CA2540117A1 - Method for producing paper, paperboard and cardboard - Google Patents
Method for producing paper, paperboard and cardboard Download PDFInfo
- Publication number
- CA2540117A1 CA2540117A1 CA002540117A CA2540117A CA2540117A1 CA 2540117 A1 CA2540117 A1 CA 2540117A1 CA 002540117 A CA002540117 A CA 002540117A CA 2540117 A CA2540117 A CA 2540117A CA 2540117 A1 CA2540117 A1 CA 2540117A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- insoluble
- uncrosslinked
- water
- monomer
- 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.)
- Abandoned
Links
- 239000000123 paper Substances 0.000 title claims abstract description 54
- 239000011111 cardboard Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000011087 paperboard Substances 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 98
- 239000011859 microparticle Substances 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 43
- 230000014759 maintenance of location Effects 0.000 claims abstract description 34
- 239000000440 bentonite Substances 0.000 claims abstract description 31
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 31
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 36
- 125000002091 cationic group Chemical group 0.000 claims description 32
- 229920000620 organic polymer Polymers 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- -1 C10-alkyl methacrylate Chemical compound 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 125000000129 anionic group Chemical group 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 125000003010 ionic group Chemical group 0.000 claims description 3
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 3
- 229920005613 synthetic organic polymer Polymers 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 235000012216 bentonite Nutrition 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229920006317 cationic polymer Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000013065 commercial product Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052615 phyllosilicate Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 125000005228 aryl sulfonate group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 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
- 239000000835 fiber Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- ZLPXFBBKYQYQEA-UHFFFAOYSA-N 1-(prop-2-enoylamino)ethanesulfonic acid Chemical compound OS(=O)(=O)C(C)NC(=O)C=C ZLPXFBBKYQYQEA-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LVGSUQNJVOIUIW-UHFFFAOYSA-N 5-(dimethylamino)-2-methylpent-2-enamide Chemical compound CN(C)CCC=C(C)C(N)=O LVGSUQNJVOIUIW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/08—Mechanical or thermomechanical pulp
-
- 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
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H17/33—Synthetic macromolecular compounds
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
- 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
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
-
- 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
Landscapes
- Paper (AREA)
Abstract
The invention relates to a method for producing paper, paperboard and card board by adding (i) at least one retention agent and (ii) organic, ionic and uncrosslinked microparticles which are water-insoluble and whose mean particle size is less than 500 nm and whose ionic polymerisable monomer content is less than 1 % by weight or organic, ionic and uncrosslinked microparticles which are water-insoluble and whose mean particle size is less than 500 nm and whose ionic polymerisable monomer maximum content is equal to 10 % in weight obtainable by monomer polymerisation in the presence of silicon, waterglass, bentonite and/or the mixture thereof into a pulp and by dehydration of said pulp on a sieve.
Description
Method for producing paper, paperboard and cardboard The present invention relates to a process for the production of paper, board and cardboard by adding uncrosslinked organic microparticles and at least one retention aid to the paper stock and draining the paper stock over a wire.
Inorganic microparticles, such as bentonite or colloidal silica sots, are used in the production of paper together with cationic polymers for improving the retention and the drainage of the paper stock, cf. EP-A-0 235 893, EP-A-0 335 575, EP-A-0 310 959, US-A-4 388 150 and WO-A-94/05595. In this process, a cationic polymer is metered in an amount of more than 0.03% by weight, based on dry paper stock, the mixture is then subjected to the action of a shear field, the initially formed flocks being broken up into microflocks, bentonite or silica is then added and the pulp thus obtained is drained without further action of shear forces. According to the process of DE-A-102 36 252, a microparticle system comprising a cationic polymer and a finely divided inorganic component is metered to the paper stock after the final shear stage upstream of the headbox and the paper stock is then drained. Compared with the use of cationic polymers alone as retention aids, papers having an improved formation are obtained using the multicomponent systems comprising cationic polymers and inorganic microparticles.
EP-A-0 462 365 discloses organic microparticles which may be uncrosslinked or crosslinked and which in each case comprise at least 1, but generally at least 5, % by weight of an ionic comonomer incorporated in the form of polymerized units.
The particle size of the uncrosslinked, water-insoluble microparticles is below 60 nm, while that for the crosslinked microparticles is less than 750 nm. The organic microparticles are used in papermaking together with a high molecular weight ionic polymer as a retention aid. In addition to the organic microparticles, bentonite or finely divided silica may also be used in papermaking. Suitable high molecular weight polymers are both synthetic organic polymers and polysaccharides.
EP-A-0 810 274 discloses binders based on aqueous styrenelacrylate polymer dispersions having a mean film formation temperature of less than 10°C.
The polymers can, if appropriate, comprise up to 1 % by weight of a monomer comprising acid groups.
The particle size of the disperse polymer particles is preferably in the range from 100 to 300 nm. The binders are used, for example, for the preparation of coating materials, such as plastics dispersion renders, tile adhesives, coating materials and in particular low-emission emulsion paints.
WO-A-02/101145 discloses aqueous mixtures which comprise anionic, crosslinked, polymeric particles having a particle size in the unswollen state of less than 750 nm, in particular from 25 to 300 nm, and colloidal anionic silica particles. The mixtures are used in papermaking together with a cationic polymer as drainage and retention aids.
Inorganic microparticles, such as bentonite or colloidal silica sots, are used in the production of paper together with cationic polymers for improving the retention and the drainage of the paper stock, cf. EP-A-0 235 893, EP-A-0 335 575, EP-A-0 310 959, US-A-4 388 150 and WO-A-94/05595. In this process, a cationic polymer is metered in an amount of more than 0.03% by weight, based on dry paper stock, the mixture is then subjected to the action of a shear field, the initially formed flocks being broken up into microflocks, bentonite or silica is then added and the pulp thus obtained is drained without further action of shear forces. According to the process of DE-A-102 36 252, a microparticle system comprising a cationic polymer and a finely divided inorganic component is metered to the paper stock after the final shear stage upstream of the headbox and the paper stock is then drained. Compared with the use of cationic polymers alone as retention aids, papers having an improved formation are obtained using the multicomponent systems comprising cationic polymers and inorganic microparticles.
EP-A-0 462 365 discloses organic microparticles which may be uncrosslinked or crosslinked and which in each case comprise at least 1, but generally at least 5, % by weight of an ionic comonomer incorporated in the form of polymerized units.
The particle size of the uncrosslinked, water-insoluble microparticles is below 60 nm, while that for the crosslinked microparticles is less than 750 nm. The organic microparticles are used in papermaking together with a high molecular weight ionic polymer as a retention aid. In addition to the organic microparticles, bentonite or finely divided silica may also be used in papermaking. Suitable high molecular weight polymers are both synthetic organic polymers and polysaccharides.
EP-A-0 810 274 discloses binders based on aqueous styrenelacrylate polymer dispersions having a mean film formation temperature of less than 10°C.
The polymers can, if appropriate, comprise up to 1 % by weight of a monomer comprising acid groups.
The particle size of the disperse polymer particles is preferably in the range from 100 to 300 nm. The binders are used, for example, for the preparation of coating materials, such as plastics dispersion renders, tile adhesives, coating materials and in particular low-emission emulsion paints.
WO-A-02/101145 discloses aqueous mixtures which comprise anionic, crosslinked, polymeric particles having a particle size in the unswollen state of less than 750 nm, in particular from 25 to 300 nm, and colloidal anionic silica particles. The mixtures are used in papermaking together with a cationic polymer as drainage and retention aids.
However, they can also be used as flocculants and for treating wastewater and sludges.
Further microparticle systems which are used as an additive to the paper stock in papermaking are disclosed in EP-A-0 497 030 and EP-A-0 0635 602. US-A-6 083 discloses the preparation of an anionic nanocomposite which is used as a retention aid and drainage aid in papermaking. As is evident therefrom, waterglass is mixed with an anionic polyelectrolyte based on polysulfonates, polyacrylates or polyphosphates and either silica is added or the silica is produced in situ.
It is an object of the present invention to provide a further process for the production of paper, board and cardboard using a microparticle system.
We have found that this object is achieved, according to the invention, by a process for the production of paper, board and cardboard by adding ionic, water-insoluble, uncrosslinked, organic microparticles and at least one retention aid to a paper stock and draining the paper stock over a wire, if the organic microparticles used are water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight or water-insoluble, uncrosslinked, organic microparticles having an average particle size of less than 500 nm and a content of polymerized ionic monomers of not more than 10% by weight, which are obtainable by polymerizing the monomers in the presence of silica, waterglass, bentonite and/or mixtures thereof.
Said particle sizes are always the weight average particle sizes d50. Said particle size was determined by dynamic light scattering on a 0.01 % strength by weight dispersion at 23°C by means of an lic autosizer from Malvern Instruments, UK. The average particle size of the water-insoluble, uncrosslinked, organic polymers is preferably from 10 to 100 nm and the content of polymerized ionic monomers is from 0.1 to 0.95% by weight. Microparticles having average particle sizes of the water-insoluble, uncrosslinked, organic polymers of from 10 to 80 nm and a content of polymerized ionic monomers of from 0.2 to 0.7% by weight are particularly preferred. In general, the average particle size of the microparticles is in the range from 15 to 50 nm.
