic compound and/or the inorganic filler may comprise surface treatment additives, which may be selected from stearic acid or its salts, fatty acids or fatty acid amides, paraffin, glycerol monostearate, polyethylene glycol, polypropylene glycol, ethylene-vinyl acetate, a blend of fatty ester copolymers with acidic groups, polyoxyethylene stearate, propylene glycol monostearate, amino silane, vinyl silane, mercapto silane, epoxy silane, methacrylate silane, styryl silane, isocyanate silane, aromatic silane, alkyl or ester modified siloxane, alkane sulfonate, or mixtures thereof.
- Stearic acid salts may be selected from magnesium stearate or zinc stearate.
- the inorganic compound and/or the inorganic filler may comprise no greater than about 10.0 wt.-%, for example, no greater than about 9.0 wt.-%, or no greater than about 8.0 wt.-%, or no greater than about 7.0 wt.-%, or no greater than about 6.0 wt.-%, or no greater than about 5.0 wt.-%, or no greater than about 4.0 wt.-%, or no greater than about 3.0 wt.-%, or no greater than about 2.0 wt.-%, or no greater than about 1.0 wt.-%, or no greater than about 0.9 wt.-%,or no greater than about 0.8 wt.-%, or no greater than about 0.7 wt.-%, or no greater than about 0.6 wt.-%, or no greater than about 0.5 wt.-%, of surface treatment additives, based on the total weight of inorganic compound and the inorganic filler, respectively
- the inorganic compound and/or the inorganic filler may comprise no less than about 0.05 wt.-%, for example, no less than about 0.1 wt.-%, or no less than about 0.3 wt.-%, or no less than about 0.4 wt.-%, or no less than about 0.5 wt.-%, of surface treatment additives, based on the total weight of inorganic compound and the inorganic filler, respectively.
- the inorganic compound and/or the inorganic filler may comprise from about 0.05 wt.-%, to about 10.0 wt.-%, for example, from about 0.1 wt.-% to about 7.0 wt.-%, or from about 0.1 wt.-% to about 5.0 wt.-%, or from about 0.05 wt.-% to about 1.0 wt.-%, or from about 0.1 wt.-% to about 1.0 wt.-%, or from about 0.05 wt.-% to about 0.9 wt.-%, or from about 0.1 wt.-% to about 0.9 wt.-%, or from about 0.5 wt.-% to about 0.9 wt.-%, or from about 0.1 wt.-% to about 0.5 wt.-%, or from about 0.3 wt.-% to about 0.7 wt.-%, or from about 0.4 wt.-% to about 0.6
- the inorganic compound and/or the inorganic filler is a compressed inorganic compound and inorganic filler, respectively. It may be that the inorganic compound and/or the inorganic filler is a granulated inorganic compound and inorganic filler, respectively. It may be that the inorganic compound and/or the inorganic filler is a compressed granulated inorganic compound and inorganic filler, respectively.
- the compressed granulated inorganic compound and/or the inorganic filler is a inorganic compound and inorganic filler, respectively, in brick, briquette, pellet, pressing, mould, preform, spray-dried powder, tablet, aggregate, rod, granulate or agglomerate form, or any mixture thereof.
- the compressed granulated inorganic compound and/or the inorganic filler may have a tapped density in accordance with ISO 787/11 of no greater than about 2.0 g/cm 3 , for example, no greater than about 1.8 g/cm 3 , or no greater than about 1.6 g/cm 3 , or no greater than about 1.4 g/cm 3 , or no greater than about 1.2 g/cm 3 .
- the compressed granulated inorganic compound and/or the inorganic filler may have a tapped density in accordance with ISO 787/11 of no less than about 0.4 g/cm 3 , or no less than about 0.6 g/cm 3 , or no less than about 0.8 g/cm 3 .
- the compressed granulated inorganic compound and/or the inorganic filler may have a tapped density in accordance with ISO 787/11 of from about 0.4 g/cm 3 to about 2.0 g/cm 3 , for example from about 0.6 g/cm 3 to about 1.6 g/cm 3 , or from about 0.6 g/cm 3 to about 1.4 g/cm 3 , or from about 0.8 g/cm 3 to about 1.2 g/cm 3 .
