NO303176B1 - Process for milling calcium carbonate in aqueous medium - Google Patents
Process for milling calcium carbonate in aqueous medium Download PDFInfo
- Publication number
- NO303176B1 NO303176B1 NO895266A NO895266A NO303176B1 NO 303176 B1 NO303176 B1 NO 303176B1 NO 895266 A NO895266 A NO 895266A NO 895266 A NO895266 A NO 895266A NO 303176 B1 NO303176 B1 NO 303176B1
- Authority
- NO
- Norway
- Prior art keywords
- grinding
- calcium carbonate
- suspension
- agent
- weight
- Prior art date
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 85
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000012736 aqueous medium Substances 0.000 title claims abstract description 5
- 238000003801 milling Methods 0.000 title description 2
- 238000000227 grinding Methods 0.000 claims abstract description 79
- 239000000725 suspension Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000002609 medium Substances 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 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 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene, propylene, isobutylene Chemical group 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 2
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 claims description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 claims description 2
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- 125000005499 phosphonyl group Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
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- XFSBVAOIAHNAPC-XTHSEXKGSA-N 16-Ethyl-1alpha,6alpha,19beta-trimethoxy-4-(methoxymethyl)-aconitane-3alpha,8,10alpha,11,18alpha-pentol, 8-acetate 10-benzoate Chemical compound O([C@H]1[C@]2(O)C[C@H]3[C@@]45C6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)[C@@H]4[C@]([C@@H](C[C@@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-XTHSEXKGSA-N 0.000 claims 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- XFSBVAOIAHNAPC-UHFFFAOYSA-N Aconitin Natural products CCN1CC(C(CC2OC)O)(COC)C3C(OC)C(C(C45)(OC(C)=O)C(O)C6OC)C1C32C4CC6(O)C5OC(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229940039750 aconitine Drugs 0.000 claims 1
- STDXGNLCJACLFY-UHFFFAOYSA-N aconitine Natural products CCN1CC2(COC)C(O)CC(O)C34C5CC6(O)C(OC)C(O)C(OC(=O)C)(C5C6OC(=O)c7ccccc7)C(C(OC)C23)C14 STDXGNLCJACLFY-UHFFFAOYSA-N 0.000 claims 1
- 150000003926 acrylamides Chemical class 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims 1
- 239000001530 fumaric acid Substances 0.000 claims 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
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- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
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- 239000003973 paint Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 35
- 229910052500 inorganic mineral Inorganic materials 0.000 description 16
- 239000011707 mineral Substances 0.000 description 16
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- 239000007900 aqueous suspension Substances 0.000 description 15
- 239000000049 pigment Substances 0.000 description 13
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- 238000001033 granulometry Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 239000001175 calcium sulphate Substances 0.000 description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- 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
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
- Disintegrating Or Milling (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Crushing And Grinding (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en fremgangsmåte for oppmaling i vandig medium av kalsiumkarbonat i nærvær av et vannopp-løselig oppmalingsmiddel i en mengde langt under det som vanligvis benyttes i den kjente teknikk og som ikke desto mindre fører til raffinerte suspensjoner med en konsentrasjon av tørrstoff på minst 70 vekt-# og et granulometrisk snitt på høyst 2 pm. The present invention relates to a method for grinding calcium carbonate in an aqueous medium in the presence of a water-soluble grinding agent in an amount far below that usually used in the known technique and which nevertheless leads to refined suspensions with a concentration of dry matter of at least 70 weight # and a granulometric section of no more than 2 pm.
Det har i lang tid vært kjent å benytte mineralstoffer som kalsiumkarbonat, -sulfat eller -silikat samt titandioksyd for å fremstille industrielle produkter ment for maling, belegning av papir, som fyllstoffer for kautsjuk og synte-tiske harpikser og så videre. It has long been known to use mineral substances such as calcium carbonate, sulphate or silicate as well as titanium dioxide to produce industrial products intended for paint, coating paper, as fillers for rubber and synthetic resins and so on.
Da imidlertid disse mineralstoffer ikke har noen naturlig lamellær eller sjiktstruktur som letter deres spalting slik tilfellet er når det gjelder visse stoffer som aluminium-silikater som vanligvis er kjent som kaolin, må fagmannen omdanne stoffene ved hjelp av oppmaling til vandig suspensjon med høy finhet der kornene har en dimensjon som er så liten som mulig, det vil si noen um, for å kunne benyttes på pigmentområdet. Since, however, these mineral substances have no natural lamellar or layered structure that facilitates their cleavage as is the case with certain substances such as aluminum silicates commonly known as kaolin, the person skilled in the art must convert the substances by grinding into an aqueous suspension of high fineness in which the grains has a dimension that is as small as possible, i.e. a few um, in order to be used in the pigment area.
Ut fra antallet publikasjoner man finner på dette området, viser spesiallitteraturen viktigheten og kompleksiteten av problemet oppmaling i vandig miljø av mineralstoffer for å oppnå en kvalitet som er spesielt raffinert og tillater en pigmentanvendelse. Det er derfor slik at det spesielt på området belegning av papir er godt kjent at belegningsmassen som består av mineralpigmenter som kaolin, kalsiumkarbonat, kalsiumsulfat samt titandioksyd som benyttes i suspensjon i vann, likeledes inneholder bindemidler og dispergeringsmidler samt andre tilsetningsstoffer som fortykningsmidler og farvestoffer. Således er det ønskelig at en slik belegnings-masse har en viskositet som er lav og stabil under beleg-ningen for å lette manipulering og påføring og samtidig en mengde av faststoff som er så høy som mulig for å redusere den mengde varmeenergi som er nødvendig for ved tørking å fjerne den vandige del av belegningsmassen. En slik ideell suspensjon forener alle de fundamentale kvaliteter og løser for fagmannen problemene som er kjent ved oppmaling, lagring, transport fra produksjonsstedet til anvendelsesstedet og likeledes overføring via pumper til anvendelse. From the number of publications to be found in this area, the specialist literature shows the importance and complexity of the problem of grinding in an aqueous environment of mineral substances in order to achieve a quality that is particularly refined and allows a pigment application. It is therefore the case that, especially in the area of coating paper, it is well known that the coating mass, which consists of mineral pigments such as kaolin, calcium carbonate, calcium sulphate and titanium dioxide which is used in suspension in water, also contains binders and dispersants as well as other additives such as thickeners and colourants. Thus, it is desirable that such a coating mass has a viscosity that is low and stable during coating to facilitate manipulation and application and at the same time an amount of solids that is as high as possible to reduce the amount of heat energy that is necessary for by drying to remove the aqueous part of the coating mass. Such an ideal suspension unites all the fundamental qualities and solves the problems known to the person skilled in grinding, storage, transport from the place of production to the place of use and likewise transfer via pumps to use.
