EP1704282B2 - Filler for papermaking process - Google Patents
Filler for papermaking process Download PDFInfo
- Publication number
- EP1704282B2 EP1704282B2 EP04809143.3A EP04809143A EP1704282B2 EP 1704282 B2 EP1704282 B2 EP 1704282B2 EP 04809143 A EP04809143 A EP 04809143A EP 1704282 B2 EP1704282 B2 EP 1704282B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- filler
- cellulose derivative
- cellulose
- weight
- paper
- 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.)
- Active
Links
- 239000000945 filler Substances 0.000 title claims description 115
- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title claims description 19
- 229920002678 cellulose Chemical class 0.000 claims description 95
- 239000001913 cellulose Chemical class 0.000 claims description 95
- 159000000007 calcium salts Chemical class 0.000 claims description 58
- 238000004513 sizing Methods 0.000 claims description 42
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 40
- 125000002091 cationic group Chemical group 0.000 claims description 33
- 239000000725 suspension Substances 0.000 claims description 33
- 125000000129 anionic group Chemical group 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 description 83
- 239000000123 paper Substances 0.000 description 56
- 239000000463 material Substances 0.000 description 40
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 28
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 26
- 239000000203 mixture Substances 0.000 description 19
- 239000008186 active pharmaceutical agent Substances 0.000 description 18
- -1 alkyl ketene dimers Chemical class 0.000 description 17
- 235000010216 calcium carbonate Nutrition 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 229920002472 Starch Polymers 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000008107 starch Substances 0.000 description 12
- 235000019698 starch Nutrition 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229920001131 Pulp (paper) Polymers 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920002401 polyacrylamide Polymers 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003010 ionic group Chemical group 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 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 4
- 150000002561 ketenes Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 101100508080 Entamoeba histolytica ICP2 gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 201000002159 intrahepatic cholestasis of pregnancy 3 Diseases 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000005418 vegetable material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- GPFVWKXABQQNEM-BMRADRMJSA-N 3-[(e)-16-methylheptadec-1-enyl]oxolane-2,5-dione Chemical compound CC(C)CCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O GPFVWKXABQQNEM-BMRADRMJSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 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 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011436 cob Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-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
- D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
-
- 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
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/26—Ethers thereof
-
- 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
-
- 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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
Definitions
- the present invention relates to a filler comprising calcium salt and cellulose derivative.
- the invention further relates to a method of making the filler, the use of the filler in papermaking, a process for papermaking in which the filler is used as an additive as well as paper comprising the filler.
- Highly filled paper is an established trend in the paper industry not only due to the savings in the decreased use of fibre, but also due to improved product quality, such as higher opacity and better printability.
- Calcium carbonate-based fillers are commonly used, because of their superior light scattering properties.
- a major drawback in the production of highly filled paper, particularly with fillers having high surface area, is the high consumption of sizing agent.
- sizing agent is required in order to obtain corresponding sizing results.
- cellulosic suspensions are more difficult to size when the amount of filler increases.
- Sizing is primarily performed in order to achieve water repellence in paper or board and reduce edge wicking. It will also affect mechanical properties of paper and board, such as dimensional stability, friction coefficient, pliability and folding endurance. Additionally, sizing may improve printability specifically by controlling ink spreading and adhesion.
- the sizing process involves the deposition of hydrophobic substances, commonly referred to as sizing agents, on the fibre surface.
- sizing agents are non-cellulose-reactive sizing agents, e.g. rosin-based sizing agents, and cellulose-reactive sizing agents, e.g. alkyl ketene dimers (“AKD”) and acid anhydrides such as alkenyl succinic anhydride (“ASA”).
- ASA alkenyl succinic anhydride
- Voutilainen has shown that fillers with high surface area adsorb AKD even better than fibres ( Voutilainen, P., "Competitive Adsorption of Alkyl Ketene Dimer on Pulp Fibers and CaCO3 Fillers", Proceedings from International Paper and Coating Chemistry Symposium, 1996 ).
- the presence of Al- and Si-oxides on the filler surface may additionally adsorb cationic starch contained in the AKD particles.
- the surface of the pigment can be modified with an anionic starch-soap complex.
- Cooked starch from corn or potato is complexed with fatty acid salts and precipitated onto pigment surfaces when mixed with precipitated calcium slurry or papermaking furnish containing high levels of calcium ions.
- U.S. Patent No. 5,972,100 suggests a system consisting of a cellulose-reactive size (such as AKD), a cationic dispersing agent (such as cationic starch or polyamides) and a filler. Aside from improved sizing, the invention allows independent control of both filler loading and sizing separately.
- a cellulose-reactive size such as AKD
- a cationic dispersing agent such as cationic starch or polyamides
- WO 95/13324 refers to calcium carbonate treated with a cellulose derivative such as sodium carboxymethyl cellulose ("CMC") having a degree of substitution of 0.7. Said treated calcium carbonate is used as filler in alkaline papermaking suspensions whereby the brightness of the paper is increased.
