EP3332063A1 - Method for producing paper - Google Patents
Method for producing paperInfo
- Publication number
- EP3332063A1 EP3332063A1 EP16750742.5A EP16750742A EP3332063A1 EP 3332063 A1 EP3332063 A1 EP 3332063A1 EP 16750742 A EP16750742 A EP 16750742A EP 3332063 A1 EP3332063 A1 EP 3332063A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- units
- water
- acid
- monomer
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 239000000123 paper Substances 0.000 claims abstract description 84
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000011859 microparticle Substances 0.000 claims abstract description 47
- 239000000945 filler Substances 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical group 0.000 claims abstract description 28
- 125000000129 anionic group Chemical group 0.000 claims abstract description 26
- 125000002091 cationic group Chemical group 0.000 claims abstract description 18
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000011087 paperboard Substances 0.000 claims abstract description 3
- 239000011111 cardboard Substances 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims description 79
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 46
- -1 alkali metal salts Chemical class 0.000 claims description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 25
- 239000000440 bentonite Substances 0.000 claims description 21
- 229910000278 bentonite Inorganic materials 0.000 claims description 21
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 230000007062 hydrolysis Effects 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000001409 amidines Chemical group 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 11
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000007900 aqueous suspension Substances 0.000 abstract description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 239000007787 solid Substances 0.000 description 24
- 235000012216 bentonite Nutrition 0.000 description 21
- 229940092782 bentonite Drugs 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 150000003009 phosphonic acids Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000008107 starch Substances 0.000 description 7
- 235000019698 starch Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001412 amines Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010893 paper waste Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052615 phyllosilicate Inorganic materials 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 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
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 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
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler 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
- 239000004571 lime Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- SHIGCAOWAAOWIG-UHFFFAOYSA-N n-prop-2-enylformamide Chemical compound C=CCNC=O SHIGCAOWAAOWIG-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- ZICNIEOYWVIEQJ-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1C ZICNIEOYWVIEQJ-UHFFFAOYSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- REWARORKCPYWIH-UHFFFAOYSA-N 1-(prop-2-enoylamino)butan-2-ylphosphonic acid Chemical compound CCC(P(O)(O)=O)CNC(=O)C=C REWARORKCPYWIH-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- NEWDOBPJIKOWPV-UHFFFAOYSA-N 1-ethenyl-3-oxidoimidazol-3-ium Chemical compound [O-][N+]=1C=CN(C=C)C=1 NEWDOBPJIKOWPV-UHFFFAOYSA-N 0.000 description 1
- DJABNVJZYFGAJE-UHFFFAOYSA-N 1-ethenyl-5-ethylpyrrolidin-2-one Chemical compound CCC1CCC(=O)N1C=C DJABNVJZYFGAJE-UHFFFAOYSA-N 0.000 description 1
- HQGPZXPTJWUDQR-UHFFFAOYSA-N 1-ethenyl-5-methylpyrrolidin-2-one Chemical compound CC1CCC(=O)N1C=C HQGPZXPTJWUDQR-UHFFFAOYSA-N 0.000 description 1
- GIQLJJKZKUIRIU-UHFFFAOYSA-N 1-ethenyl-6-ethylpiperidin-2-one Chemical compound CCC1CCCC(=O)N1C=C GIQLJJKZKUIRIU-UHFFFAOYSA-N 0.000 description 1
- FFDNCQYZAAVSSF-UHFFFAOYSA-N 1-ethenyl-6-methylpiperidin-2-one Chemical compound CC1CCCC(=O)N1C=C FFDNCQYZAAVSSF-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
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
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- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- DQJSKCFIYCTPBV-UHFFFAOYSA-N propan-2-yl n-(propan-2-yloxycarbonylamino)peroxycarbamate Chemical compound CC(C)OC(=O)NOONC(=O)OC(C)C DQJSKCFIYCTPBV-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical class [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
-
- 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
-
- 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
- D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
- D21H17/40—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups unsaturated
-
- 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
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
-
- 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
- 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
- D21H21/20—Wet strength 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
- 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
- D21H23/22—Addition to the formed paper
- D21H23/24—Addition to the formed paper during paper manufacture
- D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
- D21H23/28—Addition before the dryer section, e.g. at the wet end or press section
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J1/00—Fibreboard
Definitions
- the invention relates to a process for producing paper and board comprising the addition of this aqueous slurry to a pulp, dewatering of the resulting pulp and subsequent pressing of the paper sheet and drying.
- the production of paper is a process in which a solid phase consisting of cellulose or wood fiber and various inorganic additives is separated from an aqueous phase.
- the initial concentration of the solid phase in the pulp suspension (thin material) is typically in a range between 15 g / l and 1, 5 g / l.
- the separation of solid phase and aqueous phase takes place in several stages and can be modulated within these stages by the choice of mechanical parameters or the targeted addition of chemical additives.