Således er det fastslått at teknikkene for oppmaling i vandig miljø av mineralstoffer fører til ustabile suspensjoner med tiden, dette på grunn av en sedimentasjon av mineralstoffene og en økning av viskositeten. Dette er grunnen til at fagmannen, ved metoder som synes å høre til de eldste i teknikken for ved oppmaling å oppnå pigmentstoffer av mineralmaterialet i vandig suspensjon har måttet ty til å gjennomføre oppmalingen i ett eller flere suksessive trinn og derefter å tørke og klassifisere det oppmalte materialet for å fjerne partikler som ikke er tilstrekkelig fine, så å separere det partikkelformige materialet med den ønskede pigmentdimensjon for å oppnå et fint pulverformig mineral med liten vannmengde. Derefter kan dette fine pulver, ment for pigmentanvendelse, lett transporteres fra produksjons- til bruksstedet der det på ny underkastes suspensjon i vann for å kunne benyttes som pigmentprodukt. Thus, it has been established that the techniques for grinding in an aqueous environment of mineral substances lead to unstable suspensions over time, this due to a sedimentation of the mineral substances and an increase in viscosity. This is the reason why the person skilled in the art, using methods that seem to belong to the oldest in the technique of obtaining pigment substances from the mineral material in aqueous suspension by grinding, has had to resort to carrying out the grinding in one or more successive steps and then drying and classifying the ground the material to remove particles that are not sufficiently fine, then to separate the particulate material with the desired pigment dimension to obtain a fine powdery mineral with a small amount of water. After that, this fine powder, intended for pigment use, can be easily transported from the production site to the place of use, where it is again subjected to suspension in water in order to be used as a pigment product.
Det faktum at man ikke kan bevare det mineralske pigment-materialet i form av en vandig suspensjon mellom oppmalingen og anvendelsen har vært et incitament for fagmannen til å forfølge forskning på dette området, en forskning består i å realisere oppmalingen av mineralmaterialet i vandig suspensjon for efter oppmaling å oppnå en pigmentsuspensjon som har lav viskositet og som er stabil med tiden. Dette er for eksempel det som foreslås i FR-PS 1 506 724, nemlig en fremgangsmåte for ved oppmaling å fremstille en vandig tidsstabil kalsiumkarbonatsuspensjon og denne omfatter under omrøring å tildanne en vandig suspensjon inneholdende 25 til 50 vekt-# kalsiumkarbonat og å male opp dette vandige materialet ved hjelp av et egnet oppmalingslegeme i nærvær av et dispergeringsmiddel. Dette dispergeringsmiddel er en akrylpolymer som er oppløselig i vann og som man setter til oppmalingsmedium i en mengde av 0,2 til 0,4 vekt-#, beregnet på vekten av tilstedeværende kalsiumkarbonat. På tross av den uomtvistelige fordel det er å disponere en pigmentær mineralsuspensjon med god tidsstabilitet viser det seg at en slik suspensjon oppviser mangler som kan vise seg å være vesentlige for fagmannen. Dette er for eksempel tilfellet når det gjelder mengden av tørrstoff i en slik suspensjon som er ment for oppmaling og som imperativt må ligge mellom 25 og 50 vekt-# og fortrinnsvis være lik ca. 40 vekt-%. I det tilfellet der denne konsentrasjon er under 25$, er den beskrevne prosess lite interessant på grunn av den lave produktivitet og når konsentrasjonen av utgangstørrstoff er over 50$ reduseres effektiviteten ved oppmalingsprosessen på grunn av den sterke økning av viskositeten i miljøet, noe som blir et hinder for gjennomføring av selve oppmalingen og som således gir en suspensjon med for stor granulometri. The fact that you cannot preserve the mineral pigment material in the form of an aqueous suspension between the grinding and the application has been an incentive for the person skilled in the art to pursue research in this area, research consists in realizing the grinding of the mineral material in aqueous suspension for after grinding to obtain a pigment suspension which has a low viscosity and which is stable over time. This is, for example, what is proposed in FR-PS 1 506 724, namely a method for producing an aqueous, time-stable calcium carbonate suspension by grinding, and this comprises, while stirring, forming an aqueous suspension containing 25 to 50 wt-# of calcium carbonate and grinding this water the material by means of a suitable grinding body in the presence of a dispersant. This dispersant is an acrylic polymer which is soluble in water and which is added to the grinding medium in an amount of 0.2 to 0.4 by weight, calculated on the weight of calcium carbonate present. Despite the indisputable advantage of having a pigmentary mineral suspension with good time stability, it turns out that such a suspension exhibits defects which may prove to be significant for the person skilled in the art. This is, for example, the case when it comes to the quantity of dry matter in such a suspension which is intended for grinding and which imperatively must lie between 25 and 50 weight-# and preferably be equal to approx. 40% by weight. In the case where this concentration is below 25$, the described process is of little interest due to the low productivity and when the concentration of starting solids is above 50$, the efficiency of the grinding process is reduced due to the strong increase in the viscosity of the environment, which becomes an obstacle to carrying out the grinding itself and which thus gives a suspension with too large a granulometry.
Når konsentrasjonen av tørrstoff i suspensjonen ment for oppmaling velges innen området 25 til 50%, oppnår man en kalsiumkarbonatgranulometri efter meget lang oppmaling og i nærvær av et dispergeringsmiddel, som kan ansees som gunstig for pigmentanvendelse idet 95% av partiklene har sin største dimensjon under 2 pm. When the concentration of dry matter in the suspension intended for grinding is chosen within the range of 25 to 50%, a calcium carbonate granulometry is obtained after very long grinding and in the presence of a dispersant, which can be considered favorable for pigment use as 95% of the particles have their largest dimension below 2 p.m.