- CMC sodium carboxymethyl cellulose
- U.S. Patent No. 3,730,830 discloses a process for making paper, specifically photographic paper, comprising the use of synthetic polymer fibres. Prior to the addition of the synthetic fibres to the fibre suspension, inorganic pigment or carbon is added to a slurry containing carboxymethyl cellulose and the synthetic fibres thereby achieving uniform dispersion of the polymer fibres among the cellulose fibres in the paper stock.
- WO 02/086238 disclosesa filler for paper comprising specific cellulose material. The use of a cellulose derivative of the invention is not disclosed or suggested.
- EP 0 758 695 A discloses the use of fibrous cellulose to make water-dispersible paper sheets. There is no disclosure or suggestion to use a cellulose material according to the invention.
- US 5,492,560 discloses to use a specific carboxymethyl cellulose to treat an inorganic filler.
- the use of a cellulose material of the invention is not disclosed or suggested.
- the present invention generally relates to a filler comprising calcium salt and an amphoteric cellulose derivative.
- the present invention further generally relates to a filler comprising calcium salt and an amphoteric carboxyalkyl cellulose derivative.
- the invention also generally relates to a method of making the filler by mixing a calcium salt-containing material with a cellulose derivative, the use of the filler as an additive in papermaking as well as paper comprising the filler.
- the invention further generally relates to a papermaking process in which the filler is introduced into an aqueous cellulosic suspension.
- the invention relates to a filler according to claim 1.
- the invention further relates to a method of producing a filler which comprises mixing a calcium salt-containing material with an amphoteric cellulose derivative according to claim 1.
- the invention further relates to a filler obtainable by these methods.
- the invention further relates to a papermaking process which comprises providing an aqueous suspension containing cellulosic fibres, introducing into the suspension a filler comprising calcium salt and an amphoteric cellulose derivative according to claim 1, and dewatering the suspension to form a web or sheet of paper.
- the filler can be introduced into the cellulosic suspension by adding the calcium salt and cellulose derivative together as a single composition.
- the present invention provides a new filler that is suitable for use in papermaking. It has surprisingly been found that the filler according to the invention makes it possible to reduce some of the problems associated with fillers commonly used in papermaking and incorporated in paper. More specifically, by employing the filler of this invention in papermaking processes it is possible to provide paper with excellent printing properties, e.g. high smoothness, high opacity and whiteness, improved mechanical properties, e.g. dry strength, tensile strength, Scott bond and bending stiffness, and improved sizing effect. Additional advantages shown by the present invention include good and/or improved dewatering and fines retention, which lead to benefits in terms of paper machine runnability.
- excellent printing properties e.g. high smoothness, high opacity and whiteness
- improved mechanical properties e.g. dry strength, tensile strength, Scott bond and bending stiffness
- Additional advantages shown by the present invention include good and/or improved dewatering and fines retention, which lead to benefits in terms of paper machine runnability.
- the present invention makes it possible to reduce the sizing demand and, thus, generally improving sizing efficiency.
- the improved sizing efficiency is exhibited for different types of sizing agents, including non-cellulose and cellulose-reactive sizing agents, specifically cellulose-reactive sizing agents such as ketene dimers and acid anhydrides.
- the invention provides improved sizing efficiency and sizing stability of filled paper, especially with high filler loading and/or when fillers with high surface areas are used.
- the cellulose derivative can be mixed with and more effectively be adsorbed on or attached to the calcium salt-containing material during simple processing.
- the filler of the invention can be regarded as a modified filler, or cellulose derivative-treated filler.
- the present invention it has been found that very good results can be obtained by adding the calcium salt-containing material and amphoteric cellulose derivative to a cellulosic suspension together in a pre-mixed or pre-treated form.
- the pre-treatment of the calcium salt-containing material with the cellulose derivative provides a convenient way of separately processing only one component of the cellulosic suspension to produce a modified filler, which can be used instead of or partly replacing conventional filler.
- a modified filler which can be used instead of or partly replacing conventional filler.
- the filler according to the invention comprises a calcium salt and an amphoteric cellulose derivative.
- suitable calcium salts include calcium carbonate, calcium sulphate and calcium oxalate, preferably calcium carbonate, and mixtures thereof.
- Calcium carbonate is the main constituent in limestone, marble, chalk and dolomite. Calcium carbonate can be obtained directly from the above mentioned naturally occurring species of stone and is then referred to as ground calcium carbonate ("GCC"). Calcium carbonate can also be synthetically produced, commonly referred to as precipitated calcium carbonate (“PCC").
- GCC ground calcium carbonate
- PCC precipitated calcium carbonate
- the calcium carbonate is preferably obtained from calcium hydroxide and a material which produces carbonate ions in the aqueous phase, such as an alkali metal carbonate or carbon dioxide.