The microparticles comprising water-insoluble, uncrosslinked, organic polymers comprise either at least one anionic monomer or one cationic monomer incorporated in the form of polymerized units. Aqueous dispersions which comprise anionic microparticles are disclosed in EP-A-0 810 274, page 3, line 3 to page 15, line 59, disclosed in connection with the prior art. Suitable water-insoluble, uncrosslinked, organic polymers which carry an ionic charge are obtainable, for example, by free radical aqueous emulsion polymerization of a monomer mixture comprising (a) from 30 to 55 parts by weight of at least one monomer whose homopolymer has a glass transition temperature T9 of <20°C, (b) from 45 to 70 parts by weight of at least one monomer whose homopolymer has a glass transition temperature T9 of >50°C and (c) from 0.01 to less than 1 part by weight of a monomer having ionic groups, the sum of the parts by weight of (a) and (b) always being 100. The monomers having ionic groups can impart to the polymer either an anionic charge, if, for example, monoethylenically unsaturated monomers having acidic groups are used in the polymerization, or a cationic charge, if the polymerization is carried out in the presence of monoethylenically unsaturated, basic monomers. The glass transition temperature T9 is understood as meaning the limit of the glass transition temperature to which said glass transition temperature tends with increasing molecular weight, according to G. Kanig (cf. Kolloid-Zeitschrift & Zeitschrift fur Polymere, Volume 190, page 1, equation 1 ). It is determined by the DSC method (differential scanning calorimetry, K/min, midpoint). The T9 values for the homopolymers of most monomers are known, cf. for example Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim, 1992, Part 5, Vol. A21, page 169.
20 The monomer (a) is, for example, selected from at least one C,- to C,o-alkyl acrylate, C5- to C,o-alkyl methacrylate, CS- to C,o-cycloalkyl (meth)acrylate, C,- to C,o-dialkyl maleate and/or C,- to C,o-dialkyl fumarate. Typical monomers (b) are, for example, selected from at least one vinylaromatic monomer andlor one a,(3-unsaturated carbonitrile or carbodinitrile.
C,- to C~ alkyl groups are to be understood as meaning linear or branched alkyl radicals of 1 to n carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl and n-decyl. C5-to C,o-Cycloalkyl groups are, for example, cyclopentyl, cyclohexyl or cyclooctyl, which may optionally be substituted in each case by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms.
The water-insoluble, uncrosslinked, organic polymer is preferably composed of from 35 to 50 parts by weight of monomer units (a), from 50 to 65 parts by weight of monomer units (b) and from 0.01 to 0.95 part by weight of monomer units (c), the sum of the monomer units (a) and (b) always being 100.
Where it is an anionic monomer, the monomer (c) is, for example, selected from a,(3-unsaturated C3- to C6-carboxylic acids, a,(3-unsaturated C4- to CB-dicarboxylic acids, anhydrides thereof, monoethylenically unsaturated alkanesulfonic acids, monoethylenically unsaturated phosphonic acids and/or monoethylenically unsaturated arylsulfonic acids. The monomer (c) may be used in the polymerization if appropriate in a form partly or completely neutralized with alkali metal, alkaline earth metal andlor ammonium bases. Moreover, it is possible for polymers which comprise the monomers (c) incorporated by polymerization in the form of the free acid groups to be neutralized during or after the end of the polymerization. Suitable bases are, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, amines, such as trimethylamine, propylamine or butylamine, pyridine, piperidine, morpholine and alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine, calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide. Preferred monomers of group (c) are acrylic acid, methacrylic acid, crotonic acid, malefic acid, fumaric acid, malefic anhydride, itaconic acid, itaconic anhydride, vinylsulfonic acid, methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate and sulfopropyl (meth)acrylate.
Particularly preferred monomers of this group are acrylic acid, methacrylic acid and acrylamido-2-methylpropanesulfonic acid, mixtures of these monomers and alkali metal and ammonium salts thereof, in particular sodium salts thereof.
If the monomer (c) is a cationic monomer, this is to be understood as meaning, for example, the following monomers: diallyldimethylammonium chloride, di-C,-to Cz-alkylamino-C2- to C4-alkyl (meth)acrylates and di-C,- to CZ-alkylamino-CZ- to alkyl(meth)acrylamides. Said dialkylaminoalkyl (meth)acrylates and dialkylaminoalkyl(meth)acrylamides are preferably used in the form of salts with mineral acids or organic acids or in quaternized form. The quaternizing agent used is, for example, methyl chloride, ethyl chloride or dimethyl sulfate. Examples of preferably used cationic monomers are diallyldimethylammonium chloride and the following salts of sulfuric acid or hydrochloric acid or compounds quaternized with methyl chloride:
dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminoethylmethacrylamide and dimethylaminopropyl(meth)acrylamide. The polymers may also comprise, as cationic groups, vinylamine units in the form of salts with mineral acids or in quaternized form.
Polymers having such groups are obtained, for example, if the polymerization is carried out in the presence of vinylformamide as a comonomer, and the vinylformamide units present in the copolymer are then hydrolyzed with sulfuric acid to give vinylamine units.
Monomers of group (c) are present in an amount of less than 1 part by weight, based on 100 parts by weight of the sum of the monomers (a) and (b), in the monomer mixture which is subjected to the polymerization. Preferably, the monomer mixture comprises from 0.01 to 0.95, in particular from 0.2 to 0.7, part by weight, based on 100 parts by weight of the monomer (a) and (b), of at least one monomer (c).
In addition to said polymers of the components (a), (b) and (c), those microparticles of water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of up to 10% by weight which are obtainable by polymerizing the monomers on which these polymers are 5 based in the presence of silica, waterglass, bentonite andlor mixtures thereof are also suitable for papermaking. In the case of this type of microparticles, the content of monomers of group (c) is, for example, from 0.1 to 10, preferably from 1.5 to 7, in particular from 2 to 5, % by weight.
Examples of monomers (a) are vinyl ethers of C3- to C,o-alkanols, branched and straight-chain C3- to C,o-olefins, C,- to C,o-alkyl acrylates, CS- to C,o-alkyl methacrylates, CS- to C,o-cycloalkyl (meth)acrylates, C,- to C,o-dialkyl maleates and/or C,- to Coo-diallkyl fumarates. Particularly preferred monomers of this group are, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleate andlor di-n-butyl fumarate.
Examples of suitable monomers (b) are vinylaromatic monomers, such as styrene or a-methylstyrene, and styrene or a-methylstyrene substituted by 1, 2 or 3 C,- to C4-alkyl groups, chlorine andlor methoxy groups. Preferred monomers of group (b) have a glass transition temperature above 80°C. Examples of these are styrene, a-methylstyrene, o- or p-vinyltoluene, acrylonitrile, methacrylonit~ile, maleodinitrile, fumarodinitrile or mixtures thereof.
The copolymers may if appropriate comprise further monoethylenically unsaturated monomers, such as acrylamide, methacrylamide, N-vinylpyrrolidone and N-vinylcaprolactam, incorporated in the form of polymerized units. The amounts are, for example, from 0 to 10 parts by weight, based on 100 parts by weight of the monomers (a) and (b).
The polymerization of the monomers is effected by the known methods of emulsion polymerization in the presence of initiators which form free radicals under the polymerization conditions, such as peroxides, hydroperoxides, azo compounds or redox initiators, and in the presence of emulsifiers. Further information in this context can be obtained from the abovementioned EP-A-0 810 274, pages 4 and 5. The polymerization of the suitable monomers can, however, also be carried out in the presence of silica, waterglass, bentonite and/or mixtures thereof. Aqueous dispersions of ionic, water-insoluble, uncrosslinked, organic polymers having an average particle size below 500 nm are obtained. The polymerization can, however, also be effected by preparing an emulsion from water, the monomers, a hydrocarbon which is liquid at room temperature, such as hexane, pentane, isooctane, toluene and/or xylene, and at least one surfactant and polymerizing the monomers in the presence of free radical initiators.
Preferred polymers are those which comprise (a) at least one monomer from the group consisting of n-butylacrylate, isobutyl acrylate, n-propyl acrylate, isopropyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and methyl acrylate, (b) at least one monomer from the group consisting of styrene, a-methylstyrene, acrylonitrile and methacrylonitrile and (c) at least one monomer from the group consisting of acrylic acid, methacrylic acid, malefic acid and acrylamido-2-methylpropanesulfonic acid in the abovementioned amounts, incorporated in the form of polymerized units.
Copolymers which comprise, incorporated in the form of polymerized units n-butyl acrylate and styrene in the weight ratio of 1 : 1 and from 0.2 to 0.7% by weight of methacrylic acid or acrylic acid are particularly preferred.
The average molar mass MW of the polymers is, for example, from 500 000 to 5 million, preferably from 1 to 3 million.
The ionic, water-insoluble, uncrosslinked, organic microparticles described above are added together with at least one retention aid to the paper stock in papermaking. The organic microparticles promote the action of the retention aid. The organic microparticles are used, for example, in amounts of from 0.1 to 1, preferably in amounts of from 0.2 to 0.6, % by weight, based on dry paper stock. The amounts of retention aid are, for example, from 0.01 to 0.09, preferably from 0.02 to 0.04, % by weight, based on dry paper stock. Retention aids which may be used are all conventional polymers which are known for this purpose, for example polyacrylamides, cationic polyacrylamides, such as copolymers of acrylamide and dimethylaminoethyl acrylate which is quaternized with methyl chloride, polyvinylamines, polydiallyldimethylammonium chlorides, anionic polyacrylamides, such as copolymers of acrylamide and acrylic acid or copolymers of acrylamide and methacrylic acid, and also polydialkylaminoalkyl(meth)acrylamides, such as polydimethylaminoethyl-acrylamide and polydimethylaminoethylmethacrylamide, which in each case are used in protonated or in quaternized form, and polyethylene oxides, which if appropriate may be cationically andlor anionically modified. Furthermore, polyamidoamines which are grafted with ethylenimine and crosslinked with dichlorohydrin ethers of polyethylene glycols are suitable as retention aids. Further conventional retention aids are cationic starches. Such starches are prepared, for example, by reacting starch with cationizing agents, such as 3-chloro-2-hydroxypropyltrimethylammonium chloride. The degree of substitution of the cationic starch is, for example from 0.01 to 1, preferably from 0.02 to 0.5. Amphoteric starches may also be used as retention aids provided that they have an excess cationic charge. The retention aids are known to have a high molecular weight and thus differ substantially from fixing agents which are based on the same monomers. The molecular weight M", of the retention aids is, for example, at least 500 000, preferably >1 million, generally >2 million, in particular >5 million.