- the dewatering of the paper stock takes place by spraying onto a sieve or by injection between two sieves, which are referred to as Untersieb or Obersieb depending on the relative position to the injected pulp.
- the water is separated from the pulp solely by gravity or by a combination of gravity and centrifugal forces and drains through the openings of the sieves.
- EP-A-950138 teaches the two-stage treatment of paper stock with a cationic polymer and microparticles and after shear in the second stage with a crosslinked anionic polymer.
- WO-A-04/087818, WO-A-05/012637 and WO-A-2006/066769 describe aqueous slurries of finely divided fillers which have been treated with water-soluble amphoteric copolymers based on polyvinylamine. These slurries allow an increase in the filler content in papers while preserving the paper properties, in particular the dry strength.
- the dry content reached in the wire section in addition to the mechanical requirements of the wire section and the choice of chemical additives, depends very much on the pulp system and the basis weight of the paper web. Even if primarily efficient dewatering of the pulp is a goal, good final properties of the paper should continue to be achieved become. Too rapid dewatering can lead to a premature immobilization of the paper fibers and thus lead to poor strength properties or poor optical properties.
- the wet strength and the initial wet strength of paper are to be distinguished from the initial wet texture strength because both properties are measured on papers which are moistened again to a defined water content after drying.
- Initial wet web strength refers to the strength of a wet paper that has never been dried. This is the strength of a wet paper, as is the case in papermaking after passing through the wire and press section of the paper machine. It typically contains about 50% water. An increase in the initial wet structural strength allows the use of higher take-off forces and thus a faster operation of the paper machine (see EP-A-0 780 513) or the use of larger amounts of filler.
- WO 2009/156274 teaches the use of amphoteric copolymers obtainable by copolymerization of N-vinylcarboxamide with anionic comonomers and subsequent hydrolysis of the vinylcarboxamide as a stock additive to increase the initial wet strength of paper.
- the treatment is e.g. in thick stock or thin paper in the papermaking process.
- WO 2014/029593 teaches a process for the production of high initial wet strength paper with the addition of a water-soluble amphoteric copolymer obtained by Hofmann degradation of an acrylamide- and / or methacrylamide-containing polymer and pressing the formed paper sheet in the press section at one defined solids content of> 48 wt .-%.
- the object of the invention was to increase the initial wet strength of the still moist paper web prior to transfer to the dryer section in the production of paper in order to achieve higher machine speeds compared to known processes in the papermaking process.
- the water-soluble, amphoteric polymer is obtainable by copolymerizing a monomer mixture comprising a) at least one N-vinylcarboxamide of the general formula wherein R 1 and R 2 independently of one another are H or C 1 -C 6 -alkyl, at least one monoethylenically unsaturated monomer having at least one free acid group or at least one acid group in salt form optionally at least one of the components (a) and (b) different monoethylenic unsaturated monomer, and optionally at least one compound having at least two ethylenically unsaturated double bonds in the molecule, and subsequent partial or complete hydrolysis of the groups -CO-R 1 of the polymer, wherein the difference in the proportions of cationic and anionic monomer units in moles, respectively based on the total number of moles of all monomer units, absolute maximum 10 mol%.
- total paper stock is meant the paper stock after addition of all filler slurries and auxiliaries.
- total paper stock also referred to as total paper stock (solid)
- Fillers are provided as so-called aqueous slurry and blended with the remaining stock.
- the term filler encompasses all pigments customarily used in the paper industry on the basis of metal oxides, silicates and / or carbonates which have a BET specific surface area of ⁇ 20 m 2 / g.
- GCC ground
- PCC precipitated calcium carbonate
- talc kaolin
- bentonite satin white
- calcium sulfate barium sulfate
- titanium dioxide titanium dioxide
- Particularly preferred as fillers calcium carbonate is
- filler is to be understood as meaning particles having an average particle size (volume average) of 10 ⁇ m, preferably of 0.3 to 5 ⁇ m, in particular of up to 0.5 to 2 ⁇ m.
- the determination of the average particle size (volume average) of the fillers in the context of this document generally by the method of quasi-elastic light scattering (DIN-ISO 13320-1), for example, with a Mastersizer 2000 from. Malvern Instruments Ltd.
- Filler materials are usually a BET specific surface area of ⁇ 20 m 2 / g.
- aqueous slurry a composition containing filler which generally has a filler content of> 5 wt., Based on the aqueous slurry.
- the slurry contains 10 to 70 wt .-%, in particular 20 to
- the aqueous slurry of the filler may also contain additional organic or inorganic adjuvants.
- an aqueous slurry comprising at least an inorganic filler, a water-soluble amphoteric polymer, and microparticles.
- the water-soluble amphoteric polymer is obtainable by copolymerization of the monomer mixture comprising the monomers a) and b) and subsequent complete or partial hydrolysis of the groups -CO-R1 of the polymer.
- the water-soluble amphoteric polymers contain the following structural units: amidine
- the ratio of amidine units to amine units is 100: 1 to 1: 30, preferably 40: 1 to 1:15, particularly preferably 8: 1 to 1: 8.
