JP2004514796A - How to size paper - Google Patents
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- JP2004514796A JP2004514796A JP2002517894A JP2002517894A JP2004514796A JP 2004514796 A JP2004514796 A JP 2004514796A JP 2002517894 A JP2002517894 A JP 2002517894A JP 2002517894 A JP2002517894 A JP 2002517894A JP 2004514796 A JP2004514796 A JP 2004514796A
- Authority
- JP
- Japan
- Prior art keywords
- sizing
- polymer
- cationic
- polysaccharide
- accelerator
- 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.)
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- 238000004513 sizing Methods 0.000 claims abstract description 235
- 125000002091 cationic group Chemical group 0.000 claims abstract description 125
- 125000003118 aryl group Chemical group 0.000 claims abstract description 124
- 229920000642 polymer Polymers 0.000 claims abstract description 123
- 239000006185 dispersion Substances 0.000 claims abstract description 101
- 238000000034 method Methods 0.000 claims abstract description 91
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 85
- 239000000725 suspension Substances 0.000 claims abstract description 74
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 67
- 239000005017 polysaccharide Substances 0.000 claims abstract description 67
- 229920000620 organic polymer Polymers 0.000 claims abstract description 59
- 150000004676 glycans Chemical class 0.000 claims abstract description 57
- 125000000129 anionic group Chemical group 0.000 claims abstract description 54
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 40
- 239000000835 fiber Substances 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 19
- -1 cationic polysaccharide Chemical class 0.000 claims description 72
- 239000003795 chemical substances by application Substances 0.000 claims description 68
- 125000004432 carbon atom Chemical group C* 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 59
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical group C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 28
- 150000001450 anions Chemical class 0.000 claims description 27
- 229920006317 cationic polymer Polymers 0.000 claims description 24
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- 229920002472 Starch Polymers 0.000 claims description 22
- 235000019698 starch Nutrition 0.000 claims description 22
- 239000008107 starch Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 15
- 150000004804 polysaccharides Polymers 0.000 claims description 15
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 229920001732 Lignosulfonate Polymers 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- 229920003043 Cellulose fiber Polymers 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 229920005610 lignin Polymers 0.000 claims description 11
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 11
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 11
- 125000004018 acid anhydride group Chemical group 0.000 claims 1
- 238000007792 addition Methods 0.000 description 23
- 239000000123 paper Substances 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 18
- 239000002994 raw material Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 11
- 239000001913 cellulose Substances 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920002907 Guar gum Polymers 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 239000000665 guar gum Substances 0.000 description 4
- 235000010417 guar gum Nutrition 0.000 description 4
- 229960002154 guar gum Drugs 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 150000002561 ketenes Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 238000007155 step growth polymerization reaction Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- FAMIQNOUNCNXNK-UHFFFAOYSA-M 1-chloro-3-pyridin-1-ium-1-ylpropan-2-ol;chloride Chemical compound [Cl-].ClCC(O)C[N+]1=CC=CC=C1 FAMIQNOUNCNXNK-UHFFFAOYSA-M 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GFVJWUVFVLFWNG-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;terephthalic acid Chemical compound CCC(CO)(CO)CO.OC(=O)C1=CC=C(C(O)=O)C=C1 GFVJWUVFVLFWNG-UHFFFAOYSA-N 0.000 description 2
- WZISPVCKWGNITO-UHFFFAOYSA-N 4-(diethylamino)-2-methylidenebutanamide Chemical compound CCN(CC)CCC(=C)C(N)=O WZISPVCKWGNITO-UHFFFAOYSA-N 0.000 description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 2
- NFKIMJJASFDDJG-UHFFFAOYSA-N 5-amino-N,N-diethyl-2-methylpent-2-enamide Chemical compound NCCC=C(C(=O)N(CC)CC)C NFKIMJJASFDDJG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
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- 239000004375 Dextrin Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
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- 240000005979 Hordeum vulgare Species 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 235000021307 Triticum Nutrition 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
- NRGNIRIWTPPPCH-UHFFFAOYSA-N [3-(dimethylamino)-3-hydroxypropyl] prop-2-enoate Chemical compound CN(C)C(O)CCOC(=O)C=C NRGNIRIWTPPPCH-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