According to the novel process, all paper qualities can be produced, for example cardboard, single-ply/multiply cardboard for folding cartons, single-ply/multiply liners, corrugated material, newsprint, so-called medium-ply writing and printing papers, natural gravure printing paper and light-weight coating papers. In order to produce these papers, it is possible to start, for example, from groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood (PGIIIn, wood pulp and sulfite and sulfate pulp. The chemical pulps may be either short-fiber or long-fiber. According to the novel process, wood-free qualities, which give highly white paper products, are preferably produced.
The papers can if appropriate comprise up to 40, in general from 5 to 35, % by weight of fillers. Suitable fillers are, for example, titanium dioxide, natural and precipitated chalk, talc, kaolin, satin white, calcium sulfate, barium sulfate, clay and/or alumina.
Paper can also be produced in the presence of conventional process chemicals.
For example, at least one fixing agent, strength agent for paper and/or an engine size can also be added to the paper stock. Suitable fixing agents are, for example, polymers comprising vinylamine units, polydiallyldimethylammonium chloride, polyethylenimines, polyalkylenepolyamines and/or dicyandiamide polymers. The molecular weight MW
of the fixing agent is, for example, up to 300 000, in general in the range from 50 000 to 1 million.
According to the invention, water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight are metered together with at least one cationic, anionic, amphoteric or neutral synthetic organic polymer and/or cationic starch as a retention aid to the paper stock before the final shear stage upstream of the headbox.
In an embodiment of the novel process, water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight are metered together with at least one retention aid and a finely divided inorganic component to the paper stock after the final shear stage upstream of the headbox. However, it is also possible to use a procedure in which the retention aid is metered before the final shear stage upstream of the headbox and water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight, alone or together with the finely divided inorganic component, are metered after the final shear stage upstream of the headbox.
In addition, combinations of a polymeric organic retention aid and those water-insoluble, uncrosslinked, organic microparticles having an average particle size of less than 500 nm and a content of polymerized ionic monomers of not more than 10%
by weight which are obtainable by polymerizing the monomers in the presence of silica, waterglass, bentonite andlor mixtures thereof can be used in papermaking.
In a further embodiment of the novel process, water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight are used together with polymers of monoethylenically unsaturated carboxylic acids, for example homopolymers of acrylic acid or methacrylic acid, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and malefic acid andlor copolymers of methacrylic acid and malefic acid. These polymers may if appropriate comprise further monomers, such as acrylamide and/or methacrylamide, incorporated in the form of polymerized units. The molecular weight MW of this group of polymers is, for example, from 2 000 to 200 000, preferably in the range from 5 000 to 110 000. These polymers result in an increase in the charge of the microparticles or preaggregation of the microparticles and hence improved retention in papermaking.
According to a further process variant, the water-insoluble, uncrosslinked, organic polymers having a content of polymerized ionic monomers of less than 1 % by weight are used together with inorganic microparticles from the group consisting of bentonite, colloidal silica, sheet silicates and/or finely divided calcium carbonate. The particle size of said inorganic substances is, for example, from 1 to 100 000 nm, preferably from 5 to 500 nm. These particle size data are based in each case on the inorganic substances dispersed in water. For example, from 0.01 to 10, preferably from 0.05 to 2, in particular from 0.1 to 1.2, parts by weight of at least one type of inorganic microparticles are used per part by weight of the organic microparticles. If organic microparticles containing up to not more than 10% by weight of monomers of group (c) are prepared by polymerizing the monomers in the presence of silica, waterglass andlor bentonite, corresponding amounts, based on the weight of the microparticles formed, of inorganic microparticles are used in the polymerization.
For example, bentonite, colloidal silica, silicates and/or calcium carbonate are suitable as the inorganic component of the microparticle system. Colloidal silica is to be understood as meaning those products which are based on silicates, e.g. silica microgel, silica sol, polysilicates, aluminum silicates, borosilicates, polyborosilicates, clay or zeolites. Calcium carbonate may be used, for example, in the form of chalk, ground calcium carbonate or precipitated calcium carbonate as the inorganic component of the microparticle system.. Bentonite is understood generally as meaning sheet silicates which are swellable in water. These are in particular the clay mineral montmorillonite and similar clay minerals, such as nontronite, hectorite, saponite, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite. These sheet silicates are preferably activated before they are used, .i.e. converted into a form better swellable in water by treating the sheet silicates with an aqueous base, such as aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate. Bentonite in the form treated with sodium hydroxide solution is preferably used as the inorganic component of the microparticle system. The platelet diameter of the bentonite dispersed in water, in the form treated with sodium hydroxide solution, is, for example, from 1 to 2 Nm, and the thickness of the platelets is about 1 nm. Depending on the type and activation, the bentonite has a specific surface area of from 60 to 800 m2/g. Typical bentonites are described, for example, in EP-B-0235893.
In the papermaking process, bentonite is added to the cellulose suspension typically in the form of an aqueous bentonite slurry. This bentonite slurry may comprise up to 10%
by weight of bentonite. Usually, the slurries comprise about 3 - 5% by weight of bentonite.
Products from the group consisting of silicon-based particles, silica microgels, silica sols, aluminum silicates, borosilicates, polyborosilicates or zeolites may be used as colloidal silica. These have a specific surface area of 50 -1 000 m2lg and an average particle size distribution of 1 - 250 nm, usually in the range 40 - 100 nm.
The preparation of such components is described, for example, in EP-A-0041056, EP-A-0185068 and US-A-5176891.
Clay or kaolin is a water-containing aluminum silicate having a lamellar structure. The crystals have a layer structure and an aspect ratio (ratio of diameter to thickness) of up to 30:1. The particle size is such that at least 50% of the particles are smaller than 2 mm.
Carbonates, preferably calcium carbonate, used may be natural calcium carbonate (ground calcium carbonate, GCC) or precipitated calcium carbonate (PCC). GCC
is prepared by milling and classification processes using milling assistants. It has a particle size such that 40 - 95% of the particles are smaller than 2 mm, and the specific surface area is in the range of 6 - 13 m2/g. PCC is prepared by passing carbon dioxide into calcium hydroxide solution. The average particle size is in the range of 0.03 0.6 mm, and the specific surface area can be greatly influenced by the choice of the precipitation conditions. It is in the range from 6 -13 m2/g.
Papers having a particularly good strength are obtained by the novel process.
The retention of fillers is improved compared with known processes.
Unless evident otherwise from the context, the stated percentages in the examples are always by weight. The molar masses of the polymers were determined by light scattering.
5 Examples Test methods:
- Sheet formation 10 Apparatus: Rapid-Kothen laboratory sheet former with accessories; testing according to DIN 54 358 Part 1 Production of laboratory sheets for physical tests = Rapid-Kothen method ISO 5269/2 - Ash retention: First Pass Ash Retention (FPAR) A dynamic drainage jar was brought to 900 rpm and then filled with 500 ml of stock suspension (8 g/l). After stirring for 10 seconds, x% of a polyacrylamide solution were added and stirring was effected for 20 seconds at 900 rpm and then reduced to 400 rpm. Thereafter, x%, based on stock, of the anionic flocculant component were added as dilute dispersion and stirring was effected for a further 15 seconds at 400 rpm. The dead volume of 25 ml was removed and discarded. 100 ml were collected in a volumetric flask and filtered with suction over a weighed Weissband filter. The filters were dried in a drying oven at 120°C, weighed, and ashed at 550°C. Depending on the filler composition, the filler content was calculated from the residue according to the following relationship (1-(filler in the filtrate/filler in the sample))x100 - Dry breaking length, wet breaking length:
Apparatus: BXC-FR2.5TN.D09-002 from Zwick/Roell - Structural strength Apparatus: BXZ2.5/TS1S-006 from Zwick-Roell Tests according to DIN ISO 3 781 Starting materials Cationic polymer A
Commercial cationic polyacrylamide having a molar mass of from 4 to 6 million and a solids content of 45% (Polymin~ KE 2020 from BASF Aktiengesellschaft) Silica Commercial colloidal silica having an average particle size of from 5 to 10 nm and a solids content of 10% by weight.
Bentonite Commercial swellable clay of the montmorillonite type having a solids content of 90%
and 10% of water (cf. US-A-4 306 781), obtainable under the trademark Mikrofloc~ XFB from BASF Aktiengeseilschaft Fixing agent A
Commercial polyvinylamine having a molecular weight MW of 250 000 and a solids content of 21 %, obtainable under the name Catiofast~ VFH from BASF
AktiengeseUschaft Anionic polymer A
Copolymer of acrylic acid and malefic acid having a molecular weight Mw of 70 000 and a solids content of 45%, obtainable under the name Sokalan~ CP45 from BASF
Aktiengesellschaft Nanohybrids A
Mixture of polymer 1 and silica in the weight ratio 1 : 1 Solvitose~ BPN
Cold-soluble starch having a solids content of 95%, obtainable from Avebe.
Preparation of polymers 1 to 4 Polymer 1 560 g of water and 633 g of a 15 percent strength by weight aqueous solution of aryl sulfonate were initially taken in a polymerization vessel, the solution was heated to 85°C and 50 g of a 7% strength aqueous sodium persulfate solution were then added.
The monomer mixture (feed 1 ) and the amount of initiator (feed 2) were then metered into the polymerization vessel via two separate feeds, beginning at the same time, in the course of 180 minutes, while maintaining the temperature.
Further microparticle systems which are used as an additive to the paper stock in papermaking are disclosed in EP-A-0 497 030 and EP-A-0 0635 602. US-A-6 083 discloses the preparation of an anionic nanocomposite which is used as a retention aid and drainage aid in papermaking. As is evident therefrom, waterglass is mixed with an anionic polyelectrolyte based on polysulfonates, polyacrylates or polyphosphates and either silica is added or the silica is produced in situ.