Det at man ikke har kunnet gjennomføre oppmalingen av en vandig suspensjon av mineralmaterialet ved konsentrasjoner utover 50% på grunn av den brutale viskositetsøkning har incitert fagmannen til å finne en ny vei. Det er derfor foreslått fremgangsmåter for anvendelse av vandig suspensjon og ikke lenger oppmaling av mineralmaterialet med høyt innhold av tørrstoff. FR-PS 1 562 326 angår for eksempel en fremgangsmåte for fremstilling av en vandig suspensjon av mineralmaterialer. Det tilsiktede mål ved denne fremgangsmåte er å oppnå en vandig suspensjon med høy konsentrasjon av tørrstoff og som er tilstrekkelig stabil til at den kan transporteres i denne form fra fabrikasjonsstedet til bruksstedet. Den foreslåtte fremgangsmåte består i å tildanne en vandig suspensjon av mineralmateriale inneholdende 70 til 85 vekt-% tørrstoff hvorav minst 99 vekt% av de opprinnelige partikler har en dimensjon lik eller mindre enn 50 um, derefter å omrøre suspensjonen i nærvær av et dispergeringsmiddel som kan være et natrium- eller kaliumsalt av en polyfosforsyre, en polyakrylsyre, en polysilisiumsyre og så videre, oppnådd ved total nøytralisering ved hjelp av et natrium- eller kaliumhydroksyd. Derefter innføres dette dispergeringsmiddel i en mengde av 0,05 til 0,5 vekt-% i forhold til vekten tørrstoff i suspensjonen. Forfatterne har fastslått at tørrstoffmengden i suspensjonen ikke må være høyere enn 85 vekt-% på grunn av den sterke økning av viskositeten og ikke kan være under 70 vekt-% uten å fremtvinge en skadelig sedimentering. The fact that it has not been possible to grind up an aqueous suspension of the mineral material at concentrations above 50% due to the brutal increase in viscosity has prompted the expert to find a new way. Methods have therefore been proposed for using an aqueous suspension and no longer grinding up the mineral material with a high content of dry matter. FR-PS 1 562 326 relates, for example, to a method for producing an aqueous suspension of mineral materials. The intended goal of this method is to obtain an aqueous suspension with a high concentration of dry matter and which is sufficiently stable that it can be transported in this form from the place of manufacture to the place of use. The proposed method consists in forming an aqueous suspension of mineral material containing 70 to 85% by weight of dry matter of which at least 99% by weight of the original particles have a dimension equal to or less than 50 µm, then stirring the suspension in the presence of a dispersant which can be a sodium or potassium salt of a polyphosphoric acid, a polyacrylic acid, a polysilicic acid and so on, obtained by total neutralization with a sodium or potassium hydroxide. This dispersant is then introduced in an amount of 0.05 to 0.5% by weight in relation to the weight of dry matter in the suspension. The authors have determined that the amount of solids in the suspension must not be higher than 85% by weight due to the strong increase in viscosity and cannot be below 70% by weight without forcing a harmful sedimentation.
Således foreslår den kjente teknikk oppløsninger som ikke helt kan være tilfredsstillende for fagmannen. Thus, the known technique proposes solutions that cannot be completely satisfactory for the person skilled in the art.
En av disse løsninger angår oppmalingen i nærvær av et dispergeringsmiddel, av en vandig suspensjon av kalsiumkarbonat med en for lav konsentrasjon av tørrstoff til å være interessant selv om den har fordelen av å gi en pigmentsuspensjon med lav viskositet og godt oppmalt og som gir opptil 95% partikler med dimensjoner under 2 um. One of these solutions concerns the milling, in the presence of a dispersing agent, of an aqueous suspension of calcium carbonate with too low a concentration of solids to be interesting even though it has the advantage of giving a pigment suspension of low viscosity and well milled and which gives up to 95 % particles with dimensions below 2 µm.
Den andre av disse løsninger består i å preparere en vandig suspensjon med høyt innhold av tørrstoff inneholdende 70 til 85 vekt-% mineralmateriale hvorav 99% av de opprinnelige partikler har en dimensjon under eller lik 50 um ved til dette medium å sette et dispergeringsmiddel som tillater å stabilisere partiklene. The second of these solutions consists in preparing an aqueous suspension with a high content of dry matter containing 70 to 85% by weight of mineral material of which 99% of the original particles have a dimension below or equal to 50 µm by adding to this medium a dispersant which allows to stabilize the particles.
Tallrike arbeider foreligger for å forbedre ydelsene til oppmalingsmidler på basis av karboksyliske polymerer som tillater å oppnå konsentrerte suspensjoner hva angår finoppmalt kalsiumkarbonat. Numerous works exist to improve the performance of grinding agents based on carboxylic polymers which allow to obtain concentrated suspensions of finely ground calcium carbonate.
Således beskriver FR-PS 2 539 137 et oppmalingsmiddel på basis av akryliske polymerer og/eller kopolymerer hvis molekylvekt er valgt innen et område for den spesifikke viskositet lik 0,50 til 0,60 og hvis nøytralisering gjennom-føres ved hjelp av minst et nøytraliseringsmiddel med en monovalent funksjon og minst et nøytraliseringsmiddel med en polyvalent funksjon. Thus, FR-PS 2 539 137 describes a grinding agent based on acrylic polymers and/or copolymers whose molecular weight is selected within a range for the specific viscosity equal to 0.50 to 0.60 and whose neutralization is carried out with the aid of at least one neutralizing agent with a monovalent function and at least one neutralizing agent with a polyvalent function.
På den annen side foreslår EP-PS 0 108 842 en forbedring av oppmalingsmidlet som består i å innføre en sulfonert komonomer som akrylamidopropansulfonsyre i karboksylpolymer-molekylet. On the other hand, EP-PS 0 108 842 proposes an improvement of the grinding agent which consists in introducing a sulphonated comonomer such as acrylamidopropane sulphonic acid into the carboxyl polymer molecule.
I alle disse tilfeller blir imidlertid kalsiumkarbonatsuspensjonene med høy konsentrasjon og stor finhet oppnådd med et vesentlig energiforbruk som fremtvinger en forhøyelse av temperaturen i mediet som i mesteparten av tiden over-skrider 100°C, et høyt forbruk i størrelsesorden 1% av oppmalingsmidlet i tørr tilstand i forhold til vekten av kalsiumkarbonat hvis man vil oppnå mer enn 60% partikler under 1 pm og en kalsiumkarbonatkonsentrasjon over 70%. In all these cases, however, the calcium carbonate suspensions with high concentration and great fineness are obtained with a significant energy consumption which forces an increase in the temperature of the medium which in most of the time exceeds 100°C, a high consumption of the order of 1% of the grinding agent in the dry state in relation to the weight of calcium carbonate if you want to achieve more than 60% particles below 1 pm and a calcium carbonate concentration above 70%.