- Both GCC and PCC can be used in the present invention, preferably PCC, including any of the various crystalline forms or morphologies that exist, e.g. calcite of rhombohedral, prismatic, tabular, cuboid and scalenohedral forms and aragonite of acicular form.
- the PCC usually has a specific area of from about 2 to about 20 m 2 /g, suitably from about 7 to about 12 m 2 /g.
- the calcium salt can be present as essentially pure calcium salt, including mixtures of one or more calcium salts. It can also be present in the form of a mixture together with one or more other components.
- calcium salt-containing materials comprising fibres or fibrils of cellulose, lignocellulose or similar vegetable materials
- at least part of the calcium salt can be deposited on the fibres or fibrils.
- the average thickness of the fibrils can be from about 0.01 up to about 10 ⁇ m, suitably up to about 5 ⁇ m and preferably up to about 1 ⁇ m.
- the average length of the fibrils can be from about 10 ⁇ m up to about 1500 ⁇ m.
- suitable calcium salt-containing materials include the composite materials disclosed in U.S. Patent Nos. 5,731,080 ; 5,824,364 ; 6,251,222 ; 6,375,794 ; and 6,599,391 , commercially available composite materials of this type include SuperFill ® of M-Real Oy.
- the filler according to the invention further comprises an amphoteric cellulose derivative.
- the cellulose derivative is water-soluble or at least partly water-soluble or water-dispersible, preferably water-soluble or at least partly water-soluble.
- the cellulose derivative is ionic.
- the cellulose derivative can be anionic and/or amphoteric.
- suitable cellulose derivatives include cellulose ethers, e.g. anionic and amphoteric cellulose ethers.
- the cellulose derivative preferably has ionic or charged groups, or substituents.
- suitable ionic groups include anionic and cationic groups.
- suitable anionic groups include carboxylate, e.g. carboxyalkyl, sulphonate, e.g.
- the alkyl group can be methyl, ethyl propyl and mixtures thereof, suitably methyl; suitably the cellulose derivative contains an anionic group comprising a carboxylate group, e.g. a carboxyalkyl group.
- the counter-ion of the anionic group is usually an alkali metal or alkaline earth metal, suitably sodium.
- Suitable cationic groups of cellulose derivatives according to the invention include salts of amines, suitably salts of tertiary amines, and quaternary ammonium groups, preferably quaternary ammonium groups.
- the substituents attached to the nitrogen atom of amines and quaternary ammonium groups can be same or different and can be selected from alkyl, cycloalkyl, and alkoxyalkyl, groups, and one, two or more of the substituents together with the nitrogen atom can form a heterocyclic ring.
- the substituents independently of each other usually comprise from 1 to about 24 carbon atoms, preferably from 1 to about 8 carbon atoms.
- the nitrogen of the cationic group can be attached to the cellulose or derivative thereof by means of a chain of atoms which suitably comprises carbon and hydrogen atoms, and optionally O and/or N atoms.
- the chain of atoms is an alkylene group with from 2 to 18 and suitably 2 to 8 carbon atoms, optionally interrupted or substituted by one or more heteroatoms, e.g. O or N such as alkyleneoxy group or hydroxy propylene group.
- Preferred cellulose derivatives containing cationic groups include those obtained by reacting cellulose or derivative thereof with a quaternization agent selected from 2, 3-epoxypropyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and mixtures thereof.
- the cellulose derivatives of this invention can contain non-ionic groups such as alkyl or hydroxy alkyl groups, e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxylbutyl and mixtures thereof, e.g. hydroxyethyl methyl, hydroxypropyl methyl, hydroxybutyl methyl, hydroxyethyl ethyl, hydroxypropoyl and the like.
- the cellulose derivative contains both ionic groups and non-ionic groups.
- the filler comprises a calcium salt containing fibres or fibrils of cellulose or lignocellulose and a cellulosic derivative containing cationic groups.
- the cationic groups can be any one of those listed in this application.
- the filler comprises a calcium salt which is substantially free from fibres or fibrils of cellulose or lignocellulose and an amphoteric cellulosic derivative.
- degree of substitution or "DS”, as used herein, mean the number of substituted ring sites of the beta-anhydroglucose rings of the cellulose derivative. Since there are three hydroxyl groups on each anhydroglucose ring of the cellulose that are available for substitution, the maximum value of DS is 3.0.
- the net ionic substitution of the cellulose derivative is net anionic.
- net anionic groups the average number of anionic groups minus the average number of cationic groups, if any, per glucose unit
- DS NI degree of substitution of net ionic groups
- DS NA is up to about 0.60, suitably up to about 0.50, preferably up to about 0.45 and more preferably up to 0.40, whereas DS NA is at least 0.01, suitably at least about 0.05, preferably at least about 0.10 and more preferably at least about 0.15.