It is an object of the present invention to provide a further process for the production of paper, board and cardboard using a microparticle system.
We have found that this object is achieved, according to the invention, by a process for the production of paper, board and cardboard by adding ionic, water-insoluble, uncrosslinked, organic microparticles and at least one retention aid to a paper stock and draining the paper stock over a wire, if the organic microparticles used are water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight or water-insoluble, uncrosslinked, organic microparticles having an average particle size of less than 500 nm and a content of polymerized ionic monomers of not more than 10% by weight, which are obtainable by polymerizing the monomers in the presence of silica, waterglass, bentonite and/or mixtures thereof.
Said particle sizes are always the weight average particle sizes d50. Said particle size was determined by dynamic light scattering on a 0.01 % strength by weight dispersion at 23°C by means of an lic autosizer from Malvern Instruments, UK. The average particle size of the water-insoluble, uncrosslinked, organic polymers is preferably from 10 to 100 nm and the content of polymerized ionic monomers is from 0.1 to 0.95% by weight. Microparticles having average particle sizes of the water-insoluble, uncrosslinked, organic polymers of from 10 to 80 nm and a content of polymerized ionic monomers of from 0.2 to 0.7% by weight are particularly preferred. In general, the average particle size of the microparticles is in the range from 15 to 50 nm.
The microparticles comprising water-insoluble, uncrosslinked, organic polymers comprise either at least one anionic monomer or one cationic monomer incorporated in the form of polymerized units. Aqueous dispersions which comprise anionic microparticles are disclosed in EP-A-0 810 274, page 3, line 3 to page 15, line 59, disclosed in connection with the prior art. Suitable water-insoluble, uncrosslinked, organic polymers which carry an ionic charge are obtainable, for example, by free radical aqueous emulsion polymerization of a monomer mixture comprising (a) from 30 to 55 parts by weight of at least one monomer whose homopolymer has a glass transition temperature T9 of <20°C, (b) from 45 to 70 parts by weight of at least one monomer whose homopolymer has a glass transition temperature T9 of >50°C and (c) from 0.01 to less than 1 part by weight of a monomer having ionic groups, the sum of the parts by weight of (a) and (b) always being 100. The monomers having ionic groups can impart to the polymer either an anionic charge, if, for example, monoethylenically unsaturated monomers having acidic groups are used in the polymerization, or a cationic charge, if the polymerization is carried out in the presence of monoethylenically unsaturated, basic monomers. The glass transition temperature T9 is understood as meaning the limit of the glass transition temperature to which said glass transition temperature tends with increasing molecular weight, according to G. Kanig (cf. Kolloid-Zeitschrift & Zeitschrift fur Polymere, Volume 190, page 1, equation 1 ). It is determined by the DSC method (differential scanning calorimetry, K/min, midpoint). The T9 values for the homopolymers of most monomers are known, cf. for example Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim, 1992, Part 5, Vol. A21, page 169.
20 The monomer (a) is, for example, selected from at least one C,- to C,o-alkyl acrylate, C5- to C,o-alkyl methacrylate, CS- to C,o-cycloalkyl (meth)acrylate, C,- to C,o-dialkyl maleate and/or C,- to C,o-dialkyl fumarate. Typical monomers (b) are, for example, selected from at least one vinylaromatic monomer andlor one a,(3-unsaturated carbonitrile or carbodinitrile.
C,- to C~ alkyl groups are to be understood as meaning linear or branched alkyl radicals of 1 to n carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl and n-decyl. C5-to C,o-Cycloalkyl groups are, for example, cyclopentyl, cyclohexyl or cyclooctyl, which may optionally be substituted in each case by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms.
The water-insoluble, uncrosslinked, organic polymer is preferably composed of from 35 to 50 parts by weight of monomer units (a), from 50 to 65 parts by weight of monomer units (b) and from 0.01 to 0.95 part by weight of monomer units (c), the sum of the monomer units (a) and (b) always being 100.
Where it is an anionic monomer, the monomer (c) is, for example, selected from a,(3-unsaturated C3- to C6-carboxylic acids, a,(3-unsaturated C4- to CB-dicarboxylic acids, anhydrides thereof, monoethylenically unsaturated alkanesulfonic acids, monoethylenically unsaturated phosphonic acids and/or monoethylenically unsaturated arylsulfonic acids. The monomer (c) may be used in the polymerization if appropriate in a form partly or completely neutralized with alkali metal, alkaline earth metal andlor ammonium bases. Moreover, it is possible for polymers which comprise the monomers (c) incorporated by polymerization in the form of the free acid groups to be neutralized during or after the end of the polymerization. Suitable bases are, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, amines, such as trimethylamine, propylamine or butylamine, pyridine, piperidine, morpholine and alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine, calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide. Preferred monomers of group (c) are acrylic acid, methacrylic acid, crotonic acid, malefic acid, fumaric acid, malefic anhydride, itaconic acid, itaconic anhydride, vinylsulfonic acid, methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate and sulfopropyl (meth)acrylate.
Particularly preferred monomers of this group are acrylic acid, methacrylic acid and acrylamido-2-methylpropanesulfonic acid, mixtures of these monomers and alkali metal and ammonium salts thereof, in particular sodium salts thereof.
If the monomer (c) is a cationic monomer, this is to be understood as meaning, for example, the following monomers: diallyldimethylammonium chloride, di-C,-to Cz-alkylamino-C2- to C4-alkyl (meth)acrylates and di-C,- to CZ-alkylamino-CZ- to alkyl(meth)acrylamides. Said dialkylaminoalkyl (meth)acrylates and dialkylaminoalkyl(meth)acrylamides are preferably used in the form of salts with mineral acids or organic acids or in quaternized form. The quaternizing agent used is, for example, methyl chloride, ethyl chloride or dimethyl sulfate. Examples of preferably used cationic monomers are diallyldimethylammonium chloride and the following salts of sulfuric acid or hydrochloric acid or compounds quaternized with methyl chloride:
dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminoethylmethacrylamide and dimethylaminopropyl(meth)acrylamide. The polymers may also comprise, as cationic groups, vinylamine units in the form of salts with mineral acids or in quaternized form.
Polymers having such groups are obtained, for example, if the polymerization is carried out in the presence of vinylformamide as a comonomer, and the vinylformamide units present in the copolymer are then hydrolyzed with sulfuric acid to give vinylamine units.
Monomers of group (c) are present in an amount of less than 1 part by weight, based on 100 parts by weight of the sum of the monomers (a) and (b), in the monomer mixture which is subjected to the polymerization. Preferably, the monomer mixture comprises from 0.01 to 0.95, in particular from 0.2 to 0.7, part by weight, based on 100 parts by weight of the monomer (a) and (b), of at least one monomer (c).
In addition to said polymers of the components (a), (b) and (c), those microparticles of water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of up to 10% by weight which are obtainable by polymerizing the monomers on which these polymers are 5 based in the presence of silica, waterglass, bentonite andlor mixtures thereof are also suitable for papermaking. In the case of this type of microparticles, the content of monomers of group (c) is, for example, from 0.1 to 10, preferably from 1.5 to 7, in particular from 2 to 5, % by weight.
Examples of monomers (a) are vinyl ethers of C3- to C,o-alkanols, branched and straight-chain C3- to C,o-olefins, C,- to C,o-alkyl acrylates, CS- to C,o-alkyl methacrylates, CS- to C,o-cycloalkyl (meth)acrylates, C,- to C,o-dialkyl maleates and/or C,- to Coo-diallkyl fumarates. Particularly preferred monomers of this group are, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleate andlor di-n-butyl fumarate.
Examples of suitable monomers (b) are vinylaromatic monomers, such as styrene or a-methylstyrene, and styrene or a-methylstyrene substituted by 1, 2 or 3 C,- to C4-alkyl groups, chlorine andlor methoxy groups. Preferred monomers of group (b) have a glass transition temperature above 80°C. Examples of these are styrene, a-methylstyrene, o- or p-vinyltoluene, acrylonitrile, methacrylonit~ile, maleodinitrile, fumarodinitrile or mixtures thereof.
The copolymers may if appropriate comprise further monoethylenically unsaturated monomers, such as acrylamide, methacrylamide, N-vinylpyrrolidone and N-vinylcaprolactam, incorporated in the form of polymerized units. The amounts are, for example, from 0 to 10 parts by weight, based on 100 parts by weight of the monomers (a) and (b).
The polymerization of the monomers is effected by the known methods of emulsion polymerization in the presence of initiators which form free radicals under the polymerization conditions, such as peroxides, hydroperoxides, azo compounds or redox initiators, and in the presence of emulsifiers. Further information in this context can be obtained from the abovementioned EP-A-0 810 274, pages 4 and 5. The polymerization of the suitable monomers can, however, also be carried out in the presence of silica, waterglass, bentonite and/or mixtures thereof. Aqueous dispersions of ionic, water-insoluble, uncrosslinked, organic polymers having an average particle size below 500 nm are obtained. The polymerization can, however, also be effected by preparing an emulsion from water, the monomers, a hydrocarbon which is liquid at room temperature, such as hexane, pentane, isooctane, toluene and/or xylene, and at least one surfactant and polymerizing the monomers in the presence of free radical initiators.
Preferred polymers are those which comprise (a) at least one monomer from the group consisting of n-butylacrylate, isobutyl acrylate, n-propyl acrylate, isopropyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and methyl acrylate, (b) at least one monomer from the group consisting of styrene, a-methylstyrene, acrylonitrile and methacrylonitrile and (c) at least one monomer from the group consisting of acrylic acid, methacrylic acid, malefic acid and acrylamido-2-methylpropanesulfonic acid in the abovementioned amounts, incorporated in the form of polymerized units.