Således representerer anvendelsen av mengder av meget høye mengder oppmalingsmidler, ikke desto mindre nødvendige for i dag for å oppnå de finfordelte konsentrerte suspensjoner med reologi og akseptabel stabilitet for papirbelegningsformål, vesentlige mangler som for eksempel de som angis nedenfor: en første mangel manifesterer seg i papirindustrien ved resirkulering av "skrap". Fordi nemlig resirkulering av en meget vesentlig mengde anionisk polyakrylat fremtvinger en i det minste partiell inhibering av de kationiske retensjonsmidler som benyttes og som forstyrrer ark-dannelsen; Thus, the use of quantities of very high amounts of grinding agents, nevertheless necessary today to obtain the finely divided concentrated suspensions with rheology and acceptable stability for paper coating purposes, represents significant deficiencies such as those indicated below: a first deficiency manifests itself in the paper industry by recycling of "scrap". Because, namely, recycling a very significant amount of anionic polyacrylate forces an at least partial inhibition of the cationic retention agents used and which interfere with sheet formation;
en andre mangel ligger i det faktum at midlene kan gjenfinnes delvis i spillvannet og forstyrre klaringen av dette og derved bidra til å øke det kjemiske oksygen-behovet, COD i bassenget; a second shortcoming lies in the fact that the agents can be partially found in the waste water and interfere with its clarification and thereby contribute to increasing the chemical oxygen demand, COD in the pool;
videre en mangel i forbindelse med beskyttelse av mennesket mot giftighet, det er innenfor nasjonale lover på papirområdet og spesielt de som gjelder papir som kommer i forbindelse med næringsmidler at de skal ha et innhold innenfor visse grenser av slike mengder, mengder som ikke er forenelige med de oppmal ingsprosesser og midler som benyttes i dag; og further a deficiency in connection with the protection of humans against toxicity, it is within national laws in the area of paper and especially those that apply to paper that comes in connection with foodstuffs that they must have a content within certain limits of such amounts, amounts that are not compatible with the painting processes and means used today; and
til slutt utgjør overskuddet av oppmalingsmidlet en finally, the surplus of the grinding agent amounts to one
unødvendig utgift som er uhensiktsmessig. unnecessary expense that is inappropriate.
Alle disse grunner har bragt søkeren til å fortsette sin forskning og å komme frem til en oppmalingsprosess som, på overraskende måte, tillater å realisere pigmentsuspensjoner som tilsvarer de samme kvalitetskriterier som den kjente teknikk, mens man samtidig benytter meget lavere mengder oppmalingsmiddel. All these reasons have led the applicant to continue his research and to arrive at a painting process which, in a surprising way, allows the realization of pigment suspensions that correspond to the same quality criteria as the known technique, while at the same time using much lower amounts of painting agent.
I henhold til dette angår foreliggende oppfinnelse en fremgangsmåte for oppmaling i vandig medium av kalsiumkarbonat i nærvær av oppmalingslegemer og et vannoppløselig oppmalingsmiddel, og denne fremgangsmåte karakteriseres ved at oppmalingsmediet omfattende oppmalingslegemer, den vandige fase inneholdende oppmalingsmiddel bestående av minst en sur polymer og/eller kopolymer, oppnådd fra minst en karboksylert etylen-mononer, i en mengde av 0,46 til 0,73 vekt-%, beregnet på tørrvekten av kalsiumkarbonat, samt kalsiumkarbonatet som skal oppmales i suspensjon med en tørrstoff-konsentrasjon mellom 75 og 77 vekt-%, der de raffinerte partikler har et tverrsnitt på mindre enn 2 um og minst 75 % av partiklene har en dimensjon under 1 um, holdes ved en temperatur under 60°C under oppmalingsprosessen. According to this, the present invention relates to a method for grinding in an aqueous medium of calcium carbonate in the presence of grinding bodies and a water-soluble grinding agent, and this method is characterized by the grinding medium comprising grinding bodies, the aqueous phase containing grinding agent consisting of at least one acidic polymer and/or copolymer , obtained from at least one carboxylated ethylene monone, in an amount of 0.46 to 0.73% by weight, calculated on the dry weight of calcium carbonate, as well as the calcium carbonate to be ground in suspension with a dry matter concentration between 75 and 77% by weight , where the refined particles have a cross-section of less than 2 µm and at least 75% of the particles have a dimension of less than 1 µm, is maintained at a temperature below 60°C during the grinding process.
Fortrinnsvis blir temperaturen i oppmalingsmediet holdt ved 45"C og aller helst under 30°C. Preferably, the temperature in the grinding medium is kept at 45°C and most preferably below 30°C.
Avkjølingen av kalsiumkarbonatsuspensjonen som underkastes oppmaling kan gjennomføres på en hvilken som helst kjent måte, enten ved føring gjennom en varmeveksler, eller et system med avkjøling av de ytre vegger av oppmalingsinnret-ningen, eller videre med interne impulsgivere og eventuelle motskiver. The cooling of the calcium carbonate suspension that is subjected to grinding can be carried out in any known way, either by passing through a heat exchanger, or a system with cooling of the outer walls of the grinding device, or further with internal impulse generators and any counter discs.
Oppmalingsmiddelet består fortrinnsvis av minst en sur polymer og/eller kopolymer oppnådd fra minst en karboksylert etylenmonomer. The coloring agent preferably consists of at least one acidic polymer and/or copolymer obtained from at least one carboxylated ethylene monomer.
Den karboksylerte etylenmonomer velges blant akryl-, metakryl-, itakon-, kroton-, fumar- eller maleinsyreanhydrid, eller videre isokroton-, akonitin-, mesakon-, sinapin-, undecylen-, angelika- eller hydroksyakrylsyre, men velges fortrinnsvis mellom akryl- eller metakrylsyre. The carboxylated ethylene monomer is selected from acrylic, methacrylic, itaconic, crotonic, fumaric or maleic anhydride, or further isocrotonic, aconitic, mesaconic, sinapic, undecylenic, angelica or hydroxyacrylic acid, but is preferably chosen from acrylic or methacrylic acid.