- the ranges of DS NA are from about 0.01 to about 0.60, suitably from about 0.05 to about 0.50, preferably from about 0.10 to about 0.45 and more preferably from about 0.15 to about 0.40.
- Cellulose derivatives that are amphoteric have a degree of anionic substitution ("DS A ") in the range of from 0.01 to about 1.0 as long as DS NI and DS NA are as defined herein; suitably from about 0.05, preferably from about 0.10, and more preferably from about 0.15 and suitably up to about 0.75, preferably up to about 0.5, and more preferably up to about 0.4.
- DS A can of course be higher than 0.65 as long as DS NA is as defined herein. For example, if DS A is 0.75 and DSc (degree of cationic substitution) is 0.15, then DS NA is 0.60.
- Suitable cellulose derivatives having degrees of substitution as defined above include the water-soluble low DS carboxyalkyl cellulose derivatives disclosed in copending patent applications filed in the name of Akzo Nobel N.V. of even date.
- the water-soluble cellulose derivatives suitably has a solubility of at least 85 % by weight, based on total weight of dry cellulose derivative, in an aqueous solution, preferably at least 90 % by weight, more preferably at least 95 % by weight, and most preferably at least 98 % by weight.
- the cellulose derivative usually has an average molecular weight which is at least 20,000 Dalton, preferably at least 50,000 Dalton, and the average molecular weight is usually up to 1,000,000 Dalton, preferably up to 500,000 Dalton.
- the cellulose derivative is at least in part adsorbed on or attached to the calcium salt or other components present in the calcium salt-containing material.
- at least about 10 % by weight, preferably at least about 30 % by weight, more preferably at least about 45 % by weight and most preferably at least about 60 % by weight of the cellulose derivate is adsorbed on or attached to the calcium salt or other components present in the calcium salt-containing material.
- the filler according to the invention usually has a calcium salt content of at least 0.0001 % by weight; the calcium salt content can be from about 0.0001 to about 99.5 % by weight, suitably from about 0.1 to about 90 % by weight, and preferably from about 60 to about 80 % by weight, based on the weight of the solids of the filler, i.e. based on the dry weight of the filler.
- the filler usually has a cellulose derivative content of at least 0.01 % by weight; the cellulose derivative content can be from about 0.01 to about 30 % by weight, suitably from about 0.1 to about 20 % by weight, and preferably from about 0.3 to about 10 % by weight, based on the weight of the solids of the filler.
- the filler according to the invention can be supplied as a solid material that can be essentially free of water. It can also be supplied as an aqueous composition.
- the content of aqueous phase, or water, can vary within wide limits, depending on the method of production and intended use.
- the present invention also relates to a method of making a filler which comprises mixing an amphoteric cellulose derivative, e.g. any one of the cellulose derivatives defined herein, with a calcium salt-containing material, e.g. any one of the calcium salt-containing materials defined herein, which comprises calcium salt, and optionally one or more other components.
- a calcium salt-containing material e.g. any one of the calcium salt-containing materials defined herein, which comprises calcium salt, and optionally one or more other components.
- the cellulose derivative and calcium salt-containing material are suitably used in amounts so as to provide a filler according to the invention having contents of cellulose derivative and calcium salt as defined herein.
- the cellulose derivative and calcium salt-containing material used can be present as solids or in aqueous compositions, and mixtures thereof.
- the calcium salt-containing material is suitably present as a finely divided material.
- the mixing can be achieved by adding the cellulose derivative to the filler, or vice versa, in a batch, semi-batch or continuous process.
- the cellulose derivative is added as a solid to an aqueous composition of the calcium salt-containing material and the composition obtained is then suitably subjected to effective dispersing to dissolve the cellulose derivative.
- the mixing is carried out by first forming a neutral to alkaline aqueous phase, suitably an aqueous solution, of cellulose derivative which is then mixed with an aqueous composition of calcium salt-containing material.
- a neutral to alkaline aqueous phase suitably an aqueous solution
- the aqueous phase of cellulose derivative can be subjected to pre-treatment, e.g. homogenisation, centrifugation and/or filtration, for example for separating undissolved cellulose derivative, if any, from the aqueous phase.
- the cellulose derivative is mixed with the calcium salt-containing material to allow at least part of the cellulose derivative to adsorb on or attach to the calcium salt-containing material, preferably so that it is hardly removed from the material by dilution with water.
- This can be accomplished by carrying out mixing under a period of time that is sufficient long to allow the adsorption on attachment.
- the mixing time is at least about 1 min, preferably at least about 5 min, more preferably at least about 10 min and most preferably at least about 20 min. Mixing periods of even several hours (1 - 10 h) are possible if it is desired to reach a high degree of attachment.
- At least about 10 % by weight, preferably at least about 30 % by weight, more preferably at least about 45 % by weight and most preferably at least about 60 % by weight of the cellulose derivate is transferred from the aqueous phase and adsorbed on or attached to the calcium salt or other components present in the calcium salt-containing material.