Copolymers which comprise, incorporated in the form of polymerized units n-butyl acrylate and styrene in the weight ratio of 1 : 1 and from 0.2 to 0.7% by weight of methacrylic acid or acrylic acid are particularly preferred.
The average molar mass MW of the polymers is, for example, from 500 000 to 5 million, preferably from 1 to 3 million.
The ionic, water-insoluble, uncrosslinked, organic microparticles described above are added together with at least one retention aid to the paper stock in papermaking. The organic microparticles promote the action of the retention aid. The organic microparticles are used, for example, in amounts of from 0.1 to 1, preferably in amounts of from 0.2 to 0.6, % by weight, based on dry paper stock. The amounts of retention aid are, for example, from 0.01 to 0.09, preferably from 0.02 to 0.04, % by weight, based on dry paper stock. Retention aids which may be used are all conventional polymers which are known for this purpose, for example polyacrylamides, cationic polyacrylamides, such as copolymers of acrylamide and dimethylaminoethyl acrylate which is quaternized with methyl chloride, polyvinylamines, polydiallyldimethylammonium chlorides, anionic polyacrylamides, such as copolymers of acrylamide and acrylic acid or copolymers of acrylamide and methacrylic acid, and also polydialkylaminoalkyl(meth)acrylamides, such as polydimethylaminoethyl-acrylamide and polydimethylaminoethylmethacrylamide, which in each case are used in protonated or in quaternized form, and polyethylene oxides, which if appropriate may be cationically andlor anionically modified. Furthermore, polyamidoamines which are grafted with ethylenimine and crosslinked with dichlorohydrin ethers of polyethylene glycols are suitable as retention aids. Further conventional retention aids are cationic starches. Such starches are prepared, for example, by reacting starch with cationizing agents, such as 3-chloro-2-hydroxypropyltrimethylammonium chloride. The degree of substitution of the cationic starch is, for example from 0.01 to 1, preferably from 0.02 to 0.5. Amphoteric starches may also be used as retention aids provided that they have an excess cationic charge. The retention aids are known to have a high molecular weight and thus differ substantially from fixing agents which are based on the same monomers. The molecular weight M", of the retention aids is, for example, at least 500 000, preferably >1 million, generally >2 million, in particular >5 million.
According to the novel process, all paper qualities can be produced, for example cardboard, single-ply/multiply cardboard for folding cartons, single-ply/multiply liners, corrugated material, newsprint, so-called medium-ply writing and printing papers, natural gravure printing paper and light-weight coating papers. In order to produce these papers, it is possible to start, for example, from groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood (PGIIIn, wood pulp and sulfite and sulfate pulp. The chemical pulps may be either short-fiber or long-fiber. According to the novel process, wood-free qualities, which give highly white paper products, are preferably produced.
The papers can if appropriate comprise up to 40, in general from 5 to 35, % by weight of fillers. Suitable fillers are, for example, titanium dioxide, natural and precipitated chalk, talc, kaolin, satin white, calcium sulfate, barium sulfate, clay and/or alumina.
Paper can also be produced in the presence of conventional process chemicals.
For example, at least one fixing agent, strength agent for paper and/or an engine size can also be added to the paper stock. Suitable fixing agents are, for example, polymers comprising vinylamine units, polydiallyldimethylammonium chloride, polyethylenimines, polyalkylenepolyamines and/or dicyandiamide polymers. The molecular weight MW
of the fixing agent is, for example, up to 300 000, in general in the range from 50 000 to 1 million.
According to the invention, water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight are metered together with at least one cationic, anionic, amphoteric or neutral synthetic organic polymer and/or cationic starch as a retention aid to the paper stock before the final shear stage upstream of the headbox.
In an embodiment of the novel process, water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight are metered together with at least one retention aid and a finely divided inorganic component to the paper stock after the final shear stage upstream of the headbox. However, it is also possible to use a procedure in which the retention aid is metered before the final shear stage upstream of the headbox and water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight, alone or together with the finely divided inorganic component, are metered after the final shear stage upstream of the headbox.
In addition, combinations of a polymeric organic retention aid and those water-insoluble, uncrosslinked, organic microparticles having an average particle size of less than 500 nm and a content of polymerized ionic monomers of not more than 10%
by weight which are obtainable by polymerizing the monomers in the presence of silica, waterglass, bentonite andlor mixtures thereof can be used in papermaking.
In a further embodiment of the novel process, water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1 % by weight are used together with polymers of monoethylenically unsaturated carboxylic acids, for example homopolymers of acrylic acid or methacrylic acid, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and malefic acid andlor copolymers of methacrylic acid and malefic acid. These polymers may if appropriate comprise further monomers, such as acrylamide and/or methacrylamide, incorporated in the form of polymerized units. The molecular weight MW of this group of polymers is, for example, from 2 000 to 200 000, preferably in the range from 5 000 to 110 000. These polymers result in an increase in the charge of the microparticles or preaggregation of the microparticles and hence improved retention in papermaking.
According to a further process variant, the water-insoluble, uncrosslinked, organic polymers having a content of polymerized ionic monomers of less than 1 % by weight are used together with inorganic microparticles from the group consisting of bentonite, colloidal silica, sheet silicates and/or finely divided calcium carbonate. The particle size of said inorganic substances is, for example, from 1 to 100 000 nm, preferably from 5 to 500 nm. These particle size data are based in each case on the inorganic substances dispersed in water. For example, from 0.01 to 10, preferably from 0.05 to 2, in particular from 0.1 to 1.2, parts by weight of at least one type of inorganic microparticles are used per part by weight of the organic microparticles. If organic microparticles containing up to not more than 10% by weight of monomers of group (c) are prepared by polymerizing the monomers in the presence of silica, waterglass andlor bentonite, corresponding amounts, based on the weight of the microparticles formed, of inorganic microparticles are used in the polymerization.
For example, bentonite, colloidal silica, silicates and/or calcium carbonate are suitable as the inorganic component of the microparticle system. Colloidal silica is to be understood as meaning those products which are based on silicates, e.g. silica microgel, silica sol, polysilicates, aluminum silicates, borosilicates, polyborosilicates, clay or zeolites. Calcium carbonate may be used, for example, in the form of chalk, ground calcium carbonate or precipitated calcium carbonate as the inorganic component of the microparticle system.. Bentonite is understood generally as meaning sheet silicates which are swellable in water. These are in particular the clay mineral montmorillonite and similar clay minerals, such as nontronite, hectorite, saponite, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite. These sheet silicates are preferably activated before they are used, .i.e. converted into a form better swellable in water by treating the sheet silicates with an aqueous base, such as aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate. Bentonite in the form treated with sodium hydroxide solution is preferably used as the inorganic component of the microparticle system. The platelet diameter of the bentonite dispersed in water, in the form treated with sodium hydroxide solution, is, for example, from 1 to 2 Nm, and the thickness of the platelets is about 1 nm. Depending on the type and activation, the bentonite has a specific surface area of from 60 to 800 m2/g. Typical bentonites are described, for example, in EP-B-0235893.
In the papermaking process, bentonite is added to the cellulose suspension typically in the form of an aqueous bentonite slurry. This bentonite slurry may comprise up to 10%
by weight of bentonite. Usually, the slurries comprise about 3 - 5% by weight of bentonite.
Products from the group consisting of silicon-based particles, silica microgels, silica sols, aluminum silicates, borosilicates, polyborosilicates or zeolites may be used as colloidal silica. These have a specific surface area of 50 -1 000 m2lg and an average particle size distribution of 1 - 250 nm, usually in the range 40 - 100 nm.
The preparation of such components is described, for example, in EP-A-0041056, EP-A-0185068 and US-A-5176891.
Clay or kaolin is a water-containing aluminum silicate having a lamellar structure. The crystals have a layer structure and an aspect ratio (ratio of diameter to thickness) of up to 30:1. The particle size is such that at least 50% of the particles are smaller than 2 mm.
Carbonates, preferably calcium carbonate, used may be natural calcium carbonate (ground calcium carbonate, GCC) or precipitated calcium carbonate (PCC). GCC
is prepared by milling and classification processes using milling assistants. It has a particle size such that 40 - 95% of the particles are smaller than 2 mm, and the specific surface area is in the range of 6 - 13 m2/g. PCC is prepared by passing carbon dioxide into calcium hydroxide solution. The average particle size is in the range of 0.03 0.6 mm, and the specific surface area can be greatly influenced by the choice of the precipitation conditions. It is in the range from 6 -13 m2/g.
Papers having a particularly good strength are obtained by the novel process.
The retention of fillers is improved compared with known processes.
Unless evident otherwise from the context, the stated percentages in the examples are always by weight. The molar masses of the polymers were determined by light scattering.
5 Examples Test methods:
- Sheet formation 10 Apparatus: Rapid-Kothen laboratory sheet former with accessories; testing according to DIN 54 358 Part 1 Production of laboratory sheets for physical tests = Rapid-Kothen method ISO 5269/2 - Ash retention: First Pass Ash Retention (FPAR) A dynamic drainage jar was brought to 900 rpm and then filled with 500 ml of stock suspension (8 g/l). After stirring for 10 seconds, x% of a polyacrylamide solution were added and stirring was effected for 20 seconds at 900 rpm and then reduced to 400 rpm. Thereafter, x%, based on stock, of the anionic flocculant component were added as dilute dispersion and stirring was effected for a further 15 seconds at 400 rpm. The dead volume of 25 ml was removed and discarded. 100 ml were collected in a volumetric flask and filtered with suction over a weighed Weissband filter. The filters were dried in a drying oven at 120°C, weighed, and ashed at 550°C. Depending on the filler composition, the filler content was calculated from the residue according to the following relationship (1-(filler in the filtrate/filler in the sample))x100 - Dry breaking length, wet breaking length:
Apparatus: BXC-FR2.5TN.D09-002 from Zwick/Roell - Structural strength Apparatus: BXZ2.5/TS1S-006 from Zwick-Roell Tests according to DIN ISO 3 781 Starting materials Cationic polymer A
Commercial cationic polyacrylamide having a molar mass of from 4 to 6 million and a solids content of 45% (Polymin~ KE 2020 from BASF Aktiengesellschaft) Silica Commercial colloidal silica having an average particle size of from 5 to 10 nm and a solids content of 10% by weight.