- Wollastonite refers to the calcium inosilicate mineral (CaSiOs), which may also contain smallamounts of iron, magnesium and/or manganese substituting for calcium. Wollastonite may also contain associated minerals such as garnets, vesuvianite, diopside, tremolite, epidote, plagioclase feldspar, pyroxene and calcite.
- the wollastonite has a dso particle size, determined by microtrac (laser) of about 3.0 to about 30 pm and/or a BET surface area of about 0.7 to about 4.2 m 2 /g. In a further embodiment, the wollastonite has an aspect ratio greater than 4, and a dso particle size, determined by microtrac (laser) of about 7 to about 30 pm and/or a BET surface area of about 0.7 to about 3.0 m 2 /g.
- the wollastonite has an aspect ratio of 4 or less, and a dso particle size, determined by microtrac (laser) of about 3.0 to about 14 pm and/or a BET surface area of about 1.2 to about 4.2 m 2 /g.
- Kaolin clay also referred to as china clay or hydrous kaolin, predominately comprises the mineral kaolinite (Al2Si2Os(OH)4), a hydrous aluminum silicate, and small amounts of various impurities, such as quartz, micas, smectite, graphite, iron oxides, iron sulfides, and/or titania-based impurities.
- mineral kaolinite Al2Si2Os(OH)4
- impurities such as quartz, micas, smectite, graphite, iron oxides, iron sulfides, and/or titania-based impurities.
- the term “kaolin” encompasses hydrous kaolin as well as calcined kaolin but is not limited thereto. In one embodiment, the kaolin is selected from the group consisting of hydrous kaolin and calcined kaolin.
- the kaolin may have a dso particle size, determined by sedigraph of about 0.1 to about 2.0 pm.
- the kaolin comprises or consists of hydrous kaolin and the hydrous kaolin may have a dso particle size, determined by sedigraph of about 0.1 to about 2.0 pm.
- the kaolin comprises or consists of calcined kaolin and the calcined kaolin may have a dso particle size, determined by sedigraph, of about 0.3 to about 1.5 pm.
- Ground calcium carbonate (GCC) is obtained from a natural source by grinding. Ground calcium carbonate (GCC) is typically obtained by crushing and then grinding a mineral source such as chalk, marble or limestone, which may be followed by a particle size classification step, in order to obtain a product having the desired degree of fineness. Other techniques such as bleaching, flotation and magnetic separation may also be used to obtain a product having the desired degree of fineness and/or colour.
- the particulate solid material may be ground autogenously, i.e., by attrition between the particles of the solid material themselves, or, alternatively, in the presence of a particulate grinding medium comprising particles of a different material from the calcium carbonate to be ground.
- these processes may be carried out with or without the presence of a dispersant, which may be added at any stage of the process.
- the ground calcium carbonate (GCC) has a dso particle size, determined by sedigraph, of about 0.7 to about 3.0 pm and/or a calcite content of at least about 87 wt.-%.
- Precipitated calcium carbonate may be produced by any of the known methods available in the art.
- TAPPI Monograph Series No 30, "Paper Coating Pigments", pages 34-35 describes the three main commercial processes for preparing precipitated calcium carbonate which may be used in the practice of the present disclosure.
- a calcium carbonate feed material such as limestone
- the quicklime is then slaked in water to yield calcium hydroxide or milk of lime.
- the milk of lime is directly carbonated with carbon dioxide gas. This process has the advantage that no by-product is formed, and it is relatively easy to control the properties and purity of the calcium carbonate product.
- the milk of lime is contacted with soda ash to produce, by double decomposition, a precipitate of calcium carbonate and a solution of sodium hydroxide.
- the sodium hydroxide may be substantially completely separated from the calcium carbonate if this process is used commercially.
- the milk of lime is first contacted with ammonium chloride to give a calcium chloride solution and ammonia gas.
- the calcium chloride solution is then contacted with soda ash to produce by double decomposition precipitated calcium carbonate and a solution of sodium chloride.
- the crystals can be produced in a variety of different shapes and sizes, depending on the specific reaction process that is used.
- the precipitated calcium carbonate (PCC) has a dso particle size, determined by sedigraph, of about 0.1 to about 1.0 pm.