Den karboksylerte etylenmonomer kan være bundet til minst en annen etylenmonomer som ikke inneholder noen karboksyl-funksjoner. Disse andre monomerer kan for eksempel være grupper bestående av akrolein, akrylamid eller substituenter derav, akrylnitril, akryl- og metakrylsyreestre og spesielt C^g-akrylater og -metakrylater som eventuelt kvaternisert dimetylaminoetylmetakrylat, imidazoler, vinylpyrrolidon, vinylkaprolaktam, etylen, propylen, isobutylen, diisobutylen, vinylacetat, styren og substituenter derav, a-metylstyren, metylvinylketon, vinylklorider, hydroksylerte monomerer og spesielt etylenglykolakrylater og -metakrylater, propylenglykol samt fosfat-, fosfon-, fosfonyl-, sulfat-, sulfon-, nitro- og nitrosoderivater. The carboxylated ethylene monomer may be attached to at least one other ethylene monomer which does not contain any carboxyl functions. These other monomers can, for example, be groups consisting of acrolein, acrylamide or substituents thereof, acrylonitrile, acrylic and methacrylic acid esters and especially C^g acrylates and methacrylates such as optionally quaternized dimethylaminoethyl methacrylate, imidazoles, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene and its substituents, α-methylstyrene, methyl vinyl ketone, vinyl chlorides, hydroxylated monomers and especially ethylene glycol acrylates and methacrylates, propylene glycol as well as phosphate, phosphonic, phosphonyl, sulphate, sulphonic, nitro and nitroso derivatives.
De sure polymerer og/eller kopolymerer oppnås ved polymeri-sering og/eller kopolymerisering ifølge kjente teknikker i nærvær av initiatorer og egnede regulatorer i vandig, alkoholisk, hydroalkoholisk, aromatisk, alifatisk miljø eller i et halogenert oppløsningsmiddel av minst en av de monomere akryl- og/eller metakrylsyrer. The acidic polymers and/or copolymers are obtained by polymerization and/or copolymerization according to known techniques in the presence of initiators and suitable regulators in an aqueous, alcoholic, hydroalcoholic, aromatic, aliphatic environment or in a halogenated solvent of at least one of the monomeric acrylic and/or methacrylic acids.
Som polymeriseringsmiddel kan man velge vann, metanol, etanol, propanol, isopropanol, "butanolene, eller videre dimetylformamid, dimetylsulfoksyd, tetrahydrofuran, aceton, metyletylketon, butylacetat, heksan, heptan, benzen, toluen, etylbenzen, xylen, merkaptoetanol, tert-dodecylmerkaptan, tioglykolsyre og estre derav, n-dodecylmerkaptan, eddik-syrene, vin-, melke-, sitron-, glukon-, glukohepton- eller 2-merkaptopropionsyre, tiodietanol, halogenerte oppløsnings-midler som karbontetraklorid, kloroform, metylenklorid, metylklorid, monopropylenglykoletre eller dietylenglykol. As a polymerization agent, one can choose water, methanol, ethanol, propanol, isopropanol, "butanols, or further dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, butyl acetate, hexane, heptane, benzene, toluene, ethylbenzene, xylene, mercaptoethanol, tert-dodecyl mercaptan, thioglycolic acid and its esters, n-dodecyl mercaptan, acetic acids, tartaric, lactic, citric, gluconic, glucoheptonic or 2-mercaptopropionic acid, thiodiethanol, halogenated solvents such as carbon tetrachloride, chloroform, methylene chloride, methyl chloride, monopropylene glycol ether or diethylene glycol .
I henhold til en variant som har vist seg meget interessant kan polymerene og/eller kopolymerene i henhold til oppfinnelsen og i vandig oppløsning helt eller partielt nøytrali-seres ved hjelp av et nøytraliseringsmiddel som disponerer en monovalent funksjon. Imidlertid kan dette monovalente middel være bundet til et nøytraliseringsmiddel med en polyvalent funksjon. According to a variant which has proved very interesting, the polymers and/or copolymers according to the invention and in aqueous solution can be completely or partially neutralized with the aid of a neutralizing agent which disposes of a monovalent function. However, this monovalent agent may be bound to a neutralizing agent with a polyvalent function.
I det førstnevnte tilfellet velges nøytraliseringsmidlet fortrinnsvis blant gruppen omfattende alkalikationer og lignende, spesielt litium, natrium, kalium, ammonium eller eventuelt polysubstituert amin. Dette middel kan i det andre tilfellet være bundet til et middel fra gruppen jordalkali-metaller eller lignende, fortrinnsvis kalsium eller magnesium, sink eller aluminium. In the first-mentioned case, the neutralizing agent is preferably selected from the group comprising alkali cations and the like, especially lithium, sodium, potassium, ammonium or optionally polysubstituted amine. In the second case, this agent can be bound to an agent from the group of alkaline earth metals or the like, preferably calcium or magnesium, zinc or aluminium.
Den flytende fase som oppstår ved polymeriseringen og/eller kopolymeriseringen og som inneholder den sure polymer og/eller kopolymer kan benyttes i denne form som oppmalingsmiddel for det kalsiumkarbonat som skal raffineres. The liquid phase which occurs during the polymerization and/or copolymerization and which contains the acidic polymer and/or copolymer can be used in this form as a grinding agent for the calcium carbonate to be refined.
I praksis omfatter oppmalingen følgende faser: In practice, the repainting includes the following phases:
a) man realiserer under omrøring prepareringen av en vandig suspensjon av grov kalsiumkarbonat ved helt eller delvis å innføre oppmalingsmidlet i den vandige fase og derefter kalsiumkarbonatet for å oppnå en fluid og fortrinnsvis homogen suspensjon; b) man innfører den under a) preparerte suspensjon til en oppmalingssone bestående av en mølle med mikroelementer; c) man holder temperaturen i suspensjonen under oppmalingen på et nivå under 60°C og fortrinnsvis under 45 °C og aller helst under 30°C; d) man maler opp suspensjonen som skal behandles i nærvær av mikroelementene i det tidsrom som er nødvendig for å oppnå den tilsiktede midlere granulometri; e) man innfører eventuelt minst en gang under oppmalingen en komplementær fraksjon av oppmalingsmiddel og f) man separerer ved utløpet av møllen kontinuerlig suspensjonen av finoppmalt kalsiumkarbonat fra oppmalingslegemene og kalsiumkarbonatpartikler som avvises på grunn av for høy grovhet. a) one realizes, while stirring, the preparation of an aqueous suspension of coarse calcium carbonate by fully or partially introducing the grinding agent into the aqueous phase and then the calcium carbonate to obtain a fluid and preferably homogeneous suspension; b) it is introduced under a) prepared suspension to a grinding zone consisting of a mill with microelements; c) the temperature in the suspension during grinding is kept at a level below 60°C and preferably below 45°C and most preferably below 30°C; d) one grinds up the suspension to be treated in the presence of the microelements for the time necessary to achieve the intended mean granulometry; e) optionally, at least once during grinding, a complementary fraction of grinding agent is introduced and f) at the outlet of the mill, the suspension of finely ground calcium carbonate is continuously separated from the grinding bodies and calcium carbonate particles that are rejected due to excessive coarseness.