Bentonite Commercial swellable clay of the montmorillonite type having a solids content of 90%
and 10% of water (cf. US-A-4 306 781), obtainable under the trademark Mikrofloc~ XFB from BASF Aktiengeseilschaft Fixing agent A
Commercial polyvinylamine having a molecular weight MW of 250 000 and a solids content of 21 %, obtainable under the name Catiofast~ VFH from BASF
AktiengeseUschaft Anionic polymer A
Copolymer of acrylic acid and malefic acid having a molecular weight Mw of 70 000 and a solids content of 45%, obtainable under the name Sokalan~ CP45 from BASF
Aktiengesellschaft Nanohybrids A
Mixture of polymer 1 and silica in the weight ratio 1 : 1 Solvitose~ BPN
Cold-soluble starch having a solids content of 95%, obtainable from Avebe.
Preparation of polymers 1 to 4 Polymer 1 560 g of water and 633 g of a 15 percent strength by weight aqueous solution of aryl sulfonate were initially taken in a polymerization vessel, the solution was heated to 85°C and 50 g of a 7% strength aqueous sodium persulfate solution were then added.
The monomer mixture (feed 1 ) and the amount of initiator (feed 2) were then metered into the polymerization vessel via two separate feeds, beginning at the same time, in the course of 180 minutes, while maintaining the temperature.
After the end of the feeds, the 85°C were maintained for a further 30 minutes, and the reaction mixture was then cooled to room temperature. A pH of 4 was established with 3% strength aqueous sodium hydroxide solution.
Feed 1:
245 g Styrene 250 g n-Butyl acrylate 3 g Methacrylic acid Feed 2:
1.5 g Sodium persulfate 20 g Demineralized water The solids content of the dispersion was about 33%. The copolymer comprised 0.6% of methacrylic acid incorporated in the form of polymerized units. The light transmittance of a 0.01 % strength solution was 99%. The weight average particle size d50 was 61 nm. The pH of the dispersoin was 4.0 and the glass transition temperature T9 of the polymer was 23°C.
Polymer 2 800 g of a 2.5% strength Zeofloc~ solution (J.M. Huber Corporation) and 253 g of a 15% strength aqueous solution of aryl sulfonate were initially taken in a polymerization vessel, the solution was heated to 85°C and 20 g of a 7% strength aqueous sodium persulfate solution were then added.
Thereafter, the monomer emulsion (feed 1 ) was added to the polymerization vessel in the course of 180 minutes and the initiator solution (feed 2) in the course of 195 minutes, via two separate feeds, beginning at the same time, while maintaining the temperature.
After the end of the feed, the 85°C were maintained for a further 30 minutes, and the reaction mixture was then cooled to room temperature and filtered over a filter having a mesh size of 45 Nm. The pH was then brought to 4.0 by adding 3% strength aqueous sodium hydroxide.
Feed 1:
100 g n-Butyl acrylate 98 g Styrene 1.9 g Methacrylic acid Feed 2:
1.0 g Sodium persulfate 26 g Demineralized water The solids content of the dispersion was about 16%. The copolymer comprised 0.95%
of methacrylic acid incorporated in the form of polymerized units. The weight average particle size d50 was 76 nm. The pH of the dispersion was 4.0 and the glass transition temperature T9 of the polymer was 31 °C.
Polymer 3 300 g of water, 507 g of a 15% strength aqueous solution of aryl sulfonate, 12 g of methacrylic acid and 800 g of a 5% strength aqueous soda waterglass solution having a pH of 11.2 were initially taken in a polymerization vessel, the solution was heated to 85°C and 40 g of a 7% strength aqueous sodium persulfate solution were added.
Thereafter, the monomer mixture (feed 1) was added to the polymerization vessel in the course of 180 minutes and the initiator solution (feed 2) in the course of 210 minutes, via two separate feeds, beginning at the same time, while maintaining the temperature.
After the end of the feeds, the 85°C was maintained for a further 30 minutes and the dispersion formed was then cooled to room temperature and filtered over a filter having a mesh size of 400 Nm. The pH was then brought to 6.7 by adding 3% strength aqueous sodium hydroxide.
Feed 1:
176 g Styrene 200 g n-Butyl acrylate 12 g Methacrylic acid Feed 2:
40 g ~ Sodium persulfate solution (7% strength, aqueous) The solids content of the dispersion was about 25%. The copolymer comprised 3%
of methacrylic acid incorporated in the form of polymerized units. The weight average particle size d50 was 68 nm. The pH of the dispersion was 6.7. The glass transition temperature Tg of the polymer was 21 °C. The dispersion was divided. A
3% strength aqueous sodium hydroxide was then added to one part of the dispersion in an amount sufficient to bring the pH to 10.5. An aqueous dispersion having a solids content of about 23.5% was obtained.
Feed 1:
245 g Styrene 250 g n-Butyl acrylate 3 g Methacrylic acid Feed 2:
1.5 g Sodium persulfate 20 g Demineralized water The solids content of the dispersion was about 33%. The copolymer comprised 0.6% of methacrylic acid incorporated in the form of polymerized units. The light transmittance of a 0.01 % strength solution was 99%. The weight average particle size d50 was 61 nm. The pH of the dispersoin was 4.0 and the glass transition temperature T9 of the polymer was 23°C.
Polymer 2 800 g of a 2.5% strength Zeofloc~ solution (J.M. Huber Corporation) and 253 g of a 15% strength aqueous solution of aryl sulfonate were initially taken in a polymerization vessel, the solution was heated to 85°C and 20 g of a 7% strength aqueous sodium persulfate solution were then added.
Thereafter, the monomer emulsion (feed 1 ) was added to the polymerization vessel in the course of 180 minutes and the initiator solution (feed 2) in the course of 195 minutes, via two separate feeds, beginning at the same time, while maintaining the temperature.
After the end of the feed, the 85°C were maintained for a further 30 minutes, and the reaction mixture was then cooled to room temperature and filtered over a filter having a mesh size of 45 Nm. The pH was then brought to 4.0 by adding 3% strength aqueous sodium hydroxide.
Feed 1:
100 g n-Butyl acrylate 98 g Styrene 1.9 g Methacrylic acid Feed 2:
1.0 g Sodium persulfate 26 g Demineralized water The solids content of the dispersion was about 16%. The copolymer comprised 0.95%
of methacrylic acid incorporated in the form of polymerized units. The weight average particle size d50 was 76 nm. The pH of the dispersion was 4.0 and the glass transition temperature T9 of the polymer was 31 °C.
Polymer 3 300 g of water, 507 g of a 15% strength aqueous solution of aryl sulfonate, 12 g of methacrylic acid and 800 g of a 5% strength aqueous soda waterglass solution having a pH of 11.2 were initially taken in a polymerization vessel, the solution was heated to 85°C and 40 g of a 7% strength aqueous sodium persulfate solution were added.
Thereafter, the monomer mixture (feed 1) was added to the polymerization vessel in the course of 180 minutes and the initiator solution (feed 2) in the course of 210 minutes, via two separate feeds, beginning at the same time, while maintaining the temperature.
After the end of the feeds, the 85°C was maintained for a further 30 minutes and the dispersion formed was then cooled to room temperature and filtered over a filter having a mesh size of 400 Nm. The pH was then brought to 6.7 by adding 3% strength aqueous sodium hydroxide.
Feed 1:
176 g Styrene 200 g n-Butyl acrylate 12 g Methacrylic acid Feed 2:
40 g ~ Sodium persulfate solution (7% strength, aqueous) The solids content of the dispersion was about 25%. The copolymer comprised 3%
of methacrylic acid incorporated in the form of polymerized units. The weight average particle size d50 was 68 nm. The pH of the dispersion was 6.7. The glass transition temperature Tg of the polymer was 21 °C. The dispersion was divided. A
3% strength aqueous sodium hydroxide was then added to one part of the dispersion in an amount sufficient to bring the pH to 10.5. An aqueous dispersion having a solids content of about 23.5% was obtained.
Polymer 4 The other part of the aqueous dispersion of polymer 3, having a pH of 6.7, was brought to a pH of 10.5 by adding 5% strength aqueous soda waterglass solution. The solids content of the dispersion thus obtainable was 19.7%.
Examples 1 to 6, comparative examples 1 to 4 The efficiency of the polymers described above as retention aids was first tested on a stock model comprising a 70130 pine sulfate/birch sulfate mixture with 70%
Schopper Riegler 33 and 30% Schopper Riegler 70, 30% of Hydrocarb OG (based on pulp) and 0.6% of Solvitose~ BPN (based on pulp) by the abovementioned test method. The pulp had in each case a consistency of 8 gll and the pH of the pulp was 6.7. The type and amount of the starting material and the results are stated in tables 1 to 4.