- Micas usually have the general formula X2Y4-6Zs02o(OH,F)4, wherein X is K, Na, or Ca; Y is Al, Mg, or Fe; and Z is Si, Al, Fe 3+ , or Ti, although micas may include Ba, Cs, Fe 2+ , Li, Cr, Mn, V, Zn, Be, or a combination thereof.
- Mica minerals suitable for the compositions herein include, but are not limited to, muscovite, paragonite, phlogopite, biotite, and combinations thereof.
- the mica is selected from the group consisting of muscovite mica and phlogopite mica.
- the mica may have a dso particle size, determined by sedigraph, of about 4.0 to about 45 pm and/or a dso particle size, determined by microtrac (laser) of about 20 to about 200 pm.
- the mica comprises or consists of muscovite mica and the muscovite mica may have a dso particle size, determined by sedigraph, of about 4.0 to about 40 pm and/or a dso particle size, determined by microtrac (laser) of about 20 to about 200 pm.
- the mica comprises or consists of phlogopite mica and the phlogopite mica may have a dso particle size, determined by sedigraph, of about 8.0 to about 45 pm and/or a dso particle size, determined by microtrac (laser) of about 25 to about 200 pm.
- Diatomaceous earth is, in general, a sedimentary biogenic silica deposit comprising the fossilized skeletons of diatoms, one-celled algae-like plants that accumulate in marine or fresh water environments.
- Honeycomb silica structures generally give diatomaceous earth (DE) useful characteristics such as absorptive capacity and surface area, chemical stability, and low-bulk density.
- DE diatomaceous earth
- natural diatomaceous earth comprises about 90% SiC>2 mixed with other substances.
- crude diatomaceous earth comprises about 90% SiC>2, plus various metal oxides, such as but not limited to Al, Fe, Ca, and Mg oxides.
- the particulate diatomaceous earth (DE) is typically a natural diatomaceous earth, which may be obtained from a saltwater source or from a freshwater source.
- the diatomaceous earth (DE) may be in its crude form or after subjecting the material to one or more processing steps.
- the diatomaceous earth has a dso particle size, determined by microtrac (laser) of about 5.0 to about 40 pm.
- Perlite is a naturally occurring siliceous volcanic glass rock, generally distinguishable from other volcanic glasses due to its expansion from about four to about twenty times its original volume when heated to a temperature within its softening range.
- Perlite is a hydrated material that may contain, for example, about 72 to about 75 wt.-% SiC>2, about 12 to about 14 wt.-% AI2O3, about 0.5 to about 2 wt.-% Fe2C>3, about 3 to about 5 wt.-% Na2 ⁇ D, about 4 to about 5 wt.-% K2O, about 0.4 to about 1.5 wt.-% CaO, and trace amounts of other metallic elements.
- Perlite may be used in its expanded and in its unexpanded form.
- the perlite has a dso particle size, determined by microtrac (laser) of about 20 to about 40 pm both in its expanded and unexpanded form.
- the inorganic filler comprises an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof, wherein inorganic compounds have the following particle sizes: or any embodiment thereof as herein-described.
- the polymer composition comprises a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, and may be selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof.
- the polymer is a polyamide, for example wherein the polyamide is selected from the group consisting of PA6, PA66, PA11 , PA12, PA46 and mixtures thereof and for example, the polyamide may be PA66.
- a suitable polymer for example, is Vydyne® 21SPC, a Nylon 66, obtainable from Ascend Performance Materials.
- base resin denotes the entirety of polymeric parts present in the polymer composition.
- the base resin may further comprise one or more further polymeric compounds, such as a polymeric impact modifier, a polymeric process aid and/or a polymeric scratch additive.
- the base resin of the polymer composition comprises at least about 70 wt.-%, or at least about 85, or at least about 90 wt.-% or essentially consists of the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, for example, the base resins comprises at least about 99.5 wt.-% of the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof.
- the total amount of polyamides, polyesters, polycarbonates, acrylonitrile butadiene styrenes (ABS) present in the base resin, based on the total amount of the base resin may be at least about 70 wt.-%, such as at least about 85 wt.-% or at least about 99.5 wt.-%.