Oppmalingsmidlet som anvendes ved fremgangsmåten ifølge oppfinnelsen innføres i den vandige kalsiumkarbonatsuspensjon i en mengde av 0,46 til 0,73 vekt-% av aktive stoffer beregnet på tørrvekten av grov kalsiumkarbonat som skal oppmales. The grinding agent used in the method according to the invention is introduced into the aqueous calcium carbonate suspension in an amount of 0.46 to 0.73% by weight of active substances calculated on the dry weight of coarse calcium carbonate to be ground.
Suspensjonen har under oppmalingen og ved slutten av denne generelt en konsentrasjon av tørrstoff på 75 og 77 vekt-% med et pigmentpartikkelsnitt på under 2 um idet 75 % derav har en dimensjon på under 1 um. During the grinding and at the end of this, the suspension generally has a concentration of dry matter of 75 and 77% by weight with a pigment particle size of less than 2 µm, 75% of which has a dimension of less than 1 µm.
Den vandige kalsiumkarbonatsuspensjon som oppnås ved fremgangsmåten ifølge oppfinnelsen kan fordelaktig benyttes på papirområdet (fyllmasse eller belegg) og i malings-industrien. Det oppnådde og oppmalte kalsiumkarbonat fra en slik prosess kan tørkes og likeledes benyttes som fyllstoff på polymermaterialområdet. The aqueous calcium carbonate suspension obtained by the method according to the invention can advantageously be used in the paper area (filler or coating) and in the paint industry. The obtained and ground calcium carbonate from such a process can be dried and likewise used as a filler in the polymer material area.
Oppfinnelsen skal beskrives nærmere under henvisning til de følgende eksempler: The invention shall be described in more detail with reference to the following examples:
Eksempel 1 Example 1
Dette eksempel hvis formål er å illustrere den kjente teknikk, angår fremstilling av en suspensjon av grov kalsiumkarbonat som underkastes en oppmaling for raffinering til mikropartikkelsuspensjon. This example, the purpose of which is to illustrate the known technique, concerns the production of a suspension of coarse calcium carbonate which is subjected to a grinding process for refining into a microparticle suspension.
For dette formål prepareres det en suspensjon av grov kalsiumkarbonat fra naturlig kalsiumkarbonat med en midlere diameter på 50 um ved som oppmal ingsmiddel å benytte en polyakrylsyre med molekylvekt 4000 hvorav 70% av funksjonene er nøytralisert med natriumioner og 30% med kalsiumioner. For this purpose, a suspension of coarse calcium carbonate is prepared from natural calcium carbonate with an average diameter of 50 µm by using a polyacrylic acid with a molecular weight of 4000, of which 70% of the functions are neutralized with sodium ions and 30% with calcium ions.
Dette eksempel angår således preparering og oppmaling av vandige suspensjoner av kalsiumkarbonat med en tørrstoff-konsentrasjon på 75 vekt-% uten å benytte avkjølings-innretninger. This example thus relates to the preparation and grinding of aqueous suspensions of calcium carbonate with a solids concentration of 75% by weight without using cooling devices.
Eksempel 2 Example 2
En andre gruppe eksempler, nemlig eksemplene 2-1, 2-2, 2-3 og 2-4, angår preparering og oppmaling av den samme vandige kalsiumkarbonatsuspensjon med den samme tørrstoffkonsentra-sjon i nærvær av den samme natrium/kalsium-polyakrylat-blanding med midlere molekylvekt 4000, men der temperaturen kontrolleres til 60°C, for eksempel 2-1, 45°C for eksempel 2-2, og 25°C for eksemplene 2-3 og 2-4. A second group of examples, namely examples 2-1, 2-2, 2-3 and 2-4, relate to the preparation and grinding of the same aqueous calcium carbonate suspension with the same solids concentration in the presence of the same sodium/calcium polyacrylate mixture with average molecular weight 4000, but where the temperature is controlled to 60°C, for example 2-1, 45°C for example 2-2, and 25°C for examples 2-3 and 2-4.
Disse eksempler gjennomføres under de samme forsøkskriterier for gjennomføring av oppmalingen i den samme apparatur for å oppnå sammenlignbare resultater. These examples are carried out under the same test criteria for carrying out the grinding in the same apparatus in order to achieve comparable results.
For hvert eksempel prepareres det en vandig original kalsiumkarbonatsuspensjon som angitt ovenfor og med en granulometri under 50 um. For each example, an aqueous original calcium carbonate suspension is prepared as indicated above and with a granulometry below 50 µm.
Den vandige suspensjon har en konsentrasjon, uttrykt i vekt-% i forhold til den totale masse, slik mengdene er angitt i tabell 1. The aqueous suspension has a concentration, expressed in % by weight in relation to the total mass, as the quantities are indicated in table 1.
Oppmalingsmidlet er til stede i suspensjonen i mengder som angitt i tabell 1, uttrykt i vekt-% i forhold til mengden kalsiumkarbonat som skal males opp, denne mengde justeres slik at man holder viskositeten i suspensjonen under oppmalingen på mellom 100 og 500 cP, målt på et Brookfield-viskosimeter ved 100 omdr./min. og med spindel nr. 3. The grinding agent is present in the suspension in quantities as indicated in table 1, expressed in % by weight in relation to the amount of calcium carbonate to be ground up, this amount is adjusted so that the viscosity in the suspension during the grinding up is kept between 100 and 500 cP, measured on a Brookfield viscometer at 100 rpm. and with No. 3 spindle.
Den således preparerte suspensjon anbringes i en mølle av typen Dyno-Mill med fast sylinder og dreiende impulsgiver og der oppmalingslegemene består av korundkuler med en diameter i området 0,6 mm til 1,0 mm. The thus prepared suspension is placed in a mill of the Dyno-Mill type with a fixed cylinder and rotating impulse generator and where the grinding bodies consist of corundum balls with a diameter in the range of 0.6 mm to 1.0 mm.