- cationic units are to be understood as meaning the sum of amine and amidine units, while anionic units are taken to mean the acid units which result from the copolymerization of the monomers of group (b) and which are present in the form of the free acid groups and / or Salt form present.
- Examples of monomers of group (a) are open-chain N-vinylamide compounds of the formula (I), such as, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N- ethylacetamide, N-vinylpropionamide and N-vinyl-N-methylpropionamide and N-vinylbutyramide.
- the monomers of group (a) may be used alone or in admixture in the copolymerization with the monomers of the other groups. From this group, N-vinylformamide is preferably used in the copolymerization.
- the copolymers to be used according to the invention contain at least one monomer of
- Group (b) that is a monoethylenically unsaturated monomer having at least one free acid group or at least one acid group in salt form.
- the acid group may be present as a free acid group or in salt form.
- Preferred salts are the water-soluble salts such as alkali metal, alkaline earth metal or ammonium salts.
- Suitable bases for the partial or complete neutralization of the acid groups of the monomers (b) are, for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines.
- alkali metal or alkaline earth metal bases ammonia, amines and / or alkanolamines.
- examples of these are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
- Suitable monomers of this group (b) are, for example, monoethylenically unsaturated sulfonic acids, phosphonic acids, monocarboxylic acids and dicarboxylic acids and in each case their salts. Also suitable are monoethylenically unsaturated monoesters of phosphonic acids, monoamides of phosphonic acids, and dicarboxylic anhydrides. Suitable monomers (b) are also esters of phosphoric acid with alcohols having a polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond. In this case, one or the other two protons of the phosphoric acid group can be neutralized by suitable bases. In addition, another acid function can be esterified with alcohols which have no polymerizable double bonds.
- Suitable saturated alcohols for esterifying the phosphoric acid are, for example, C 1 -C 6 alkanols, such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol and their isomers.
- Suitable monomers of group (b) are, for example, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts, such as alkali metal, alkaline earth metal or ammonium salts of these carboxylic acids.
- This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, aconitic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid. Also suitable are the dicarboxylic acid anhydrides of the abovementioned acids.
- the copolymers may contain at least one further monomer of group (c) in copolymerized form for modification.
- these monomers are nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, such as acrylonitrile and methacrylonitrile. In the hydrolysis of such copolymers, 5 ring amidines are then obtained.
- Further suitable monomers of group (c) are:
- Examples of members of this group (c) are e.g. Methyl (meth) acrylate (the formulation
- (meth) acrylate “means both methacrylate” and acrylate "), methyl ethacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl
- (meth) acrylate tert-butyl methacrylate, n-ocytl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate and mixtures thereof.
- Suitable additional monomers (c) are furthermore the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, preferably C 2 -C 12 -aminoalcohols. These may be d-Ce-monoalkylated or -dialkylated on the amine nitrogen.
- the acid component of these esters e.g. Acrylic, methacrylic, fumaric, maleic, itaconic, crotonic, maleic, monobutyl, and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof.
- N-methylaminomethyl (meth) acrylate N-methylaminoethyl (meth) acrylate, N, N-dimethylamino-methyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth ) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and
- N, N-dimethylaminocyclohexyl (meth) acrylate N, N-dimethylaminocyclohexyl (meth) acrylate.
- Suitable additional monomers (c) are furthermore acrylamide, methacrylamide,
- N-methyl (meth) acrylamide (the formulation (meth) acrylamide "in each case stands for acrylamide” and for methacrylamide "), N-ethyl (meth) acrylamide, n-propyl (meth) acrylamide, N- (n-butyl) -
- Further suitable monomers (c) are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and mixtures thereof.
- Suitable monomers (c) are also N-vinyl lactams and their derivatives, e.g. may have one or more C 1 -C 6 -alkyl substituents (as defined above). These include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2- piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-ca-prolactam, N-vinyl-7-ethyl-2-caprolactam and mixtures thereof.
- esters of vinyl alcohol and allyl alcohol with Ci-C3o monocarboxylic acids are also suitable.
- N-vinylimidazoles and alkylvinylimidazoles in particular methylvinylimidazoles such as, for example, 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridine N-oxides and betaine derivatives and quaternization products of these monomers.
- Additional monomers are ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
- the aforementioned monomers (c) can be used individually or in the form of any mixtures.
- copolymers are possible by using in the copolymerization monomers (d) which contain at least two double bonds in the molecule, for example triallylamine, methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glycerol triacrylate, pentaerythritol triallyl ether, at least two times with acrylic acid and / or Methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, Sobit or glucose. Also suitable are allyl and vinyl ethers of polyalkylene glycols or polyols such as pentaerythritol, Sobit o- the glucose.
- the amounts used are up to 2 mol%, for example 0.001 to 1 mol%.