- the pH of the aqueous phase of cellulose derivative is usually adjusted for sorption of the specific cellulose derivative used at a value from about 4 to about 13, preferably from about 6 to about 10, more preferably from about 7 to about 8.5.
- a suitable base or acid can be used for adjusting the pH.
- suitable bases include bicarbonates and carbonates of alkali metals and alkali metal hydroxides, suitably sodium bicarbonate, sodium carbonate and sodium hydroxide.
- suitable acids include mineral acids, organic acids and acid salts, suitably sulphuric acid and its acid salts, such as alum. In general, at a lower pH, i.e. a pH from about 4.0 to neutral, adsorption of the cellulose derivative is higher but solubility is decreased, whereas at higher pH the adsorption is reduced but solubility is increased.
- the temperature is not critical; in operations in non-pressurized conditions the temperature is typically from about 10 to about 100 °C, preferably from about 20 to about 80 °C. However, higher temperatures are more favourable, suitably the temperature of the aqueous composition during mixing is from about 30 up to about 70 °C, more preferably from about 40 up to about 60 °C.
- the mixing and attaching of cellulose derivative can be done simultaneously with precipitation of the calcium salt on the fibrils or fibres or after the precipitation. It is also possible to add the cellulose derivative before the precipitation. In that case the cellulose derivative is added either during beating or in a separate sorption after beating.
- the cellulose derivative can be adsorbed on or attached to the calcium salt-containing material or fibre or fibril surfaces and/or sorbed into the fibres or fibrils.
- the filler obtained by the method of the invention can be used as such, for example in papermaking. If present as an aqueous composition, it can be used directly or it can be dried, if desired, for example to simplify shipping.
- the present invention also relates to a process for the production of paper which comprises providing an aqueous suspension containing cellulosic fibres ("cellulosic suspension”), introducing into the cellulosic suspension a filler, e.g. any one of the fillers defined herein, and dewatering the cellulosic suspension to form a web or sheet of paper.
- the filler is introduced into the cellulosic suspension by adding it as a single composition.
- the calcium salt, or calcium salt-containing material e.g. any one of the calcium salt-containing materials defined herein
- amphoteric cellulose derivative e.g. any one of the cellulose derivatives defined herein
- other components may of course be introduced into the cellulosic suspension.
- components include conventional fillers, optical brightening agents, sizing agents, drainage and retention aids, dry strength agents, wet strength agents, etc.
- suitable conventional fillers include kaolin, china clay, titanium dioxide, gypsum, talc, natural and synthetic calcium carbonates, e.g. chalk, ground marble and precipitated calcium carbonate, hydrogenated aluminum oxides (aluminum trihydroxides), calcium sulphate, barium sulphate, calcium oxalate, etc.
- the filler according to the invention can be present in an amount of at least 1 % by weight, suitably at least 5 % by weight, preferably at least 10 % by weight, more preferable at least about 20 % by weight, and suitably up to about 99 % by weight, based on the dry weight of all fillers.
- suitable sizing agents include non-cellulose-reactive sizing agents, e.g. rosin-based sizing agents like rosin-based soaps, rosin-based emulsions/dispersions, and cellulose-reactive sizing agents, e.g.
- emulsions/dispersions of acid anhydrides like alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and multimers.
- suitable drainage and retention aids include organic polymeric products, e.g. cationic, anionic and non-ionic polymers including cationic polyethylene imines, cationic, anionic and non-ionic polyacrylamides, cationic polyamines, cationic starch, and cationic guar; inorganic materials, e.g. aluminium compounds, anionic microparticulate materials like colloidal silica-based particles, clays of smectite type, e.g.
- suitable combinations of drainage and retention aids include cationic polymers and anionic microparticulate materials, e.g. cationic starch and anionic colloidal silica-based particles, cationic polyacrylamide and anionic colloidal silica-based particles as well as cationic polyacrylamide and bentoinite or montmorillonite.
- suitable wet strength agents include polyamines and polyaminoamides. Paper containing filler according to the invention and cationic starch shows very good strength properties.
- At least one sizing agent is introduced into the cellulosic suspension to produce sized paper containing filler.
- the sizing agents are cellulose-reactive sizing agents of the types mentioned herein.
- Suitable ketene dimers have the general formula (I) below, wherein R 1 and R 2 represent saturated or unsaturated hydrocarbon groups, usually saturated hydrocarbons, the hydrocarbon groups suitably having from 8 to 36 carbon atoms, usually being straight or branched chain alkyl groups having 12 to 20 carbon atoms, such as hexadecyl and octadecyl groups.
- the ketene dimers may be liquid at ambient temperature, i.e.