Det totale volum som oppnås av oppmalingslegemene er 5 liter, mens massen er 10 kg. The total volume achieved by the grinding bodies is 5 litres, while the mass is 10 kg.
Oppmalingskammeret har et volum på 5 liter. The grinding chamber has a volume of 5 litres.
Tangentialhastigheten for møllen er 10 m/sek. The tangential speed of the mill is 10 m/sec.
Kalsiumkarbonatsuspensjonen resirkuleres i en mengde av 50 1/time. The calcium carbonate suspension is recycled at a rate of 50 1/hour.
Utløpet av Dyno-Mi11-mø11en er utstyrt med en separator med maskevidde 300 um, noe som tillater å separere oppmalings-legemet fra suspensjonen fra oppmalingen. The outlet of the Dyno-Mi11 mill is equipped with a separator with a mesh size of 300 µm, which allows the grinding body to be separated from the suspension from the grinding.
Temperaturen i eksempel 1 stabiliseres ved 100"C. The temperature in example 1 is stabilized at 100°C.
Oppmalingen følges av resirkulering inntil man har oppnådd en granulometri for partiklene slik at 75% ligger under 1 pm. Grinding is followed by recycling until a granulometry for the particles has been achieved so that 75% is below 1 pm.
Ved slutten av oppmalingen blir viskositeten i mikro-partikkelsuspensjonen målt ved hjelp av et Brookfield-viskosimeter, ved 20° C og ved en omdreiningshastighet på 100 omdr./min. med spindel nr. 3. At the end of grinding, the viscosity of the micro-particle suspension is measured by means of a Brookfield viscometer, at 20° C. and at a rotation speed of 100 rpm. with No. 3 spindle.
Samtidig bestemmes ved slutten av oppmalingen granulometrien ved hjelp av et laser HR 850-granulometer fra Cilas Alcatel. At the same time, at the end of the grinding, the granulometry is determined using a laser HR 850 granulometer from Cilas Alcatel.
De oppnådde resultater er angitt i tabell 1. The results obtained are shown in table 1.
Det er her klart at en kontroll av temperaturen til verdier under 60°C tillater å oppnå vandige CaC03-suspensjoner med de samme karakteristika for reologi, finhet og konsentrasjon, som det som oppnås ved høyere temperaturer, men man oppnår en vesentlig økonomisk besparelse med henblikk på oppmalingsmidlet og som kan gå utover 50%. It is clear here that a control of the temperature to values below 60°C allows to obtain aqueous CaCO3 suspensions with the same characteristics of rheology, fineness and concentration, as that obtained at higher temperatures, but a substantial economic saving is achieved in terms of on the grinding agent and which can exceed 50%.
Videre tillater en styring av temperaturen å øke tørrstoff-konsentrasjonen i den oppmalte suspensjon, mens denne ikke desto mindre bibeholder sin gode karakteristika med henblikk på finhet og viskositet. Furthermore, a control of the temperature allows the dry matter concentration in the milled suspension to be increased, while this nevertheless retains its good characteristics with regard to fineness and viscosity.
Videre har man kontrollert utviklingen med tiden av viskositeten i de oppnådde kalsiumkarbonatsuspensjoner ved oppmaling ved forskjellige temperaturer for å observere de eventuelle konsekvenser av anvendelse av for lite dispergeringsmiddel mens man arbeider ved riktig temperatur. Furthermore, the development with time of the viscosity of the obtained calcium carbonate suspensions when grinding at different temperatures has been checked to observe the possible consequences of using too little dispersant while working at the correct temperature.
Resultatene som oppnås er angitt i tabell 2. The results obtained are listed in Table 2.
Herav fremgår det at kalsiumkarbonatsuspensjonene som oppnås ved oppmaling ved lav temperatur og som inneholder reduserte mengder dispergeringsmiddel ikke desto mindre oppviser en hedre lagringsstabilitet enn tilfellet er ved den kjente teknikk, noe som gir seg utslag i en viskositet som er mer stabil og som er lavere med tiden. From this it appears that the calcium carbonate suspensions which are obtained by grinding at low temperature and which contain reduced amounts of dispersant nevertheless show a better storage stability than is the case with the known technique, which results in a viscosity which is more stable and which is lower with the time.
Claims (9)
Applications Claiming Priority (1)
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FR8901317A FR2642415B1 (en) | 1989-01-27 | 1989-01-27 | PROCESS FOR GRINDING CALCIUM CARBONATE IN AQUEOUS MEDIA |
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NO895266D0 NO895266D0 (en) | 1989-12-27 |
NO895266L NO895266L (en) | 1990-07-30 |
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EP0542643B1 (en) * | 1991-11-12 | 1998-01-21 | Coatex S.A. | Grinding and/or dispersion aid based on polymers and/or copolymers partially neutralised by magnesium for aqueous suspensions of mineral materials which are convenient for pigmentary applications |
FR2683537B1 (en) * | 1991-11-12 | 1993-12-31 | Coatex Sa | GRINDING AND / OR DISPERSING AGENT BASED ON POLYMERS AND / OR COPOLYMERS NEUTRALIZED IN PART BY MAGNESIUM FOR AQUEOUS SUSPENSIONS OF MINERAL MATERIALS FOR PIGMENTARY APPLICATIONS. |
FR2683539B1 (en) * | 1991-11-12 | 1993-12-31 | Coatex Sa | AQUEOUS SUSPENSION GRINDING PROCESS IN THE PRESENCE OF A GRINDING AGENT NEUTRALIZED IN PART BY MAGNESIUM. |
FR2683538B1 (en) * | 1991-11-12 | 1993-12-31 | Coatex Sa | AQUEOUS SUSPENSION GRINDING PROCESS IN THE PRESENCE OF A GRINDING AGENT NEUTRALIZED IN PART BY MAGNESIUM. |