- the polymerization is carried out using a monomer mixture comprising at least one monoethylenically unsaturated monomer as component (b). selected from the group consisting of monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides, this monomer having at least one free acid group or at least one acid group in salt form.
- a monomer mixture is used for the polymerization, the monoethylenically unsaturated monomer having at least one free acid group or at least one acid group in salt form (component (b) is selected from the group consisting of sulfonic acids, phosphonic acids, monoesters of phosphonic acids, monoamides of phosphonic acids and esters of phosphoric acid with alcohols having a polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond.
- component (b) is selected from the group consisting of sulfonic acids, phosphonic acids, monoesters of phosphonic acids, monoamides of phosphonic acids and esters of phosphoric acid with alcohols having a polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond.
- Typical water-soluble amphoteric polymers are obtainable by copolymerizing a monomer composition and subsequent partial or complete hydrolysis of the groups -CO-R 1 of the polymer, wherein the monomer composition of a) 1 to 99 wt .-%, preferably 5 to 95 wt .-%, in particular from 20 to 90% by weight, based on the total weight of the monomers used for the polymerization, of at least one N-vinylcarboxamide of the general formula wherein R 1 and R 2 independently of one another are H or C 1 -C 6 -alkyl, b) 1 to 99% by weight, preferably 5 to 95% by weight, in particular 10 to 80% by weight, based on the Total weight of the monomers used for the polymerization, at least one monoethylenically unsaturated monomer having at least one free acid group or at least one acid group in salt form, preferably at least one monomer selected from the group consisting of monocarboxylic acids, dicarboxylic acids and di
- % preferably 0.1 to 85% by weight, in particular 1 to 80% by weight, based on the total weight of the monomers used for the polymerization, of at least one monoethylenically unsaturated monomer other than components (a) and (b), and d) 0 to 5 wt .-%, preferably 0.0001 to 3 wt .-%, based on the total weight of the monomers used for the polymerization, of at least one compound containing at least two ethylenically unsaturated Doppelb having indices in the molecule,
- the hydrolysis of the polymers obtained by the process described above is carried out by known methods by the action of acids, bases or enzymes, for example hydrochloric acid, sodium hydroxide solution or potassium hydroxide solution.
- the copolymerized monomers (a) of the abovementioned formula (I) are obtained by cleavage of the -CO-R 1 group copolymers which contain vinylamine units (VI) and / or amidine units (II-V)
- amidine units (II) and (III) are formed by reaction of adjacent vinylamines of the formula (VI) with vinylformamide units or those of the formula IV and V by reaction of adjacent vinylamine units of the formula (VI) with acrylonitrile or methacrylonitrile groups (if present in the polymer).
- the amphoteric polymer contains, for example (i) 1 to 98 mol%, preferably 1 to 75 mol% of vinylcarboxamide units,
- amphoteric polymers in particular consisting of
- amphoteric polymers are particularly preferably containing, in particular consisting of
- amphoteric copolymers which contain copolymerized as component (a) N-vinylformamide.
- the preparation of the water-soluble amphoteric polymers is carried out by customary methods known to the person skilled in the art. Suitable methods are e.g. in EP-A-0 251 182, WO-A-94/13882 and EP-B-0 672 212, to which reference is hereby made. Furthermore, reference is made to the preparation of the water-soluble amphoteric polymers described in WO-A-04/087818 and WO-A-05/012637.
- the preparation of the water-soluble amphoteric polymers can be carried out by solution, precipitation, suspension or emulsion polymerization. Preference is given to solution polymerization in aqueous media.
- aqueous media are water and mixtures of water and at least one water-miscible solvent, for example an alcohol, such as methanol, ethanol, n-propanol, isopropanol, etc.
- the polymerization temperatures are preferably in a range of about 30 to 200 ° C, more preferably 40 to 1 10 ° C.
- the polymerization is usually carried out under atmospheric pressure, but it can also proceed under reduced or elevated pressure.
- a suitable pressure range is between 0.1 and 5 bar.
- the acid group-containing monomers (b) are preferably used in the salt form.
- the pH is preferably adjusted to a value in the range of 6 to 9 for copolymerization. By using a standard buffer or by measuring the pH and corresponding addition of acid or base, the pH can be kept constant during the polymerization.
- the monomers can be polymerized with the aid of radical-forming initiators.
- the peroxo and / or azo compounds customary for this purpose can be used, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, Di-tert-amyl peroxide, tert-butyl hydroperoxid
- initiator mixtures or redox initiator systems such as e.g. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H2O2 / CUI.
- the polymerization can be carried out in the presence of at least one regulator.
- a regulator the usual compounds known in the art, such as sulfur compounds, for. Mercaptoethanol,
- the average molecular weight M w of the water-soluble amphoteric polymer is, for example, at least 10,000, preferably at least 100,000 daltons and in particular at least 500,000 daltons.
- the molecular weights of the polymers are then, for example, 10 000 to 10 million, preferably 100 000 to 5 million (determined, for example, by light scattering on their unhydrolyzed precursor).