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- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000007080 aromatic substitution reaction Methods 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- AAZVLNHLLNLZEE-UHFFFAOYSA-M benzyl-(3-chloro-2-hydroxypropyl)-dimethylazanium;chloride Chemical compound [Cl-].ClCC(O)C[N+](C)(C)CC1=CC=CC=C1 AAZVLNHLLNLZEE-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
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- 150000001767 cationic compounds Chemical class 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical group [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 2
- 150000002513 isocyanates Chemical class 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
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- 238000002156 mixing Methods 0.000 description 2
- DCBBWYIVFRLKCD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-methylprop-2-enamide Chemical compound CN(C)CCNC(=O)C(C)=C DCBBWYIVFRLKCD-UHFFFAOYSA-N 0.000 description 2
- VNLHOYZHPQDOMS-UHFFFAOYSA-N n-[3-(diethylamino)propyl]-2-methylprop-2-enamide Chemical compound CCN(CC)CCCNC(=O)C(C)=C VNLHOYZHPQDOMS-UHFFFAOYSA-N 0.000 description 2
- GFOCCLOYMMHTIU-UHFFFAOYSA-N n-[3-(diethylamino)propyl]prop-2-enamide Chemical compound CCN(CC)CCCNC(=O)C=C GFOCCLOYMMHTIU-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- VCWHRHVZWITKNJ-UHFFFAOYSA-N propane-1,2,3-triol;terephthalic acid Chemical compound OCC(O)CO.OC(=O)C1=CC=C(C(O)=O)C=C1 VCWHRHVZWITKNJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
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- 229940082509 xanthan gum Drugs 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- KDAKDBASXBEFFK-UHFFFAOYSA-N 2-(tert-butylamino)ethyl prop-2-enoate Chemical compound CC(C)(C)NCCOC(=O)C=C KDAKDBASXBEFFK-UHFFFAOYSA-N 0.000 description 1
- AJTVSSFTXWNIRG-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanesulfonic acid Chemical compound OCC[NH+](CCO)CCS([O-])(=O)=O AJTVSSFTXWNIRG-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 1
- FRFUQJFVJRYYDZ-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)prop-2-enamide Chemical compound CC(C)CNC(=O)C(C)=C FRFUQJFVJRYYDZ-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- GPFVWKXABQQNEM-BMRADRMJSA-N 3-[(e)-16-methylheptadec-1-enyl]oxolane-2,5-dione Chemical compound CC(C)CCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O GPFVWKXABQQNEM-BMRADRMJSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- RBPIYINIVXGGFY-UHFFFAOYSA-N 4-(dimethylazaniumyl)-2-methylidenebutanoate Chemical compound CN(C)CCC(=C)C(O)=O RBPIYINIVXGGFY-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 244000004281 Eucalyptus maculata Species 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YIQOKWWBKOVYBX-UHFFFAOYSA-N [3-(dimethylamino)-3-hydroxypropyl] 2-methylprop-2-enoate Chemical compound CN(C)C(O)CCOC(=O)C(C)=C YIQOKWWBKOVYBX-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KQVMFSLMVJQXKC-UHFFFAOYSA-N butanedioic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound OC(=O)CCC(O)=O.CCC(CO)(CO)CO KQVMFSLMVJQXKC-UHFFFAOYSA-N 0.000 description 1
- WKZFQFQFYZJKPR-UHFFFAOYSA-N butanedioic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)CCC(O)=O WKZFQFQFYZJKPR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000007156 chain growth polymerization reaction Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 description 1
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 1
- ZTUMLBMROBHIIH-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group ClCC1=CC=CC=C1.CN(C)CCOC(=O)C(C)=C ZTUMLBMROBHIIH-UHFFFAOYSA-N 0.000 description 1
- CEJFYGPXPSZIID-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClCC1=CC=CC=C1.CN(C)CCOC(=O)C=C CEJFYGPXPSZIID-UHFFFAOYSA-N 0.000 description 1
- 239000011436 cob Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- PBSASXNAZJHOBR-UHFFFAOYSA-N n-(2-methylpropyl)prop-2-enamide Chemical compound CC(C)CNC(=O)C=C PBSASXNAZJHOBR-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
- D21H23/765—Addition of all compounds to the 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
- 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
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
Landscapes
- Paper (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本発明はセルロース繊維、及び任意のてん料を含む水性懸濁液に、（ｉ）陰イオン又は陽イオンサイジング分散液、及び（ｉｉ）一つ以上の芳香族基を有する陽イオン有機ポリマー、及び一つ以上の芳香族基を有する陰イオンポリマー（その陰イオンポリマーは段階成長ポリマー、多糖又は天然産芳香族ポリマーである）を含むサイジング促進剤を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法に関する。The present invention relates to an aqueous suspension comprising cellulosic fibers and any filler, (i) an anionic or cationic sizing dispersion, and (ii) a cationic organic polymer having one or more aromatic groups, and Add a sizing accelerator, including an anionic polymer having one or more aromatic groups, where the anionic polymer is a step growth polymer, a polysaccharide or a naturally occurring aromatic polymer, and form the resulting suspension. A sizing method for paper comprising constructing and dewatering, wherein the sizing dispersion and the sizing accelerator are separately added to the aqueous suspension.