Table 1 Examples Amount* Polymer Amount* MicroparticlesFPAR [%]
Comparison0.4 Cationic 1 Silica 68 1 polymer A
Example 0.4 Cationic 1 Polymer 1 73 polymer A
* Amount added, kg of commercial product/t of paper Table 2 Examples Amount* Polymer Amount* MicroparticlesFPAR
[%]
Comparison0.4 Cationic 4 Bentonite 87 2 polymer A
Example 0.4 Cationic 4 Polymer 1 89 polymer A
Example 0.4 Cationic 4 Nanohybrid 90 polymer A
* Amount added, kg of commercial productlt of paper Table 3 Examples Amount*Polymer Amount* MicroparticlesFPAR [%]
Comparison 0.4 Cationic 4 Bentonite 88 3 polymer A
Example 0.4 Cationic 2 Polymer 2 91 polymer A
* Amount added, kg of commercial productlt of paper 5 Table 4 Examples Amount* Polymer Amount* MicroparticlesFPAR
[%]
Comparison0.4 Cationic 3 Bentonite 90 4 polymer A
Example 0.4 Cationic 3 Polymer 3 94 polymer A
Example 0.4 Cationic 3 Polymer 4 96 polymer A
* Amount added, kg of commercial product/t of paper Example 7 and comparative example 5 The stock model used was a wood-free paper stock having a consistency of 8 gll and a pH of 6.7. 0.1 %, based on dry paper stock, of fixing agent A (commercial product) was metered, the pulp was thoroughly mixed, the amounts of cationic polymer A and microparticles stated in table 5 were then added, thorough mixing of the components was ensured and the pulp was drained as described above. The results are shown in table 5.
Example 8 Example 7 was repeated, except that the use of fixing agent A was dispensed with.
The results are shown in table 5.
Table 5:
FPAR
Examples Amount*Polymer Amount*Microparticles [%1 Comparison 0.4 Cationic polymer3 Bentonite 88 A
Example 0.4 Cationic polymer3 Polymer 1 100 Example 0.4 Cationic polymer3 Polymer 1** 77 * Amount added, kg of commerc~a~ proaucvt of paper ** Without addition of fixing agent 5 Example 9 and comparative example 6 The stock model used was a wood-free paper stock having a consistency of 8 gll and a pH of 6.7. 1 %, based on the amount of microparticles used, of anionic polymer A was added, the pulp was thoroughly mixed, the amounts of cationic polymer A and microparticles stated in table 6 were then added, thorough mixing of the components was ensured and the pulp was drained as described above. The results are shown in table 6.
Example 10 and comparative example 7 Example 9 was repeated, except that the use of anionic polymer A was dispensed with.
The results are shown in table 6.
Table 6 FPAR
Examples Amount* Polymer Amount* Microparticles [%]
Comparison 0.4 Cationic polymer4 Bentonite 79 Comparison 0.4 Cationic polymer4 Bentonite**83 Example 0.4 Cationic polymer4 Polymer 89 Example 0.4 Cationic polymer4 Polymer 83 10 A 1 **
* Amount added, kg of commercial product/t of paper ** Without addition of Sokalan CP 45 Testing of the performance characteristics 500 ml of the stock suspension described above (consistency 8 g/l) were initially taken in a stirred vessel equipped with a propeller stirrer and was stirred at a speed of 900 revolutions per minute (rpm). After 10 seconds, a polyacrylamide solution (retention agent) was added, as in the testing of the ash retention, and stirring was effected for 20 seconds at 900 rpm and then at 400 rpm. Thereafter, the products stated in table 7 (bentonite and polymer 1 ) were metered in an amount of in each case 2 kg of commercial product per t of paper. Thereafter, the mixture was introduced into a Rapid-Kothen sheet former, and sheets having a basis weight of 80 glmz were produced. Dry and wet breaking length and the structural strength of the sheets were then determined by the methods described above. The results are shown in table 7.
Table 7 Paper test Bentonite Polymer 1 Dry breaking length [m] 3 442 4 298 Wet breaking length [m] 205 299 Structural strength [F max in 366 430 N, z direction]
Example 11 Example 1 was repeated, except that 0.4 kg of commercial product of cationic polymer A per t of paper and 2 kg of polymer 1 per t of paper were used. The ash retention (FPAR) was 89%.
Comparative example 8 Example 1 was repeated, except that 0.4 kg of commercial product of cationic polymer A per t of paper and 2 kg of an anionically emulsified styrene latex having a particle size of 30 nm and a solids content of 33% were used. The ash retention (FPAR) was 81 %.
Examples 1 to 6, comparative examples 1 to 4 The efficiency of the polymers described above as retention aids was first tested on a stock model comprising a 70130 pine sulfate/birch sulfate mixture with 70%
Schopper Riegler 33 and 30% Schopper Riegler 70, 30% of Hydrocarb OG (based on pulp) and 0.6% of Solvitose~ BPN (based on pulp) by the abovementioned test method. The pulp had in each case a consistency of 8 gll and the pH of the pulp was 6.7. The type and amount of the starting material and the results are stated in tables 1 to 4.
Table 1 Examples Amount* Polymer Amount* MicroparticlesFPAR [%]
Comparison0.4 Cationic 1 Silica 68 1 polymer A
Example 0.4 Cationic 1 Polymer 1 73 polymer A
* Amount added, kg of commercial product/t of paper Table 2 Examples Amount* Polymer Amount* MicroparticlesFPAR
[%]
Comparison0.4 Cationic 4 Bentonite 87 2 polymer A
Example 0.4 Cationic 4 Polymer 1 89 polymer A
Example 0.4 Cationic 4 Nanohybrid 90 polymer A
* Amount added, kg of commercial productlt of paper Table 3 Examples Amount*Polymer Amount* MicroparticlesFPAR [%]
Comparison 0.4 Cationic 4 Bentonite 88 3 polymer A
Example 0.4 Cationic 2 Polymer 2 91 polymer A
* Amount added, kg of commercial productlt of paper 5 Table 4 Examples Amount* Polymer Amount* MicroparticlesFPAR
[%]
Comparison0.4 Cationic 3 Bentonite 90 4 polymer A
Example 0.4 Cationic 3 Polymer 3 94 polymer A
Example 0.4 Cationic 3 Polymer 4 96 polymer A
* Amount added, kg of commercial product/t of paper Example 7 and comparative example 5 The stock model used was a wood-free paper stock having a consistency of 8 gll and a pH of 6.7. 0.1 %, based on dry paper stock, of fixing agent A (commercial product) was metered, the pulp was thoroughly mixed, the amounts of cationic polymer A and microparticles stated in table 5 were then added, thorough mixing of the components was ensured and the pulp was drained as described above. The results are shown in table 5.
Example 8 Example 7 was repeated, except that the use of fixing agent A was dispensed with.
The results are shown in table 5.
Table 5:
FPAR
Examples Amount*Polymer Amount*Microparticles [%1 Comparison 0.4 Cationic polymer3 Bentonite 88 A
Example 0.4 Cationic polymer3 Polymer 1 100 Example 0.4 Cationic polymer3 Polymer 1** 77 * Amount added, kg of commerc~a~ proaucvt of paper ** Without addition of fixing agent 5 Example 9 and comparative example 6 The stock model used was a wood-free paper stock having a consistency of 8 gll and a pH of 6.7. 1 %, based on the amount of microparticles used, of anionic polymer A was added, the pulp was thoroughly mixed, the amounts of cationic polymer A and microparticles stated in table 6 were then added, thorough mixing of the components was ensured and the pulp was drained as described above. The results are shown in table 6.
Example 10 and comparative example 7 Example 9 was repeated, except that the use of anionic polymer A was dispensed with.
The results are shown in table 6.
Table 6 FPAR
Examples Amount* Polymer Amount* Microparticles [%]
Comparison 0.4 Cationic polymer4 Bentonite 79 Comparison 0.4 Cationic polymer4 Bentonite**83 Example 0.4 Cationic polymer4 Polymer 89 Example 0.4 Cationic polymer4 Polymer 83 10 A 1 **
* Amount added, kg of commercial product/t of paper ** Without addition of Sokalan CP 45 Testing of the performance characteristics 500 ml of the stock suspension described above (consistency 8 g/l) were initially taken in a stirred vessel equipped with a propeller stirrer and was stirred at a speed of 900 revolutions per minute (rpm). After 10 seconds, a polyacrylamide solution (retention agent) was added, as in the testing of the ash retention, and stirring was effected for 20 seconds at 900 rpm and then at 400 rpm. Thereafter, the products stated in table 7 (bentonite and polymer 1 ) were metered in an amount of in each case 2 kg of commercial product per t of paper. Thereafter, the mixture was introduced into a Rapid-Kothen sheet former, and sheets having a basis weight of 80 glmz were produced. Dry and wet breaking length and the structural strength of the sheets were then determined by the methods described above. The results are shown in table 7.
Table 7 Paper test Bentonite Polymer 1 Dry breaking length [m] 3 442 4 298 Wet breaking length [m] 205 299 Structural strength [F max in 366 430 N, z direction]
Example 11 Example 1 was repeated, except that 0.4 kg of commercial product of cationic polymer A per t of paper and 2 kg of polymer 1 per t of paper were used. The ash retention (FPAR) was 89%.
Comparative example 8 Example 1 was repeated, except that 0.4 kg of commercial product of cationic polymer A per t of paper and 2 kg of an anionically emulsified styrene latex having a particle size of 30 nm and a solids content of 33% were used. The ash retention (FPAR) was 81 %.
Claims (16)
1. A process for the production of paper, board and cardboard by adding ionic, water-insoluble, uncrosslinked, organic microparticles and at least one retention aid to a paper stock and draining the paper stock over a wire, wherein the organic microparticles used are water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1% by weight of water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of not more than 10% by weight, which are obtainable by polymerizing the monomers in the presence of silica, waterglass, bentonite and/or mixtures thereof.
2. The process according to claim 1, wherein the average particle size of the water-insoluble, uncrosslinked, organic polymers is from 10 to 100 nm and the content of polymerized ionic monomers is from 0.1 to 0.95% by weight.
3. The process according to claim 1 or 2, wherein the average particle size of the water-insoluble, uncrosslinked, organic polymers is from 10 to 80 nm and the content of polymerized ionic monomers is from 0.2 to 0.7% by weight.
4. The process according to any of claims 1 to 3, wherein the average particle size of the water-insoluble, uncrosslinked, organic polymers is from 15 to 50 nm.