- This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.1% by weight). Further constituents of the aqueous slurry are microparticles.
- the microparticle can have both organic or inorganic character.
- Suitable polymeric microparticles include anionic, cationic or amphoteric organic microparticles. These organic polymers have limited solubility in water and may be crosslinked. Organic microparticles have unswollen particle size of less than 750 nm.
- Anionic organic microparticles such as described in US 6,524,439, are obtainable by hydrolysis of an acrylamide polymer microparticle or by polymerization of anionic monomers such as (meth) acrylic acid and its salts, 2-acrylamido 2-methylpropanesulfonates, sulfoethyl (meth) acrylates, vinylsulfonic acid, styrenesulfonic acid, maleic acid or other dibasic acids or their salts and mixtures thereof.
- anionic monomers such as (meth) acrylic acid and its salts, 2-acrylamido 2-methylpropanesulfonates, sulfoethyl (meth) acrylates, vinylsulfonic acid, styrenesulfonic acid, maleic acid or other dibasic acids or their salts and mixtures thereof.
- anionic monomers can furthermore be copolymerized with nonionic monomers, such as (meth) acrylamide, N-alkylacrylamides, ⁇ , ⁇ -dialkylacrylamides, methyl (meth) acrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N- vinylpyrrolidone and mixtures thereof.
- nonionic monomers such as (meth) acrylamide, N-alkylacrylamides, ⁇ , ⁇ -dialkylacrylamides, methyl (meth) acrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N- vinylpyrrolidone and mixtures thereof.
- Cationic organic microparticles are obtainable by polymerization of monomers such as diallyldialkylammonium halides, acryloxyalkyltrimethylammonium chlorides, (meth) acrylates of dialkylaminoalkyl compounds, their salts and their quaternary compounds, and of monomers such as N, N Dialkylaminoalkyl (meth) acrylamides, (meth) acrylamidopropyltrimethylammonium chlorides and ⁇ , ⁇ -dimethylaminoethyl acrylate, their acids or quaternary salts or the like.
- monomers such as diallyldialkylammonium halides, acryloxyalkyltrimethylammonium chlorides, (meth) acrylates of dialkylaminoalkyl compounds, their salts and their quaternary compounds, and of monomers such as N, N Dialkylaminoalkyl (meth) acrylamides, (meth) acrylamido
- cationic monomers can furthermore be copolymerized with nonionic monomers, such as (meth) acrylamide, N-alkylacrylamides, ⁇ , ⁇ -dialkylacrylamides, methyl (meth) acrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N- vinylpyrrolidone and mixtures thereof.
- nonionic monomers such as (meth) acrylamide, N-alkylacrylamides, ⁇ , ⁇ -dialkylacrylamides, methyl (meth) acrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N- vinylpyrrolidone and mixtures thereof.
- Amphoteric organic microparticles are obtainable by polymerizing at least one anionic monomer and at least one cationic monomer and optionally one or more nonionic monomers as described above for the other microparticles.
- the polymerization of the monomers into microparticles is typically carried out in the presence of a multifunctional crosslinker.
- crosslinkers are described, for example, in US Pat. No. 6,524,439, and have at least two double bonds or one double bond and one reactive group or two reactive groups.
- the multifunctional crosslinker is used in an amount that gives a sufficiently crosslinked polymer.
- at least 4 ppm of multifunctional crosslinkers can be used per mole of monomers.
- the polymerization can be carried out in the presence of at least one regulator.
- Such polymerizations for producing polymer particles are described, for example, in US Pat. Nos. 5,961,840, 5,919,882, 5,171,808 and 5,167,766.
- the usual compounds known in the art such as sulfur compounds fertilize, z.
- sulfur compounds fertilize z.
- mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and Tribromchlormethan or other compounds which act regulating the molecular weight of the polymers obtained are used.
- Polymerization to a microparticle usually takes place by means of inverse emulsion polymerization or inverse microemulsion polymerization and is generally known to the person skilled in the art. Such polymerizations are described, for example, in US 2003/0192664 (page 6), the teaching of which is expressly incorporated by reference.
- the preparation of the microparticles is usually by means of
- Preferred anionic organic microparticles have unswollen an average particle diameter of ⁇ 750 nm, preferably of ⁇ 500 nm, in particular in the range of 25 to 300 nm.
- the anionic organic microparticles preferably contain
- the anionic organic microparticles are particularly preferred.
- the anionic organic microparticles are particularly preferred.
- the anionic organic microparticles have a charge density of at least 2 meq / g.
- Inorganic microparticles in contrast to inorganic fillers which have a BET specific surface area of ⁇ 20 m 2 / g, have a BET specific surface area of> 100 m 2 / g (BET measurement (DIN ISO 9277: 2003-05). ,
- Suitable inorganic microparticles are preferably bentonite, colloidal silicic acid, silicates and / or calcium carbonate.