Description
【０００１】
（技術分野）
本発明はセルロース繊維、及び任意のてん料を含む懸濁液に、陰イオン又は陽イオンサイジング分散液、並びに一つ以上の芳香族基を有する陽イオン有機ポリマー、及び段階成長ポリマー、多糖及び天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤を添加し、得られた懸濁液を地合構成し、脱水することを含み、そのサイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法に関する。
【０００２】
（背景技術）
サイジング剤の分散液又はエマルジョンは紙及び板紙に種々の液体による湿潤及び浸透に対する改良された抵抗を与えるために抄紙の際に使用される。サイジング分散液は通常セルロース繊維、任意のてん料及び種々の添加剤を含む水性懸濁液に添加される。水性懸濁液は懸濁液をワイヤ（そこで紙の湿潤ウェブが形成される）に放出するヘッドボックスに供給される。その懸濁液に、普通澱粉及び微粒状材料（これらはワイヤ上の懸濁液の脱水を促進する）の如き化合物が更に添加される。ワイヤから脱水された水（白水と称される）が通常抄紙方法で部分循環される。セルロース懸濁液は或る量の非繊維材料、例えば、てん料、荷電ポリマー、サイジング剤及び種々の荷電汚染物質、即ち、陰イオンくず、電解質、コロイド物質等を含む。非繊維材料はサイジング効率に影響を有し、普通サイジング効率を損なう。懸濁液中の高含量の塩の如き多量の荷電化合物はサイジングするのに、即ち、満足なサイジング特性を有する紙を得るのに次第に困難である懸濁液にする。サイジングを損なう懸濁液中に含まれるその他の化合物は種々の親油性木材抽出物であり、これらはリサイクル繊維及びメカニカルパルプに由来し得る。増大された量の添加されたサイジング剤はしばしばサイジングを改良するが、高コストだけでなく白水中のサイジング剤の増大された蓄積をもたらす。非繊維材料だけでなく懸濁液中に存在するあらゆるその他の成分の蓄積は白水が抄紙方法へのほんの少量の新鮮な水の導入でもって徹底的に循環される工場では一層顕著であろう。こうして、本発明の目的はサイジングを更に改良することである。本発明の別の目的は高導電率及び／又は多量の親油性木材抽出物を有する水性セルロース含有懸濁液をサイジングする場合にサイジングを改良することである。更に別の目的は以下に明らかになるであろう。
【０００３】
米国特許第６００１１６６号は陽イオン澱粉及び陰イオン分散剤、例えば、リグニンスルホン酸、ナフタレンスルホン酸とホルムアルデヒドの縮合物を含む水性アルキルジケテン分散液に言及している。
【０００４】
ＷＯ ００２３６５１はケテン二量体及び少なくとも陰イオン分散剤を含む陰イオンサイジング分散液及び陽イオンサイジング分散液に関する。
ＥＰ ９８４１０１はケテン二量体又は酸無水物並びにアミノポリカルボン酸、Ｎ−ビス−又はトリス−（（１，２−ジカルボキシルエトキシ）エチル）アミン及びホスホン酸から選ばれた錯生成剤を含むサイジング組成物を開示している。
【０００５】
米国特許第５９７２０９４号は熱可塑性ロジン、熱可塑性炭化水素樹脂、熱可塑性ポリアミド及び熱可塑性アミドワックスからなる群から選ばれた熱可塑性樹脂を含むサイジング組成物に関する。
米国特許第５５９５６２９号は水性セルロース抄紙スラリーを生成し、陽イオンポリマー及び陰イオンポリマーをスラリーに添加して歩留り及び／又は脱水を増大する製紙方法を開示している。その陰イオンポリマーはナフタレンスルホン酸塩のホルムアルデヒド縮合物を含む。
【０００６】
（発明の開示）