- acid anhydrides can be characterized by the general formula (II) below, wherein R 3 and R 4 can be identical or different and represent saturated or unsaturated hydrocarbon groups suitably containing from 8 to 30 carbon atoms, or R 3 and R 4 together with the -C-O-C- moiety can form a 5 to 6 membered ring, optionally being further substituted with hydrocarbon groups containing up to 30 carbon atoms.
- acid anhydrides which are used commercially include alkyl and alkenyl succinic anhydrides and particularly isooctadecenyl succinic anhydride.
- Suitable ketene dimers, acid anhydrides and organic isocyanates include the compounds disclosed in U.S. Pat. No. 4,522,686 .
- the filler according to the invention can be added to the cellulosic suspension in amounts which can vary within wide limits depending on, inter alia, type of cellulosic suspension, type of paper produced, point of addition, etc.
- the filler is usually added in an amount within the range of from 1 to about 50 % by weight, suitably from about 5 to about 40 % by weight, and usually from about 10 to about 30 % by weight, based on the weight of dry fibres.
- the paper according to the invention usually has a content of filler of this invention within the range of from 1 to about 50 % by weight, suitably from about 5 to about 40 % by weight, and usually from about 10 to about 30 % by weight, based on the weight of dry fibres.
- these components can be added to the cellulosic suspension in amounts which can vary within wide limits depending on, inter alia, type and number of components, type of cellulosic suspension, filler content, type of paper produced, point of addition, etc.
- Sizing agents are usually introduced into the cellulosic suspension in an amount of at least about 0.01 % by weight, suitably at least about 0.1 % by weight, based on the weight of dry fibres, and the upper limit is usually about 2 % by weight, suitably about 0.5 % by weight.
- drainage and retention aids are introduced into the cellulosic suspension in amounts that give better drainage and/or retention than what is obtained when not using these aids.
- Drainage and retention aids, dry strength agents and wet strength agents, independently of each other, are usually introduced in an amount of at least about 0.001% by weight, often at least about 0.005% by weight, based on dry fibres, and the upper limit is usually about 5% and suitably about 1.5% by weight.
- the term "paper”, as used herein, include not only paper and the production thereof, but also other cellulosic fibre-containing sheet or web-like products, such as for example board and paperboard, and the production thereof.
- the process can be used in the production of paper from different types of aqueous suspensions of cellulosic (cellulose-containing) fibres and the suspensions should suitably contain at least 25% by weight and preferably at least 50% by weight of such fibres, based on a dry substance.
- the cellulosic fibres can be based on virgin fibres and/or recycled fibres, including fibres of wood orannual or perennial plants.
- the cellulosic suspension can be wood-containing or wood-free, and it can be based on fibres from chemical pulp such as sulphate, sulphite and organosolve pulps, mechanical pulp such as thermo-mechanical pulp, chemo-thermo-mechanical pulp, refiner pulp and ground wood pulp, from both hardwood and softwood, and can also be based on recycled fibres, optionally from de-inked pulps, and mixtures thereof.
- the cellulosic suspension suitably has a pH in the neutral to alkaline range, e.g. from about 6 to about 10, preferably from about 6.5 to about 8.0.
- the paper produced can be dried, coated and calendered.
- the paper can be coated with, for example, calcium carbonate, gypsum, aluminium silicate, kaolin, aluminium hydroxide, magnesium silicate, talc, titanium dioxide, barium sulphate, zinc oxide, synthetic pigment, and mixtures thereof.
- the grammage of the paper produced can vary within wide limits depending on the type of paper produced; usually the grammage is within the range from about 20 to about 500 g/m 2 , suitably from about 30 to about 450 g/m 2 , and preferably from 30 to about 110 g/m 2 .
- the invention is used for the production of uncoated and coated offset paper, electrophotography paper, uncoated and coated fine paper, optionally containing mechanical pulp, as well as writing and printing papers.
- An especially preferred product is coated offset paper in which high gloss and high opacity and bulk are combined.
- Fillers according to the invention and for comparison were prepared by treating calcium salt-containing material with cellulose derivatives.
- CMC carboxymethyl celluloses
- the average molecular weights of the cellulose derivatives used were in the range of from 100,000 to 400,000.
- Calcium salt-containing materials used were different precipitated calcium carbonates (“PCC”) having a surface area of 5.7 and 10.0 m 2 /g, respectively.
- Another calcium salt-containing material used was SuperFill ® (PCC on
- the fillers were prepared by dissolving CMC into water to a consistency of 0.5 % by weight. Thereafter, the obtained CMC composition was added to PCC filler slurry and mixed during 25 to 45 minutes at a temperature of about 50 °C.
- the fillers according to the invention (“Invention Product”) and for comparison (“Comparison Product”) were the following: Comparison Product 1 ("ICP1"): CMC (DS NI 0.3)-treated PCC (5.7 m 2 /g) Comparison Product 2 (“ICP2”): CMC (DS NI 0.3)-treated PCC (10 m 2 /g) Comparison Product 3 (“ICP3"): CMC (DS NI 0.32)-treated SuperFill ® Invention Product 4 (“IP4"): QN-CMC (DS NI 0.23)-treated SuperFill ® .