- Bentonite is generally understood to be phyllosilicates which are swellable in water. These are mainly the clay mineral montmorillonite and similar clay minerals such as nontronite, hectorite, saponite, sauconite, beidellite, allevardite, lllite, halloysite, attapulgite and sepiolite.
- These sheet silicates are preferably activated prior to their application, i. into a water-swellable form by treating the phyllosilicates with an aqueous base such as aqueous solutions of caustic soda, potassium hydroxide, soda or potash.
- Bentonite in the form treated with sodium hydroxide solution is preferably used as the inorganic microparticle.
- the platelet diameter of the water-dispersed bentonite in the treated with sodium hydroxide solution for example, 1 to 2 ⁇ , the thickness of the platelets is about 1 nm.
- Typical bentonites are described, for example, in EP-B-0235893.
- bentonite is added to the cellulosic suspension, typically in the form of an aqueous bentonite slurry. This bentonite slurry may contain up to 10% by weight of bentonite. Normally, the slurries contain about 3 to 5 wt .-% bentonite.
- colloidal silica products from the group of silicon-based particles, silica microgels, silica sols, aluminum silicates, borosilicates, polyborosilicates or zeolites can be used. These have a specific surface area of 200-1000 m 2 / g and an average particle size distribution of 1-250 nm, normally in the range 40-100 nm.
- the preparation of such components is described, for example, in EP-A-0041056, EP-A-0185068 and US Pat US-A-5176891.
- Clay or kaolin is a hydrous aluminum silicate with a platelet-like structure.
- the crystals have a layer structure and an aspect ratio (diameter to thickness ratio) of up to 30: 1.
- the particle size is at least 50% less than 2 ⁇ .
- a weight ratio of fillers to anoranic microparticles of at least 30: 1 is preferably selected.
- the aqueous slurry generally has a solids content of> 3 wt .-%, preferably> 8 wt .-%, in particular 12 wt .-%, based on the aqueous ⁇ nschlämmung.
- the proportion of microparticles in the aqueous slurry is, for example
- the proportion of the water-soluble, amphoteric polymer is generally from 0.01 to 1 wt .-%, preferably 0.05 to 0.6 wt .-% based on the filler (solid).
- aqueous slurries comprising, preferably consisting of water, 5-70% by weight of filler based on the aqueous slurry, and 0.001-1% by weight of water-soluble amphoteric polymer and 0.01-1% by weight of microparticles, in each case based on Filler (solid).
- the aqueous slurry is metered into a pulp.
- the paper stock used can be any of the fibers of coniferous and hardwoods commonly used in the paper industry, e.g. Pulp, bleached and unbleached pulp and pulps from all annual plants.
- Wood pulp includes, for example, groundwood, thermo-mechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure ground,
- pulp for example, sulphate, sulphite and soda pulps come into consideration.
- unbleached pulp also referred to as unbleached kraft pulp
- Suitable annual plants for the production of paper materials are for example rice, wheat, sugar cane and kenaf.
- Waste paper may also be used to make the pulps, either alone or blended with other pulps.
- the waste paper can come from a deinking process. But it is not necessary that the waste paper to be used is subjected to such a process. Furthermore, it is also possible to assume fiber blends of a primary material and recycled coated broke.
- the aqueous slurry is added to an aqueous suspension of fibers.
- this is done in the absence of other process chemicals commonly used in papermaking.
- the water-soluble, amphoteric polymers can be added in the papermaking process, for example in an amount of from 0.01 to 1.00% by weight, based on dry fiber.
- Typical application rates are, for example, 0.1 to 10 kg, preferably 0.3 to 4 kg of the water-soluble, amphoteric polymer, per ton of a dry pulp. In most cases, the amounts of amphoteric polymer used 0.5 to 2.5 kg of polymer (solid), per ton of dry pulp.
- the process chemicals commonly used in papermaking can be used in the usual amounts, e.g. Retention aids, dehydrating agents, other dry strength agents such as, for example, starch, pigments, foams, optical brighteners, defoamers, biocides and paper dyes. These substances are preferably added to the paper stock only after the treatment according to the invention of the fibrous material.
- a paper machine consists of the successive units: headbox, wire section, press section and dryer section.
- the dewatering effect within the wire section is achieved by mechanical forces (gravity, centrifugal force).
- hydrodynamic measures are also used. These usually lead to a vacuum on the screens. These measures are particularly useful when the drainage has reached a degree at which first capillary effects in the wet paper texture play a role.
- sheet formation takes place in the wire section up to a dry content of the paper sheet of at least 18% by weight, preferably 19% by weight, in particular 20% by weight.
- the sheet formation in the wire section preferably takes place up to a dry content of the paper sheet of at most 25% by weight.
- the sheet formation takes place in the wire section up to a dry content of the paper sheet in the range of 19 to 22 wt .-%.
- the wet nonwoven fabric is doffed onto the press felt by a suction cup (suction roll or static vacuum element).
- the task of the press felt is the transport of the fibrous web by press nips of various modifications.