特許請求の範囲に記載の本発明は驚くことに本件出願に概説された問題を解決することがわかった。更に詳しくは、本発明はセルロース繊維、及び任意のてん料を含む水性懸濁液に、陰イオン又は陽イオンサイジング分散液、並びに一つ以上の芳香族基を有する陽イオン有機ポリマー及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤を添加し、得られた懸濁液を地合構成し、脱水することを含み、そのサイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法に関する。
【０００７】
サイジング分散液
本発明の方法に使用される陰イオン又は陽イオンサイジング分散液に含まれるサイジング剤は紙又は板紙に液体の湿潤及び浸透に対する抵抗を与えるあらゆるサイジング剤、ロジン、例えば、強化ロジン及び／又はエステル化ロジン、ワックス、脂肪酸及び樹脂酸誘導体、例えば、脂肪アミド及び脂肪エステル、例えば、天然脂肪酸のグリセロールトリエステルを含む非セルロース反応性薬剤、及び／又はセルロース反応性薬剤であることが好適である。このサイジング分散液はセルロース反応性サイジング剤を含むことが好ましい。該サイジング分散液中に含まれるセルロース反応性サイジング剤は当業界で知られているあらゆるセルロース反応性薬剤から選ばれる。このサイジング剤は疎水性ケテン二量体、ケテン多量体、酸無水物、有機イソシアネート、カルバモイルクロリド及びこれらの混合物、好ましくはケテン二量体及び／又は酸無水物から選ばれることが好適である。このケテン二量体は下記の一般式（Ｉ）を有することが好適であり、式中、Ｒ１及びＲ２は飽和又は不飽和炭化水素基、通常、飽和炭化水素基を表し、その炭化水素基は好適には８〜３６個の炭素原子を有し、通常、１２〜２０個の炭素原子を有する直鎖又は分岐鎖アルキル基、例えば、ヘキサデシル基及びオクタデシル基である。該ケテン二量体は周囲温度、即ち、２５℃、好適には２０℃で液体であってもよい。普通、前記酸無水物は下記の一般式（ＩＩ）を特徴とし、式中、Ｒ３及びＲ４は同じであってもよく、また異なっていてもよく、好適には８〜３０個の炭素原子を含む飽和又は不飽和炭化水素基を表し、又はＲ３及びＲ４は−Ｃ−Ｏ−Ｃ−部分と一緒になって５〜６員環を形成することができ、必要により３０個までの炭素原子を含む炭化水素基で更に置換されていてもよい。商用される酸無水物の例として、アルキル無水コハク酸及びアルケニル無水コハク酸並びに特にイソオクタデセニル無水コハク酸が挙げられる。
【０００８】
【化１５】
【０００９】
本発明の方法はセルロース繊維を含む懸濁液に陰イオン又は陽イオン水性サイジング分散液を添加することを含み、即ち、分散系と称し得る分散液中に存在する分散剤及び／又は安定剤は夫々全体としての陰イオン電荷又は陽イオン電荷を有する。この分散系は分散液又はエマルジョンの生成を促進するあらゆる薬剤、例えば、多価電解質、表面活性剤及び電解質により例示される分散剤及び／又は安定剤を含んでもよい。陰イオン水性サイジング分散液は陽イオン化合物、即ち、陽イオン多価電解質（全体として陽イオン電荷を有する陽イオン又は両性多価電解質）及び／又は陽イオン表面活性剤及び／又は当業者に知られているあらゆるその他の陽イオン化合物を含んでもよいが、分散系の全体としての電荷が陰イオンであることを条件とする。一方、陽イオン水性サイジング分散液は陰イオン化合物、即ち、陰イオン多価電解質（全体として陰イオン電荷を有する陰イオン又は両性の多価電解質）及び／又は陰イオン表面活性剤及び／又は当業者に知られているあらゆるその他の陰イオン化合物を含んでもよいが、分散系の全体としての電荷が陰イオンであることを条件とする。サイジング分散液の陰イオン電荷又は陽イオン電化はゼータマスターＳバージョンＰＣＳにより測定し得る。
【００１０】
（発明を実施するための最良の形態）