- Comparison Product 1 (“CP1"): CMC (DS NI 0.7)-treated PCC (5.7 m 2 /g) Comparison Product 1 (“CP2”): SuperFill ® .
- Paper produced according to the invention was evaluated and compared to paper used for comparison purposes.
- Paper was produced using ICP1 according to Example 1.
- Paper used for comparison was produced using CP1 according to Example 1 and using filler containing no cellulose derivative.
- Paper sheets were produced from pulp consisting of chemical pulp and containing untreated PCC in varying amounts (% by weight, based on dry paper), as indicated in Table 1.
- To the pulp suspension was added 2.0 kg/tonne dry fibres of filler according to Example 1 and filler containing no cellulose derivative; 3.0 kg/tonne dry fibres of AKD (aqueous dispersion Eka Keydime C223), and a retention system comprising cationic starch (Eka PL 1510) and silica particles (Eka NP 780). Both the cationic starch and silica particles were added in an amount of 0.15 kg/tonne dry fibres.
- the addition sequence was as follows: Addition of CMC-treated PCC: 0 sec Addition of AKD dispersion: 30 sec. Addition of cationic starch: 45 sec. Addition of silica particles: 60 sec. Sheet formation: 75 sec.
- Paper sheets were produced from pulp of the same type used in Example 2 and containing 30 % by weight, based on dry paper, of untreated PCC (surface area of 10 m 2 /g) or CMC (DS NI 0.3)-treated PCC (10 m 2 /g) (ICP2 according to Example 1).
- PCC surface area of 10 m 2 /g
- CMC DS NI 0.3
- ICP2 ICP2 according to Example 1
- PB 970 cationic starch
- AKD aqueous sizing dispersion Eka Keydime C223
- retention system comprising cationic polyacrylamide (Eka PL
- Both the cationic polyacrylamide and silica particles were added in an amount of 0.20 kg/tonne dry paper.
- untreated PCC 1.0 kg/tonne of CMC having a DS NI of 0.3 was separately added.
- No separate addition of CMC was made when adding CMC-treated PCC.
- the addition sequence was as follows: Addition of cationic starch: 0 sec Addition of CMC-treated PCC / untreated PCC: 30 sec Separate addition of CMC: 35 sec. Addition of AKD: 45 sec. Addition of cationic polyacrylamide: 60 sec. Addition of silica particles: 75 sec. Sheet formation: 90 sec.
- Paper sheets were manufactured from a fibre furnish containing 70% by weight of mixed hardwood pulp and 30% by weight of softwood pulp refined at 22° and 25° SR, respectively, in a method similar to Example 3 except that no cationic starch was used and use was made of untreated SuperFill ® filler (CP2) or CMC-treated SuperFill ® filler (ICP3 and IP4), which was added in an amount so as to give a paper sheet containing 30% by weight of SuperFill ® filler.
- the addition sequence was as follows: Addition of SuperFill ® filler: 0 sec. Addition of cationic polyacrylamide: 45 sec. Addition of silica particles: 75 sec. Addition of AKD: 90 sec.
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Priority Applications (6)
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EP10186029.4A EP2325388B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
DK08172278.7T DK2037041T3 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
DK10186029.4T DK2325388T3 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP08172278.7A EP2037041B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP04809143.3A EP1704282B2 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
PL04809143T PL1704282T3 (pl) | 2003-12-22 | 2004-12-20 | Wypełniacz do sposobu wytwarzania papieru |
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EP03445149 | 2003-12-22 | ||
EP04809143.3A EP1704282B2 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
PCT/SE2004/001970 WO2005061793A1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
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EP08172278.7A Division-Into EP2037041B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP08172278.7A Division EP2037041B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP10186029.4A Division-Into EP2325388B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP10186029.4A Division EP2325388B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
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EP1704282A1 EP1704282A1 (en) | 2006-09-27 |
EP1704282B1 EP1704282B1 (en) | 2018-04-25 |
EP1704282B2 true EP1704282B2 (en) | 2023-08-30 |