- the base resin of the polymer composition comprises at least about 70 wt.-%, or at least about 85 wt.-% or essentially consists of (a) the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof and, (b), optionally, one or more polymeric compounds, selected from the group consisting of a polymeric impact modifier, a polymeric process aid and a polymeric scratch additive, for example, the base resins comprises at least about 99.5 wt.-% of (a) the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, and, (b), optionally, one or more polymeric compounds, selected from the group consisting of a polymeric impact modifier, a polymeric process aid and a polymeric scratch additive.
- the total amount of polyamides, polyesters, polycarbonates, acrylonitrile butadiene styrenes (ABS) and polymeric impact modifiers, polymeric process aids and a polymeric scratch additives present in the base resin, based on the total amount of the base resin is in one embodiment at least about 70 wt.-%, such as at least about 85 wt.-% and or at least about 99.5 wt.-%.
- polymeric impact modifiers are, for example, selected from one or more of the following class of compounds (also non-limiting examples are provided):
- ethylene and methacrylic acid ionomers e.g., Surlyn® ionomers, obtainable from Dow;
- EPDM ethylene propylene diene monomer rubber
- SAN - styrene acrylonitrile resin
- EPDM ethylene propylene diene monomer rubber
- the polymer composition may be made by compounding one or more polymers with the inorganic filler and, optionally, further components.
- Compounding per se is a technique which is well known to persons skilled in the art of polymer processing and manufacture and consists of preparing plastic formulations by mixing and/or blending polymers and optional additives in a molten state. It is understood in the art that compounding is distinct from blending or mixing processes conducted at temperatures below that at which the constituents become molten.
- Compounding may, for example, be used to form a masterbatch composition.
- Compounding may, for example, involve adding a masterbatch composition to a polymer to form a further polymer composition.
- the optional further components may, for example, be polymeric impact modifiers, polymeric process aids and polymeric scratch additives as described herein and conventional additives, usually stabilizers and antioxidants.
- the total amount of stabilizers and antioxidants is 2.0 wt.-% or less, based on the total weight of the polymer composition.
- the polymer composition may, for example, be extruded.
- compounding may be carried out using a screw, e.g., a twin screw, compounder, for example, a Baker Perkins 25 mm twin screw compounder.
- compounding may be carried out using a co-kneader or internal mixer.
- the methods disclosed herein may, for example, include compression moulding or injection moulding.
- the polymer and/or mineral filler and/or optional additives may be premixed and fed from a single hopper.
- the resulting melt may, for example, be cooled, for example in a water bath or on a conveyor belt, and then pelletized.
- the polymer composition may comprise no greater than about 2.0 wt.-%, for example, no greater than about 1.5 wt.-%, or no greater than about 1.0 wt.-%, or no greater than about 0.5 wt.-%, or no greater than about 0.1 wt.-%, or no greater than about 0.09 wt.-%, of surface treatment additives, based on the total weight of the polymer composition.
- the polymer composition may comprise no less than about 0.01 wt.-%, for example, no less than about 0.05 wt.-%, or no less than about 0.1 wt.-%, of surface treatment additives, based on the total weight of the polymer composition.
- the polymer composition may comprise from about 0.01 wt.-% to about 2.0 wt.-%, for example, from about 0.01 wt.-% to about 1.5 wt.-%, or from about 0.01 wt.-% to about 1.0 wt.-%, or from about 0.01 wt.-% to about 0.5 wt.-%, or from about 0.01 wt.-% to about 0.1 wt.-%, or from about 0.01 wt.-% to about 0.09 wt.-%, or from about 0.05 wt.-% to about 2.0 wt.-%, or from about 0.05 wt.-% to about 1 .0 wt.-%, or from about 0.05 wt.-% to about 0.1 wt.-%, or from about 0.05 wt.-% to about 0.09 wt.-%, of surface treatment additives, based on the total weight of the polymer composition.
- the base resin makes up from about 50 to about 98 wt.-% of the polymer composition, for example from about 60 to about 95 wt.-% or from about 65 to about 92.5 wt.-%.
- the polymer of the polymer composition is a polyamide
- the polyamide may be selected from the group consisting of PA6, PA66, PA11 , PA12, PA46 and mixtures thereof, or the polyamide may be PA6, PA46, or PA66 and the base resin may comprise one or more polymeric compounds, selected from the group consisting of a polymeric impact modifier, a polymeric process aid and a polymeric scratch additive, for example, the polyamide and the one or more polymeric compounds, selected from the group consisting of a polymeric impact modifier, a polymeric process aid and a polymeric scratch additive, if present, make up at least about 95 wt.-% of the base resin.