本発明の好ましい実施態様によれば、前記陰イオン又は陽イオンサイジング分散液は一つ以上の芳香族基を有する陽イオン有機ポリマー及び／又は一つ以上の芳香族基を有する陰イオンポリマーを含む。この陽イオン有機ポリマー及び陰イオンポリマーはサイジング促進剤中に含まれる以下に記載されるもののいずれであってもよい。
【００１１】
懸濁液に添加される陰イオン又は陽イオンサイジング分散液は全分散液／エマルジョンを基準として０．１〜５０重量％、好適には２０重量％以上のサイジング剤含量を有し得る。ケテン二量体サイジング剤を含む分散液は全分散液を基準として５〜５０重量％、好ましくは１０〜３５重量％のケテン二量体含量を有してもよい。酸無水物サイジング剤を含む、分散液、又はエマルジョンは全分散液／エマルジョンを基準として０．１〜３０重量％、好適には１〜２０重量％の酸無水物含量を有してもよい。非セルロース反応性サイジング剤を含む分散液は好適には５〜５０重量％、好ましくは１０〜３５重量％のサイジング剤含量を有する。一つ以上の芳香族基を有する陰イオンポリマー及び／又は陽イオンポリマーがサイジング分散液中に含まれる場合、それらはサイジング剤を基準として約０．１重量％〜約１５重量％の量で存在することが好適である。
【００１２】
セルロース繊維を含む水性懸濁液に添加されるサイジング剤の量はセルロース繊維及び任意のてん料の乾燥重量を基準として０．０１〜５重量％、好適には０．０５〜１．０重量％であってもよく、この場合、用量はサイジングされるパルプ又は紙の品質、サイジング剤及びサイジングのレベルに依存する。
【００１３】
本発明によれば、陰イオン又は陽イオンサイジング分散液並びに一つ以上の芳香族基を有する陽イオン有機ポリマー及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤が水性懸濁液に別々に添加される。サイジング分散液はサイジング促進剤中に含まれるのと同じポリマーを含んでもよいが、サイジングに関する有意な改良はサイジング促進剤及びサイジング分散液がセルロース懸濁液に別々に添加される場合にのみ観察される。別々の添加はサイジング分散液（これはサイジング促進剤のポリマーのいずれかを含んでもよい）及びサイジング促進剤がセルロース懸濁液（濃厚原液）に異なる位置で、又は実質的に同じ位置であるが、時間的に分離されて添加されることを意味する。更に、サイジング促進剤を生成する陽イオン有機ポリマー及び陰イオンポリマーがまた別々に添加されることが好適である。陰イオンポリマーはサイジング分散液及び陽イオン有機ポリマーの両方の後に懸濁液に添加されることが好ましい。
【００１４】
本発明の好ましい実施態様によれば、紙のサイジング方法はセルロース繊維、及び任意のてん料を含む水性懸濁液に、サイジング剤及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含む陰イオン又は陽イオンサイジング分散液（懸濁液に添加されるサイジング剤の量は乾燥繊維を基準として約０．０１重量％から約５．０重量％までである）、並びに好適には陽イオン多糖又は陽イオンビニル付加ポリマーである一つ以上の芳香族基を有する陽イオンポリマー、及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤（懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３．０重量％までであり、かつ懸濁液に添加される陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３．０重量％までである）を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加する。
【００１５】