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EP04809143.3A Active EP1704282B2 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP08172278.7A Revoked EP2037041B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP10186029.4A Active EP2325388B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
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EP08172278.7A Revoked EP2037041B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
EP10186029.4A Active EP2325388B1 (en) | 2003-12-22 | 2004-12-20 | Filler for papermaking process |
Country Status (19)
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EP (3) | EP1704282B2 (ko) |
JP (1) | JP4799424B2 (ko) |
KR (1) | KR100810389B1 (ko) |
CN (2) | CN101871181A (ko) |
AR (1) | AR050757A1 (ko) |
AU (1) | AU2004303745B2 (ko) |
BR (1) | BRPI0418030B1 (ko) |
CA (1) | CA2550261C (ko) |
DK (2) | DK2325388T3 (ko) |
ES (3) | ES2630379T3 (ko) |
LT (1) | LT2037041T (ko) |
NZ (1) | NZ547789A (ko) |
PL (3) | PL2325388T3 (ko) |
PT (3) | PT2037041T (ko) |
RU (1) | RU2345189C2 (ko) |
SI (2) | SI2037041T1 (ko) |
TR (1) | TR201809764T4 (ko) |
TW (1) | TWI356862B (ko) |
WO (1) | WO2005061793A1 (ko) |
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EP1697587B1 (en) * | 2003-12-22 | 2009-04-22 | Akzo Nobel N.V. | Paper comprising quaternary nitrogen containing cellulose ether |
PL2158359T3 (pl) * | 2007-06-08 | 2014-04-30 | Fpinnovations | Zawiesiny wypełniacza poddanego obróbce lateksem do stosowania w produkcji papieru |
CL2008002019A1 (es) * | 2007-07-16 | 2009-01-16 | Akzo Nobel Chemicals Int Bv | Composicion de carga que comprende una carga, un compuesto inorganico cationico, un compuesto organico cationico y un polisacarido anionico; metodo para preparar dicha composicion; uso como aditivo para una suspension celulosica acuosa; procedimiento para producir papel; y papel. |
US8088250B2 (en) * | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
DE102007000806B3 (de) * | 2007-10-01 | 2009-04-30 | Institut für Holztechnologie Dresden gGmbH | Beschichtung für Holzmaterialien und Verfahren zu ihrer Herstellung |
FI124724B (fi) * | 2009-02-13 | 2014-12-31 | Upm Kymmene Oyj | Menetelmä muokatun selluloosan valmistamiseksi |
DK2236545T3 (en) | 2009-03-30 | 2014-12-01 | Omya Int Ag | A process for the preparation of nano-fibrillar cellulose gels |
PL3617400T3 (pl) | 2009-03-30 | 2023-01-02 | Fiberlean Technologies Limited | Zastosowanie zawiesin nanofibrylarnej celulozy |
FI124464B (fi) | 2009-04-29 | 2014-09-15 | Upm Kymmene Corp | Menetelmä massalietteen valmistamiseksi, massaliete ja paperi |
JP5601630B2 (ja) * | 2010-03-31 | 2014-10-08 | 荒川化学工業株式会社 | 製紙用填料分散液および填料含有紙 |
EP2386682B1 (en) | 2010-04-27 | 2014-03-19 | Omya International AG | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
SI2386683T1 (sl) | 2010-04-27 | 2014-07-31 | Omya International Ag | Postopek za proizvodnjo kompozitnih materialov na osnovi gela |
CA2810424C (en) * | 2010-10-01 | 2018-04-03 | Fpinnovations | Cellulose-reinforced high mineral content products and methods of making the same |
AR086593A1 (es) * | 2011-06-08 | 2014-01-08 | Akzo Nobel Chemicals Int Bv | Proceso para la produccion de papel y carton |
RU2473725C1 (ru) * | 2011-08-16 | 2013-01-27 | Общество с ограниченной ответственностью "Оптимальные химические технологии+консалтинг" | Способ получения картона с белым покровным слоем |
CN104114512B (zh) * | 2012-02-17 | 2017-09-26 | 美国石膏公司 | 具有高效散热添加剂的石膏产品 |
RU2499094C1 (ru) * | 2012-10-05 | 2013-11-20 | Российская Федерация в лице Министерства промышленности и торговли Российской Федерации | Способ получения бумажной массы |
SI2722368T1 (sl) | 2012-10-16 | 2016-10-28 | Omya International Ag | Postopek nadzorovane kemične reakcije površine iz snovi trdnega polnila in dodatki za proizvodnjo površinsko obdelovane polnilne snovi |
CA2934998C (en) * | 2013-12-30 | 2022-06-21 | Kemira Oyj | Filler aggregate composition and its production |
CN104018395B (zh) * | 2014-06-11 | 2016-11-23 | 金东纸业(江苏)股份有限公司 | 一种填料混合液及其制备方法、纸张的制造方法 |
SE539437C2 (en) * | 2015-03-31 | 2017-09-19 | Stora Enso Oyj | A method of producing filler from fractionated fly ash |
EP3118161B1 (en) * | 2015-07-17 | 2018-05-16 | Omya International AG | High solids pcc with depolymerized carboxylated cellulose |
EP3362508B1 (en) | 2015-10-14 | 2019-06-26 | FiberLean Technologies Limited | 3d-formable sheet material |
SE540790C2 (en) * | 2016-02-12 | 2018-11-13 | Stora Enso Oyj | Calcium carbonate precipitated on natural fibers and method for the production thereof |
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