- the polymer composition may comprise the base resin in an amount of from about 65 wt.-% to about 92.5 wt.-% and the inorganic filler in an amount of from about 7.5 wt.-% to about 35 wt.-%, for example, the inorganic filler comprises or consist of an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica or mixtures thereof and the polymer composition is free of talc.
- the polymer composition may further comprise up to 2 wt.-% of stabilizers and/or antioxidants.
- the polymer composition according to the first aspect fulfils two or more of the following conditions or three or more of the following conditions or all four of the following conditions: the tensile modulus of the polymer composition is improved by at least about 1.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 527-2; the flexural modulus of the polymer composition is improved by at least about 1.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 178, the tensile strength of the polymer composition is improved by at least about 0.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 527-2; the flexural strength of the polymer composition is improved by at least about 1.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 178.
- the polymer composition according to the first aspect fulfils one or more of the following conditions or two or more of the following conditions or three or more of the following conditions or all four of the following conditions the tensile modulus of the polymer composition is improved by at least about 2.0% or at least about 2.5% or at least about 3.0% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 527-2; the flexural modulus of the polymer composition is improved by at least about 2.0% or at least about 2.5% or at least about 3.0% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 178, the tensile strength of the polymer composition is improved by 0.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 527-2; the flexural strength of the polymer composition is improved by at least about 2.0% or at least about 2.5% or at least about 3.0% for each 1
- the scratch resistance AL* of the polymer composition determined by the Erichsen scratch test according to GMW 14688 Method A fulfils one or more of the following conditions: i) a AL* of 1.5 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 25 N, iii) a AL* of 0.5 or less measured at a load of 15 N.
- the scratch resistance AL* of the polymer composition determined by the Erichsen scratch test according to GMW 14688 Method A fulfils one or more of the following conditions: i) a AL* of 1.0 or less measured at a load of 40 N, ii) a AL* of 0.5 or less measured at a load of 20 N.
- the scratch resistance AL* of the polymer composition determined by the Erichsen scratch test according to GMW 14688 Method A with a load of 40 N, is about 2.0 or less, or about 1 .0 or about 0.5 or less.
- the ratio between the scratch resistance AL* of the polymer composition, determined by the Erichsen scratch test according to GMW 14688 Method A with a load of 40 N and the amount of inorganic filler in weight percent based on the total weight of the polymer composition may be below about 0.1 % -1 , for example below about 0.07% -1 .
- the ratio between the scratch resistance AL* of the polymer composition, determined by the Erichsen scratch test according to GMW 14688 Method A with a load of 20 N and the amount of inorganic filler in weight percent based on the total weight of the polymer composition may be below about 0.08% -1 , for example below about 0.06% -1 .
- the polymer composition may have a flexural modulus of at least about 3000 MPa, such as at least about 3250 MPa or at least about 4000 MPa, for example at least about 5000 MPa or at least about 6000 MPa. Usually, the flexural modulus does not exceed about 12000 MPa.
- the polymer composition may have a flexural strength of at least about 75 MPa, such as at least about 100 MPa or at least about 125 MPa. Usually, the flexural strength does not exceed about 400 MPa.
- the polymer composition may have a tensile modulus of at least about 3000 MPa, such as at least about 3500 MPa or at least about 4000 MPa, for example at least about 6000 MPa or at least about 8000 MPa. Usually, the tensile modulus does not exceed about 14000 MPa.
- the polymer composition may have a tensile strength of at least about 50 MPa, such as at least about 70 MPa or at least about 90 MPa. Usually, the tensile strength does not exceed about 250 MPa. [75] The polymer composition may have a Tensile elongation of at least about 1.0 MPa, such as at least 1.5 MPa or at least about 2.0 MPa, for example at least about 4.0 MPa or at least about 8.0 MPa.
- the polymer composition may have an impact resistance (also referred to as "impact energy” or “impact strength”), as measured by the Notched Izod test at 23°C of at least about 1.0 kJ/m 2 , such as at least about 1.5 kJ/m 2 or at least about 2.0 kJ/m 2 , for example at least about 2.5 kJ/m 2 or at least about 3.0 kJ/m 2 .