本発明の更に別の好ましい実施態様によれば、陰イオン又は陽イオンサイジング分散液はサイジング剤、一つ以上の芳香族基を有する陽イオン有機ポリマー、例えば、陽イオン多糖又は陽イオンビニル付加ポリマー、及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含み、陰イオンポリマーは段階成長ポリマー又は天然産芳香族ポリマーであることが好適である。
一つ以上の芳香族基を有する陽イオンポリマーは構造式（Ｉ）：
【００１６】
【化１６】
を有する陽イオン多糖、又は一般式（ＩＩ）：
【００１７】
【化１７】
により表される陽イオンモノマー又は陽イオンモノマーを含むモノマー混合物を重合することにより得られたビニル付加ポリマーであることが好適である。一つ以上の芳香族基を有する陽イオンポリマーは構造式（Ｉ）：
【００１８】
【化１８】
を有する陽イオン多糖であることが更に好ましい。
【００１９】
一つ以上の芳香族基を有する陽イオン有機ポリマー
サイジング促進剤の陽イオン有機ポリマー（また好適にはサイジング分散液中に存在する）は天然源又は合成源から誘導でき、線状、分岐又は架橋であってもよい。この陽イオンポリマーは水溶性又は水分散性であることが好ましい。好適な陽イオンポリマーの例として、陽イオン多糖、例えば、澱粉、グアーゴム、セルロース、キチン、キトサン、グリカン、ガラクタン、グルカン、キサンタンゴム、ペクチン、マンナン、デキストリン、好ましくは澱粉及びグアーゴム（好適な澱粉はジャガイモ、トウモロコシ、小麦、タピオカ、米、ワックス状トウモロコシ、大麦等を含む）；陽イオン合成有機ポリマー、例えば、陽イオン鎖成長ポリマー、例えば、アクリレート、アクリルアミド及びビニルアミドをベースとするポリマーのような陽イオンビニル付加ポリマー、及び陽イオン段階成長ポリマー、例えば、陽イオンポリウレタンが挙げられる。多糖、即ち、澱粉、及び芳香族基を有するアクリルアミドをベースとするポリマーのような陽イオンビニル付加ポリマーから選ばれた陽イオン有機ポリマーが特に好ましい。
【００２０】
前記陽イオン有機ポリマーの芳香族基はポリマー主鎖又はポリマー主鎖に結合される置換基、好ましくは置換基中に存在し得る。好適な芳香族基の例として、アリール基、アラルキル基及びアルカリール基、例えば、フェニル基、フェニレン基、ナフチル基、キシリレン基、ベンジル基及びフェニルエチル基、好ましくはベンジル基、窒素含有芳香族（アリール）基、例えば、ピリジニウム及びキノリニウム、並びにこれらの基の誘導体が挙げられる。陽イオンポリマー並びに陽イオンポリマーを調製するのに使用されるモノマー中に存在し得る陽イオンに荷電された基の例として、四級アンモニウム基、ターシャリーアミノ基及びこれらの酸付加塩が挙げられる。
【００２１】
好ましい実施態様によれば、芳香族基を有する陽イオン有機ポリマーは陽イオン多糖から選ばれる。多糖の芳香族基は多糖中に存在する窒素又は酸素のようなヘテロ原子に結合されてもよく、ヘテロ原子は、例えば、それが窒素である場合には必要により荷電されていてもよい。芳香族基はまたヘテロ原子を含む基、例えば、アミド、エステル又はエーテルに結合されてもよく、これらの基は、例えば、原子の鎖を介して、多糖主鎖に結合されてもよい。好適な芳香族基及び芳香族基を含む基の例として、アリール基及びアラルキル基、例えば、フェニル、フェニレン、ナフチル、フェニレン、キシリレン、ベンジル及びフェニルエチル；窒素含有芳香族（アリール）基、例えば、ピリジニウム及びキノリニウム、並びに前記芳香族基に結合された一つ以上の置換基がヒドロキシル、ハライド、例えば、塩化物、ニトロ、及び１〜４個の炭素原子を有する炭化水素基から選ばれる場合にはこれらの基の誘導体が挙げられる。
前記陽イオン有機ポリマーは一般構造式（Ｉ）：
【００２２】
【化１９】
を有する陽イオン多糖から選ばれることが好ましい。
【００２３】