- the dry content of the web is up to a maximum of 55% by weight.
- the dry content increases with the pressure exerted on the continuous paper web in the press.
- the printing and thus the dry content of the paper web can be varied over a relatively large range in many paper machines.
- the method according to the invention enables a tear-free operation of the paper machine.
- the paper web or paper sheet produced in the process shows a significantly increased initial wet structural strength.
- the percentages in the examples are by weight unless otherwise specified.
- the structural composition of the polymers was calculated from the monomer mixture used, the degree of hydrolysis and the ratio of vinylamine / amidine determined by 13 C-NMR spectroscopy. The composition ratio is in mol% unless otherwise specified.
- the determination of the dry content is carried out in accordance with DIN EN ISO 638 DE using the heating cabinet method.
- the dry content of the paper sheet is the ratio of the mass of a sample which has been dried at a temperature of (105 ⁇ 2) ° C under defined conditions to a constant mass, to the mass of the sample before drying.
- the dry content is given as percentage by mass.
- the K values were measured according to H. Fikentscher, Cellulose Chemistry, Vol. 13, 48-64 and 71-74 under the particular conditions indicated.
- the figures in parenthesis indicate the concentration of the polymer solution and the solvent.
- Solid contents of the polymers were determined by distributing 0.5 to 1.5 g of the polymer solution in a 4 cm diameter tin cover and then drying in a circulating air drying cabinet at 140 ° C. for two hours. The ratio of the mass of the sample after drying under the above conditions to the mass during sampling gives the solids content of the polymer.
- the average molecular weight M w is meant, in the preceding and hereinafter, the mass-average molecular weight M w , as can be determined by light scattering. The molecular weight was determined on the unhydrolyzed precursor. Used ingredients:
- Bentonite (Hydrocol ® from. BASF)
- amphoteric polymers were used to make slurries.
- PCC precipitated calcium carbonate
- GCC ground calcium carbonate
- a 12 wt .-% aqueous solution of the polymer P6 were placed in a beaker and then diluted with 30g of water. Subsequently, 150 g of a 20% by weight suspension of precipitated calcium carbonate (PCC) in water was added. During the addition of the PCC slurry and then the mixture was stirred by means of a Hertof stirrer at 1000 revolutions per minute (rpm). About 30 seconds after the addition of the PCC slurry, a 1% strength by weight solution of an acrylamide-containing structured anionic micropolymer (Telioform M300 from BASF) was added while the agitator was running.
- PCC precipitated calcium carbonate
- the added amount of the micropolymer solution was calculated so that the solid content of the micropolymer in the PCC slurry was 0.07 wt% of the solid PCC content. After another 30 seconds, the speed of the Heiltof stirrer was reduced to 200 rpm and left until further use of the slurry. The pH of the mixture was then adjusted to 8.5.
- Slurry A1 The procedure was as for preparing slurry A1 1, wherein the polymers P and microparticles given in Table 1 were used, but the amounts or concentrations were retained.
- Slurry A16 was prepared with ground calcium carbonate instead of precipitated calcium carbonate.
- the compositions of the prepared slurries are shown in Table 3.
- PCC precipitated calcium carbonate
- a mixture of bleached birch sulphate and bleached pine sulphate was blotted open in a ratio of 70/30 at a solids concentration of 4% by weight in the laboratory pulper until a freeness of 29-32 was reached.
- the pH of the pulp was in the range between 7 and 8.
- the milled material was then diluted by addition of water to a solids concentration of 0.8 wt .-%.
- An optical brightener (blank PSG) and a cationic starch (HiCat 5163 A) were then added to the diluted pulp.
- the digestion of the cationic starch was previously carried out as a 10 wt .-% starch slurry in a jet cooker at 130 ° C and 1 minute residence time.
- the metered amount of the optical brightener was 0.3 wt .-% commercial goods, based on total paper stock (solid).
- the dosage of the cationic starch was 0.8% by weight of starch (solid), based on the total paper stock (solid).
- sheets were prepared, each of about 25 wt .-% of an untreated PCC 's and 25 wt .-% of an untreated GCC' s included.
- the production of the paper sheets with a weight per unit area of 100 g / m 2 was carried out on a dynamic sheet former from TechPap France.
- the paper stock suspension was sprayed onto a sieve that was clamped in a vertical, rapidly rotating drum is.
- the drainage and sheet formation in this system in addition to the leaf structure mainly determined by the centrifugal forces within the rotating drum. By varying the rotational speed of the drum, the centrifugal force acting on the resulting sheet structure can also be varied.
- the number of revolutions of the drum was varied in 5 stages between 600 and 1100 revolutions per minute, whereby dry contents in the range between 14 Gew. -% and 21 Gew. -% can be adjusted.
- the amount of filler added for sheet formation must be adjusted slightly upward as the number of revolutions of the drum increases, as filler retention decreases with increasing dewatering.