- impact resistance measured by the Notched Izod test at 23°C will not exceed about 12 kJ/m 2 .
- a further method to determine the impact resistance is the Charpy test, which may be conducted with a notched or an unnotched specimen.
- the polymer composition may have an impact resistance as measured by the Notched Charpy test at 23°C of at least about 1.0 kJ/m 2 , such as at least about 1.4 kJ/m 2 or at least about 1.8 kJ/m 2 , for example at least about 2.0 kJ/m 2 or at least about 2.5 kJ/m 2 .
- the impact resistance measured by the Notched Charpy test at 23°C will not exceed about 12 kJ/m 2 .
- the polymer composition may have an impact resistance as measured by the unnotched Charpy test at 23°C of at least about 5.0 kJ/m 2 , such as at least about 7.5 kJ/m 2 or at least about 10 kJ/m 2 , for example at least about 20 kJ/m 2 or at least about 50 kJ/m 2 or at least about 100 kJ/m 2 .
- the impact resistance measured by the Notched Charpy test at 23°C will not exceed about 12 kJ/m 2 .
- a scratch-resistant polymer composition that contains an inorganic filler and, optionally, further components, the polymer composition comprising a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, wherein the scratch resistance AL* of the polymer composition, as measured by the Erichsen scratch test, according to GMW 14688 Method A, fulfils one or more of the following conditions: i) a AL* of 2.0 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 20 N; iii) a AL* of 0.5 or less measured at a load of 10 N and the polymer composition further fulfils one or more of the following conditions the tensile modulus of the polymer composition is improved by at least about 1.5% for each 1 wt.-% loading of inorganic filler compared to the unfilled resin, determined according to ISO 527-2; the flexural modulus
- Method for improving one or more of the following properties a) tensile modulus; b) flexural modulus; c) tensile strength; d) flexural strength; of a polymer composition or an article formed from the polymer composition, the polymer composition comprising a polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof, wherein the method comprises adding an inorganic filler and, optionally, further components to the polymer or the mixture thereof, while concomitantly achieving one or more of the following scratch resistances AL*, determined by the Erichsen scratch test according to GMW 14688 Method A, i) a AL* of 2.0 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 20 N; iii) a AL* of 0.5 or less measured at a load of 10 N.
- AL* scratch resistances
- the inorganic filler comprises an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- the inorganic filler comprises an inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- the polymer composition or methodaccording to numbered paragraph 3 wherein the inorganic compound is selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica or mixtures thereof.
- the polymer composition or method according to numbered paragraph 5 wherein the total amount of inorganic filler, based on the total weight of the polymer composition, is from about 5.0 wt.-% to about 40 wt.-%.
- the polymer composition or method according to numbered paragraph 6 wherein the total amount of inorganic filler, based on the total weight of the polymer composition, is from about 7.5 wt.-% to about 35 wt.-%.
- the inorganic filler comprises at least about 80 wt.-% based on the total weight of the inorganic filler, of the inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- the inorganic filler comprises at least about 80 wt.-% based on the total weight of the inorganic filler, of the inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- GCC grounded calcium carbonate
- PCC precipitated calcium carbonate
- DE diatom
- the inorganic filler comprises at least about 95 wt.-% based on the total weight of the inorganic filler, of the inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- the inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- the inorganic filler essentially consists of the inorganic compound selected from the group consisting of glass fibers, glass beads, glass spheres, perlite, carbon fiber, graphite, wollastonite, kaolin, metakaolin, grounded calcium carbonate (GCC), precipitated calcium carbonate (PCC), diatomaceous earth (DE), mica, talc or mixtures thereof.
- GCC grounded calcium carbonate
- PCC precipitated calcium carbonate
- DE diatomaceous earth
- mica talc or mixtures thereof.
- the polymer composition or method according to numbered paragraph 11 wherein the inorganic compound or the inorganic filler has a dso particle size, determined by sedigraph, of from about 0.5 pm to about 7.5 pm.
- the polymer composition or method according to numbered paragraph 12 wherein the inorganic compound or the inorganic filler has a dso particle size, determined by sedigraph, of from about 0.5 pm to about 6.0 pm.
- the base resin of the polymer composition comprises at least about 70 wt.-% of the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof.