前記芳香族基変性陽イオン多糖は広範囲にわたって変化する置換度を有し得る。陽イオン置換度（ＤＳｃ）は０．０１〜０．５、好適には０．０２〜０．３、好ましくは０．０２５〜０．２であってもよく、芳香族置換度（ＤＳＡｒ）は０．０１〜０．５、好適には０．０２〜０．３、好ましくは０．０２５〜０．２であってもよく、また陰イオン置換度（ＤＳＡ）は０〜０．２、好適には０〜０．１、好ましくは０〜０．０５であってもよい。
【００２４】
前記多糖は既知の方法で陽イオン基及び／又は芳香族基を含む一種以上の薬剤を使用して多糖を陽イオン及び芳香族変性にかけることにより、例えば、その薬剤をアルカリ物質、例えば、アルカリ金属又はアルカリ土類金属の水酸化物の存在下で多糖と反応させることにより調製し得る。陽イオン及び芳香族変性にかけられる多糖はノニオン、陰イオン、両性又は陽イオンであってもよい。好適な変性剤として、ノニオン薬剤、例えば、アラルキルハライド、例えば、塩化ベンジル及び臭化ベンジル；エピクロロヒドリンと先に定義された芳香族基を含む少なくとも一つの置換基を有するジアルキルアミンの反応生成物（３−ジアルキルアミノ−１，２−エポキシプロパンを含む）；及び陽イオン薬剤、例えば、エピクロロヒドリンと先に定義された芳香族基を含む少なくとも一つの置換基を有する三級アミン（アルカリールジアルキルアミン、例えば、ジメチルベンジルアミンを含む）の反応生成物；アリールアミン、例えば、ピリジン及びキノリンが挙げられる。この型の好適な陽イオン薬剤として、２，３−エポキシプロピルトリアルキルアンモニウムハライド及びハロヒドロキシプロピルトリアルキルアンモニウムハライド、例えば、Ｎ−（３−クロロ−２−ヒドロキシプロピル）−Ｎ−（疎水性アルキル）−Ｎ，Ｎ−ジ（低級アルキル）アンモニウムクロリド及びＮ−グリシジル−Ｎ−（疎水性アルキル）−Ｎ，Ｎ−ジ（低級アルキル）アンモニウムクロリド（その芳香族基は先に定義されたとおりであり、疎水性アルキルは特にオクチル、デシル及びドデシルであり、かつ低級アルキルはメチル又はエチルである）；並びにハロヒドロキシプロピル−Ｎ，Ｎ−ジアルキル−Ｎ−アルカリールアンモニウムハライド及びＮ−グリシジル−Ｎ−（アルカリール）−Ｎ，Ｎ−ジアルキルアンモニウムクロリド、例えば、Ｎ−（３−クロロ−２−ヒドロキシプロピル）−Ｎ−（アルカリール）−Ｎ，Ｎ−ジ（低級アルキル）アンモニウムクロリド（アルカリール及び低級アルキル基は先に定義されたとおりである）、特にＮ−（３−クロロ−２−ヒドロキシプロピル）−Ｎ−ベンジル−Ｎ，Ｎ−ジメチルアンモニウムクロリド；及びＮ−（３−クロロ−２−ヒドロキシプロピル）ピリジニウムクロリドが挙げられる。一般に、ノニオン芳香族薬剤を使用する場合、多糖は疎水性変性の前後に当業界で知られている陽イオン薬剤のいずれかを使用することにより陽イオンにされることが好適である。好適な陽イオン変性剤及び／又は芳香族変性剤、芳香族基変性多糖及びそれらの調製方法の例として、米国特許第４，６８７，５１９号及び同第５，４６３，１２７号；国際特許出願ＷＯ ９４／２４１６９、欧州特許出願第１８９９３５号；並びにＳ．Ｐ． Ｐａｔｅｌ， Ｒ．Ｇ． Ｐａｔｅｌ及びＶ．Ｓ． Ｐａｔｅｌ， Ｓｔａｒｃｈ／Ｓｔａｒｋｅ，４１（１９８９），Ｎｏ．５，ｐｐ．１９２−１９６に記載されたものが挙げられ、これらの教示が参考として本明細書に含まれる。
【００２５】