FR2683536B1 (en) * | 1991-11-12 | 1993-12-31 | Coatex Sa | GRINDING AND / OR DISPERSING AGENT BASED ON POLYMERS AND / OR COPOLYMERS NEUTRALIZED IN PART BY MAGNESIUM FOR AQUEOUS SUSPENSIONS OF MINERAL MATERIALS FOR PIGMENTARY APPLICATIONS. |
CA2080961C (en) * | 1991-11-12 | 2002-04-02 | Jean-Bernard Egraz | Partially magnesium neutralized polymer and/or copolymer-based grinding and/or dispersant medium for treatment of aqueous suspensions of minerals for pigmentary applications |
US5593488A (en) * | 1995-08-24 | 1997-01-14 | Ecc International Inc. | Acid resistant calcium carbonate composition and uses therefor |
KR19990044586A (en) * | 1995-09-12 | 1999-06-25 | 데릭 제임스 맥코마크 | How to make a ground particulate system |
AU697589B2 (en) * | 1995-09-12 | 1998-10-08 | Ecc International Limited | Preparations of suspensions of ground particulate material |
US5593489A (en) * | 1995-10-20 | 1997-01-14 | Ecc International Inc. | Acid resistant carbonate composition containing an aluminum or magnesium hydroxide methods of preparation and uses therefor |
EP0859885A4 (en) * | 1995-10-20 | 1999-06-09 | Ecc Int Inc | Acid resistant calcium carbonate filler |
GB9627002D0 (en) * | 1996-12-27 | 1997-02-12 | Ecc Int Ltd | Dispersed aqueous suspensions |
AU1869000A (en) * | 1998-12-23 | 2000-07-31 | Imerys Minerals Ltd. | Production of concentrated carbonate suspensions |
DE10209698A1 (en) | 2002-03-06 | 2003-09-18 | Sachtleben Chemie Gmbh | Process for the production of coated, finely divided, inorganic solids and their use |
DE10311617A1 (en) * | 2003-03-14 | 2004-09-23 | Basf Ag | Use of at least partly neutralised polyacrylic acid with a mol. wt. of 5000-30000 containing alkylthio end groups, as an auxiliary material for the wet-milling of calcium carbonate |
WO2004087574A1 (en) * | 2003-03-31 | 2004-10-14 | San Nopco Ltd. | Dispersant for the wet grinding of heavy calcium carbonate |
JP5207097B2 (en) * | 2006-06-16 | 2013-06-12 | 星光Pmc株式会社 | Filler modifier, filler slurry and paper making method |
CN103255680B (en) * | 2007-07-05 | 2014-11-12 | 巴斯夫欧洲公司 | Preparation of aqueous slurries of finely divided fillers and their use for the production of papers having a high filler content and high dry strength |
JP5274072B2 (en) * | 2008-03-28 | 2013-08-28 | 日本製紙株式会社 | Method for producing engineered calcium carbonate and papermaking paint using the same |
EP2199348A1 (en) | 2008-12-19 | 2010-06-23 | Omya Development AG | Process for manufacturing aqueous suspensions of mineral materials or dried mineral materials, the obtained products, as well as uses thereof |
SI2455429T1 (en) * | 2010-11-19 | 2013-12-31 | Omya International Ag | Method for preparing aqueous suspensions of mineral materials using amines combined with vinyl carboxylic polymers |
EP2628775A1 (en) | 2012-02-17 | 2013-08-21 | Omya Development AG | Mineral material powder with high dispersion ability and use of said mineral material powder |
SI2662417T1 (en) * | 2012-05-11 | 2015-12-31 | Omya International Ag | Starch-based phch |
PT2662416E (en) * | 2012-05-11 | 2015-10-09 | Omya Int Ag | Treatment of calcium carbonate containing materials for increased filler load in paper |
PT2684999E (en) | 2012-07-13 | 2015-03-03 | Omya Int Ag | High solids and low viscous aqueous slurries of calcium carbonate-comprising materials with improved rheological stability under increased temperature |
PL2910609T3 (en) | 2014-02-21 | 2018-01-31 | Omya Int Ag | Process for the preparation of a calcium carbonate filler product |
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GB949260A (en) * | 1961-12-11 | 1964-02-12 | Champion Paper Co Ltd | Improvements in method of treating calcium carbonate |
GB1204511A (en) * | 1967-03-14 | 1970-09-09 | English Clays Lovering Pochin | Improvements in or relating to pigments |
FR2531444A1 (en) * | 1982-08-06 | 1984-02-10 | Coatex Sa | MILLING AGENT BASED ON ACRYLIC POLYMERS AND / OR COPOLYMERS FOR AQUEOUS SUSPENSION OF GROSS MINERAL MATERIALS FOR PIGMENTAL APPLICATIONS |
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1989
- 1989-01-27 FR FR8901317A patent/FR2642415B1/en not_active Expired - Fee Related
- 1989-12-04 CA CA002004490A patent/CA2004490C/en not_active Expired - Fee Related
- 1989-12-27 NO NO895266A patent/NO303176B1/en not_active IP Right Cessation
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1990
- 1990-01-23 AT AT90420033T patent/ATE126251T1/en not_active IP Right Cessation
- 1990-01-23 ES ES90420033T patent/ES2077050T3/en not_active Expired - Lifetime
- 1990-01-23 DE DE69021403T patent/DE69021403T2/en not_active Expired - Fee Related
- 1990-01-23 KR KR1019900000760A patent/KR900011668A/en not_active Application Discontinuation
- 1990-01-23 EP EP90420033A patent/EP0380430B1/en not_active Expired - Lifetime
- 1990-01-25 ZA ZA90548A patent/ZA90548B/en unknown
- 1990-01-26 FI FI900435A patent/FI97373C/en not_active IP Right Cessation
- 1990-01-26 JP JP2017672A patent/JP2918596B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0380430B1 (en) | 1995-08-09 |
ES2077050T3 (en) | 1995-11-16 |
CA2004490A1 (en) | 1990-07-27 |
FI97373C (en) | 1996-12-10 |
DE69021403D1 (en) | 1995-09-14 |
JPH02243517A (en) | 1990-09-27 |
ZA90548B (en) | 1990-10-31 |
NO895266L (en) | 1990-07-30 |
EP0380430A1 (en) | 1990-08-01 |
NO895266D0 (en) | 1989-12-27 |
JP2918596B2 (en) | 1999-07-12 |
FR2642415A1 (en) | 1990-08-03 |
FI900435A0 (en) | 1990-01-26 |
ATE126251T1 (en) | 1995-08-15 |
KR900011668A (en) | 1990-08-01 |
FR2642415B1 (en) | 1991-04-05 |
FI97373B (en) | 1996-08-30 |
DE69021403T2 (en) | 1996-03-07 |
CA2004490C (en) | 2001-02-13 |
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