- a small portion of the still-wet leaf structure is used to directly determine the dry content after removal of the wet paper sheet from the screen of the dynamic sheet former.
- the wet strength and the initial wet strength of paper are to be distinguished from the initial wet texture strength because both properties are measured on papers which are moistened again after drying to a defined water content.
- the initial wet strength is an important parameter in the assessment of non-permanent wet-strength papers. A dried and then rewetted paper has a very different wet strength than a wet paper which is present just after passing through the wire and press section of a paper machine.
- the examples carried out according to the invention show a markedly increased wet fat index INF (50%) of the leaves. If the dry content is significantly lower, the INF (50%) index is only slightly above that of an untreated filler slurry.
- Reference Examples PCC 4 and PCC5 and Reference Examples GCC9 and GCC10 demonstrate that setting the dry content above 18% by weight alone (in this case, by adjusting the rotational speed of the dynamic sheet former) without additional treatment of the filler slurry with a 2-component system does not result in any significant increase in the INF (50%) index.
- Examples 84, 85, 89, 90, 94 and 95 show that treatment of the filler with only the water-soluble amphoteric polymer or only the microparticles also does not produce an effect when exceeding the dry content above 18%.
Abstract
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WO2020053393A1 (en) * | 2018-09-14 | 2020-03-19 | Solenis Technologies Cayman, L.P. | Method for the hydrolysis of a polymer |
BR112021004802A2 (en) | 2018-09-14 | 2021-06-08 | Solenis Technologies Cayman, L.P. | method for producing paper or cardboard |
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AU546999B2 (en) | 1980-05-28 | 1985-10-03 | Eka A.B. | Adding binder to paper making stock |
JPS612524A (en) | 1984-06-15 | 1986-01-08 | Sekisui Chem Co Ltd | Manufacture of thermoplastic resin pipe |
GB8602121D0 (en) | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
CA1283748C (en) | 1986-06-25 | 1991-04-30 | Takaharu Itagaki | Vinylamine copolymer, flocculating agent and paper strength increasingagent using the same, as well as process for producing the same |
US5176891A (en) | 1988-01-13 | 1993-01-05 | Eka Chemicals, Inc. | Polyaluminosilicate process |
US6191242B1 (en) | 1988-12-19 | 2001-02-20 | Cytec Technology Corp. | Process for making high performance anionic polymeric flocculating agents |
US5167766A (en) | 1990-06-18 | 1992-12-01 | American Cyanamid Company | Charged organic polymer microbeads in paper making process |
US5171808A (en) | 1990-06-11 | 1992-12-15 | American Cyanamid Company | Cross-linked anionic and amphoteric polymeric microparticles |
EP0528409B1 (en) | 1991-08-20 | 1996-05-22 | Mitsubishi Chemical Corporation | Cationic polymer flocculating agents |
DE4241117A1 (en) | 1992-12-07 | 1994-06-09 | Basf Ag | Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking |
US6273998B1 (en) | 1994-08-16 | 2001-08-14 | Betzdearborn Inc. | Production of paper and paperboard |
US20030192664A1 (en) | 1995-01-30 | 2003-10-16 | Kulick Russell J. | Use of vinylamine polymers with ionic, organic, cross-linked polymeric microbeads in paper-making |
US5919682A (en) | 1995-08-24 | 1999-07-06 | Board Of Regents, University Of Texas System | Overproduction of neuronal nitric oxide synthase |
DE19548294C1 (en) | 1995-12-22 | 1997-04-03 | Voith Sulzer Papiermasch Gmbh | Paper-making machine |
ATE215640T1 (en) | 1996-12-31 | 2002-04-15 | Ciba Spec Chem Water Treat Ltd | PAPER MAKING METHOD AND MATERIALS |
MY140287A (en) | 2000-10-16 | 2009-12-31 | Ciba Spec Chem Water Treat Ltd | Manufacture of paper and paperboard |
DE10315363A1 (en) * | 2003-04-03 | 2004-10-14 | Basf Ag | Aqueous slurries of finely divided fillers, process for their preparation and their use for the production of filler-containing papers |
DE10334133A1 (en) | 2003-07-25 | 2005-02-24 | Basf Ag | Aqueous composition and its use for papermaking |
JP5130049B2 (en) | 2004-12-17 | 2013-01-30 | ビーエーエスエフ ソシエタス・ヨーロピア | Paper with high filler content and high dry strength |
US8172983B2 (en) * | 2007-09-12 | 2012-05-08 | Nalco Company | Controllable filler prefloculation using a dual polymer system |
JP2011525572A (en) * | 2008-06-24 | 2011-09-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Paper manufacturing |
CN104583493B (en) * | 2012-08-22 | 2019-06-07 | 巴斯夫欧洲公司 | The method for producing paper, card and cardboard |
RU2015116429A (en) * | 2012-10-05 | 2016-11-27 | Спешелти Минералз (Мичиган) Инк. | SUSPENSION OF FILLER AND ITS USE IN PAPER PRODUCTION |
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