5. The process according to any of claims 1 to 4, wherein the water-insoluble, uncrosslinked, organic polymers comprise at least one anionic monomer incorporated in the form of polymerized units.
6. The process according to any of claims 1 to 4, wherein the water-insoluble, uncrosslinked, organic polymers comprise at least one cationic monomer incorporated in the form of polymerized units.
7. The process according to any of claims 1 to 6, wherein water-insoluble, uncrosslinked, organic polymers which are obtainable by free radical aqueous emulsion polymerization of a monomer mixture comprising (a) from 30 to 55 parts by weight of at least one monomer whose homopolymer has a glass transition temperature T g of < 20°C, (b) from 45 to 70 parts by weight of at least one monomer whose homopolymer has a glass transition temperature T g of > 50°C and (c) from 0.01 to less than 1 part by weight of a monomer having ionic groups, the sum of the parts by weight of (a) and (b) always being 100, are used.
8. The process according to claim 7, wherein the monomer (a) is selected from at least one C1- to C10-alkyl acrylate, C5- to C10-alkyl methacrylate, C5- to C10-cycloalkyl (meth)acrylate, C1- to C10-dialkyl maleate and/or C1- to C10-dialkyl fumarate, and the monomer (b) is selected from at least one vinylaromatic monomer and/or one a,.beta.-unsaturated carbonitrile or carbodinitrile.
9. The process according to claim 7 or 8, wherein the monomer (c) is selected from a,.beta.-unsaturated C3- to C6-carboxylic acids, a,.beta.-unsaturated C4- to C8-dicarboxylic acids, anhydrides thereof, monoethylenically unsaturated alkanesulfonic acids, monoethylenically unsaturated phosphonic acids and/or monoethylenically unsaturated arylsulfonic acids.
10. The process according to claim 9, wherein the monomer (c) is used in the polymerization in the form partly or completely neutralized with alkali metal, alkaline earth metal and/or ammonium bases.
11. The process according to any of claims 7 to 10, wherein the water-insoluble, uncrosslinked, organic polymers are composed of from 35 to 50 parts by weight of monomer units (a), from 50 to 65 parts by weight of monomer units (b) and from 0.01 to 0.95 part by weight of monomer units (c), the sum of the monomer units (a) and (b) always being 100.
12. The process according to any of claims 7 to 11, wherein the water-insoluble, uncrosslinked, organic polymers are obtainable by polymerizing the monomers in the presence of silica, waterglass, bentonite and/or mixtures thereof.
13. The process according to any of claims 1 to 12, wherein at least one fixing agent, strength agent for paper and/or an engine size are also added to the paper stock.
14. The process according to claim 13, wherein the fixing agent used is a polymer comprising vinylamine units, polydiallyldimethylammonium chloride, polyethylenimine, polyalkylenepolyamine and/or dicyandiamide polymer.
15. The process according to any of claims 1 to 14, wherein water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1% by weight are metered together with at least one cationic, anionic, amphoteric or neutral synthetic organic polymer and/or cationic starch as a retention aid to the paper stock before the final shear stage upstream of the headbox.
16. The process according to any of claims 1 to 14, wherein water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1% by weight are metered together with at least one retention aid and one finely divided inorganic component to the paper stock after the final shear stage upstream of the headbox, or wherein the retention aid is metered before the final shear stage upstream of the headbox and water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a content of polymerized ionic monomers of less than 1% by weight are metered alone or together with the finely divided inorganic component after the final shear stage upstream of the headbox.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10346750A DE10346750A1 (en) | 2003-10-06 | 2003-10-06 | Process for the production of paper, cardboard and cardboard |
DE10346750.5 | 2003-10-06 | ||
PCT/EP2004/011023 WO2005035872A1 (en) | 2003-10-06 | 2004-10-02 | Method for producing paper, paperboard and cardboard |
Publications (1)
Publication Number | Publication Date |
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CA2540117A1 true CA2540117A1 (en) | 2005-04-21 |
Family
ID=34353346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002540117A Abandoned CA2540117A1 (en) | 2003-10-06 | 2004-10-02 | Method for producing paper, paperboard and cardboard |
Country Status (7)
Country | Link |
---|---|
US (1) | US20070119560A1 (en) |
EP (1) | EP1673506A1 (en) |
CN (1) | CN1863967A (en) |
BR (1) | BRPI0414844A (en) |
CA (1) | CA2540117A1 (en) |
DE (1) | DE10346750A1 (en) |
WO (1) | WO2005035872A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109594413A (en) * | 2018-11-26 | 2019-04-09 | 苏州恒康新材料有限公司 | It is a kind of for improving the paper making additive of paper tensile strength |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2869626A3 (en) * | 2004-04-29 | 2005-11-04 | Snf Sas Soc Par Actions Simpli | METHOD FOR MANUFACTURING PAPER AND CARDBOARD, NEW CORRESPONDING RETENTION AND DRAINING AGENTS, AND PAPERS AND CARTONS THUS OBTAINED |
DE102004038132B3 (en) * | 2004-08-05 | 2006-04-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Paper product with increased relative wet tensile strength and softness, process for its preparation and its use |
US8039550B2 (en) | 2005-05-20 | 2011-10-18 | Akzo Nobel N.V. | Process for preparing a polymer dispersion and a polymer dispersion |
WO2008052970A1 (en) * | 2006-10-31 | 2008-05-08 | Basf Se | Method for producing a multi layer fiber web from cellulose fibers |
US7854110B2 (en) * | 2006-11-16 | 2010-12-21 | Siemens Energy, Inc. | Integrated fuel gas characterization system |
BRPI0719375A2 (en) * | 2006-11-23 | 2014-02-11 | Tno | USE OF A COMBINATION OF A CARBOXYLATE POLYSACARIDE AND A CATIONIC POLYMER, COMBINATION, AND PAPER, TOWEL, TISSUE OR PAPER PRODUCT |
CA2728278C (en) | 2008-06-20 | 2016-06-28 | Zheng Tan | Composition and recording sheet with improved optical properties |
JP5961619B2 (en) | 2010-10-29 | 2016-08-02 | バックマン・ラボラトリーズ・インターナショナル・インコーポレーテッドBuckman Laboratories International Incorporated | Method for producing paper using ionic crosslinked polymer fine particles and product produced by the method |
WO2013089638A1 (en) * | 2011-12-15 | 2013-06-20 | Innventia Ab | System and process for improving paper and paper board |
MX2016000879A (en) * | 2013-08-09 | 2016-05-05 | Solenis Technologies Lp | Polyethylene oxide treatment for drainage agents and dry strength agents. |
CN112726275A (en) * | 2020-12-25 | 2021-04-30 | 玖龙纸业(东莞)有限公司 | Papermaking retention aid and application thereof |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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SE432951B (en) * | 1980-05-28 | 1984-04-30 | Eka Ab | PAPER PRODUCT CONTAINING CELLULOSA FIBERS AND A BINDING SYSTEM CONTAINING COLOIDAL MILIC ACID AND COTIONIC STARCH AND PROCEDURE FOR PREPARING THE PAPER PRODUCT |
US4968435A (en) * | 1988-12-19 | 1990-11-06 | American Cyanamid Company | Cross-linked cationic polymeric microparticles |
EP0484617B2 (en) * | 1990-06-11 | 2001-12-12 | Ciba Specialty Chemicals Water Treatments Limited | Cross-linked anionic and amphoteric polymeric microparticles |
US5274055A (en) * | 1990-06-11 | 1993-12-28 | American Cyanamid Company | Charged organic polymer microbeads in paper-making process |
US5167766A (en) * | 1990-06-18 | 1992-12-01 | American Cyanamid Company | Charged organic polymer microbeads in paper making process |
US5431783A (en) * | 1993-07-19 | 1995-07-11 | Cytec Technology Corp. | Compositions and methods for improving performance during separation of solids from liquid particulate dispersions |
GB9410920D0 (en) * | 1994-06-01 | 1994-07-20 | Allied Colloids Ltd | Manufacture of paper |
US6238521B1 (en) * | 1996-05-01 | 2001-05-29 | Nalco Chemical Company | Use of diallyldimethylammonium chloride acrylamide dispersion copolymer in a papermaking process |
US6083997A (en) * | 1998-07-28 | 2000-07-04 | Nalco Chemical Company | Preparation of anionic nanocomposites and their use as retention and drainage aids in papermaking |
MY140287A (en) * | 2000-10-16 | 2009-12-31 | Ciba Spec Chem Water Treat Ltd | Manufacture of paper and paperboard |
US20030136534A1 (en) * | 2001-12-21 | 2003-07-24 | Hans Johansson-Vestin | Aqueous silica-containing composition |
-
2003
- 2003-10-06 DE DE10346750A patent/DE10346750A1/en not_active Withdrawn
-
2004
- 2004-10-02 BR BRPI0414844-4A patent/BRPI0414844A/en not_active IP Right Cessation
- 2004-10-02 EP EP04765774A patent/EP1673506A1/en not_active Withdrawn
- 2004-10-02 WO PCT/EP2004/011023 patent/WO2005035872A1/en active Application Filing
- 2004-10-02 US US10/574,344 patent/US20070119560A1/en not_active Abandoned
- 2004-10-02 CA CA002540117A patent/CA2540117A1/en not_active Abandoned
- 2004-10-02 CN CNA2004800293134A patent/CN1863967A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109594413A (en) * | 2018-11-26 | 2019-04-09 | 苏州恒康新材料有限公司 | It is a kind of for improving the paper making additive of paper tensile strength |
Also Published As
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EP1673506A1 (en) | 2006-06-28 |
WO2005035872A1 (en) | 2005-04-21 |
BRPI0414844A (en) | 2006-11-21 |
CN1863967A (en) | 2006-11-15 |
DE10346750A1 (en) | 2005-04-21 |
US20070119560A1 (en) | 2007-05-31 |
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