- the base resin of the polymer composition comprises at least about 90 wt.-% of the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof.
- the polymer composition or method according to numbered paragraph 15 wherein the base resin of the polymer composition essentially consists of the polymer selected from the group consisting of polyamide, polyester, polycarbonate, acrylonitrile butadiene styrene (ABS) and mixtures thereof.
- ABS acrylonitrile butadiene styrene
- the scratch resistance AL* of the polymer composition determined by the Erichsen scratch test according to GMW 14688 Method A fulfils one or more of the following conditions: i) a AL* of 1.5 or less measured at a load of 40 N, ii) a AL* of 1.0 or less measured at a load of 25 N, iii) a AL* of 0.5 or less measured at a load of 15 N.
- An article of manufacture for example automotive, electrical & electronics, packaging, sporting, safety, household, load bearing, structural or heat resistant goods/components, comprising the polymer composition according to any one of the preceding numbered paragraphs 1 or 3 to 22.
- Particle sizes referred to in the present disclosure as being measured by sedigraph, are measured using a SEDIGRAPH 5120 instrument as supplied by Micromeritics Corporation with the Reynolds number being set to 0.30.
- the size of a given particle is expressed in terms of the diameter of a sphere of equivalent diameter, which sediments through the suspension, /.e., an equivalent spherical diameter or ESD.
- Particle sizes referred to in the present disclosure as being measured by microtrac(laser), are measured using a Leeds and North rup Microtrac X100 laser particle size analyzer (Leeds and Northrup, North Wales, Pennsylvania, USA), which can determine particle size distribution over a particle size range from 0.12 micrometers (pm or microns) to 704 pm.
- the size of a given particle is expressed in terms of the diameter of a sphere of equivalent diameter that sediments through the suspension, also known as an equivalent spherical diameter or “ESD.”
- ESD equivalent spherical diameter
- the median particle size, or dso value is the value at which 50% by weight of the particles have an esd less than that dso value.
- BET surface area refers to the technique for calculating specific surface area of physical absorption molecules according to Brunauer, Emmett, and Teller ("BET") theory. BET surface area may be measured by any appropriate measurement technique. In one aspect, BET surface area can be measured with a Micromeritics® ASAP 2460 surface area and porosity analyzer, using the program MicroActive for ASAP 2460 Version 2.01 and pure nitrogen as the sorbent gas, from Micromeritics Instrument Corporation (Norcross, Georgia, USA).
- the Erichsen scratch test is conducted according to GMW 14688 Method A with an indicated scratch load of 10 N, 20 N or 40 N.
- the tensile modulus, the tensile strength and the tensile elongation have been determined according to ISO 527 using the preferred specimen (Type I) at a speed of 5 mm/min.
- Vydyne® PA66 obtainable from Ascend performance materials has been used in the following experiments.
- Injection Molding ISO standard test specimens were prepared using ISO molds and a 66-ton Arburg Allrounder 370E 600-170 injection molder. All compounds were dried to a moisture content of less than 0.2 wt.-% prior to injection molding. Reduced back pressure was utilized to preserve the aspect ratio of glass fiber, wollastonite, mica, and hydrous kaolin.
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Abstract
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US202063072339P | 2020-08-31 | 2020-08-31 | |
PCT/EP2021/072893 WO2022043149A1 (fr) | 2020-08-31 | 2021-08-18 | Compositions polymères à charge minérale résistante aux rayures, procédés de production et utilisations |
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DE102005023420A1 (de) * | 2005-05-20 | 2006-11-23 | Ems-Chemie Ag | Polyamidformmassen mit verbesserter Fliessfähigkeit, deren Herstellung sowie deren Verwendung |
US8119718B2 (en) * | 2008-06-27 | 2012-02-21 | Basf Se | Thermally conductive polyamides with diatomaceous earth |
US9000080B2 (en) * | 2011-11-04 | 2015-04-07 | Specialty Minerals (Michigan) Inc. | Method for producing dry ground calcium carbonate for use in thermoset polyester resin systems |
EP3250639B1 (fr) * | 2015-01-29 | 2021-08-25 | Imerys Talc America, Inc. | Matières minérales modifiées destinées à être utilisées comme charges pour polycarbonates, et leurs procédés d'utilisation pour renforcer des polycarbonates |
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