更に別の好ましい実施態様によれば、陽イオン有機ポリマーは芳香族基を有する少なくとも一種のモノマー、好適にはエチレン性不飽和モノマーを含む一種以上のモノマーから調製されたホモポリマー及びコポリマーから選ばれる。陽イオンポリマーは線状又は分岐であってもよい。合成ポリマーの芳香族基はポリマー主鎖中に存在してもよく、又は好ましくは、それはポリマー主鎖に結合され、もしくはそれから延びるペンダント基であってもよく、又はポリマー主鎖に結合され、もしくはそれから延びるペンダント基中に存在してもよい。好適な芳香族（アリール）基として、必要により置換されていてもよい、フェニル基、必要により置換されていてもよい、フェニレン基、及び必要により置換されていてもよい、ナフチル基を含むもの、例えば、一般式−Ｃ６Ｈ５、−Ｃ６Ｈ４−、−Ｃ６Ｈ３−、及び−Ｃ６Ｈ２−を有する基、例えば、フェニレン（−Ｃ６Ｈ４−）、キシリレン（−ＣＨ２−Ｃ６Ｈ４−ＣＨ２−）、フェニル（−Ｃ６Ｈ５）、ベンジル（−ＣＨ２−Ｃ６Ｈ５）、フェネチル（−ＣＨ２ＣＨ２−Ｃ６Ｈ５）、及び置換フェニル（例えば、−Ｃ６Ｈ４−Ｙ、−Ｃ６Ｈ３Ｙ２、及び−Ｃ６Ｈ２Ｙ３）（式中、フェニル環に結合された一つ以上の置換基（Ｙ）はヒドロキシル、ハライド、例えば、塩化物、ニトロ、及び１〜４個の炭素原子を有する炭化水素基から選ばれてもよい）の形態の基が挙げられる。
【００２６】
前記陽イオンポリマーはビニル付加ポリマーであることが好ましい。本明細書に使用される“ビニル付加ポリマー”という用語は、一種以上のビニルモノマー又はエチレン性不飽和モノマー（例えば、アクリルアミドをベースとするモノマー及びアクリレートをベースとするモノマーが挙げられる）の付加重合により調製されたポリマーを表す。この陽イオンポリマーは一般式（ＩＩ）：
【００２７】
【化２０】
（式中、Ｒ１はＨ又はＣＨ３であり、Ｒ２及びＲ３は夫々好ましくは１〜３個の炭素原子、通常１〜２個の炭素原子を有するアルキル基であり、Ａ１はＯ又はＮＨであり、Ｂ１は２〜８個の炭素原子、好適には２〜４個の炭素原子を有するアルキレン基、又はヒドロキシプロピレン基であり、Ｑは芳香族基、好適にはフェニル基又は置換フェニル基を含む置換基（これは通常１〜３個の炭素原子、好適には１〜２個の炭素原子を有するアルキレン基により窒素に結合し得る）であり、好ましくはＱはベンジル基（−ＣＨ２−Ｃ６Ｈ５）であり、かつＸ−は陰イオン対イオン、通常塩化物のようなハライドである）
により表される陽イオンモノマー又は陽イオンモノマーを含むモノマー混合物を重合することにより得られた陽イオンビニル付加ポリマーから選ばれることが好適である。一般式（ＩＩ）により表される好適なモノマーの例として、ジアルキルアミノアルキルアクリレート、ジアルキルアミノアルキルメタクリレート、例えば、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート及びジメチルアミノヒドロキシプロピルアクリレート、ジメチルアミノヒドロキシプロピルメタクリレート、並びにジアルキルアミノアルキルアクリルアミド、ジアルキルアミノアルキルメタクリルアミド、例えば、ジメチルアミノエチルアクリルアミド、ジメチルアミノエチルメタクリルアミド、ジエチルアミノエチルアクリルアミド、ジエチルアミノエチルメタクリルアミド、ジメチルアミノプロピルアクリルアミド、ジメチルアミノプロピルメタクリルアミド、及びジエチルアミノプロピルアクリルアミド、ジエチルアミノプロピルメタクリルアミドを塩化ベンジルで処理することにより得られた四級モノマーが挙げられる。一般式（ＩＩ）の好ましい陽イオンモノマーとして、ジメチルアミノエチルアクリレートベンジルクロリド四級塩及びジメチルアミノエチルメタクリレートベンジルクロリド四級塩が挙げられる。
【００２９】
前記陽イオンビニル付加（合成陽イオン）ポリマーは芳香族基を有する陽イオンモノマーから調製されたホモポリマー又は芳香族基を有する陽イオンモノマー及び一種以上の共重合性モノマーを含むモノマー混合物から調製されたコポリマーであってもよい。好適な共重合性ノニオンモノマーとして、一般式（ＩＩＩ）：
【００３０】
【化２１】
（式中、Ｒ４はＨ又はＣＨ３であり、Ｒ５及びＲ６は夫々Ｈ又は炭化水素基、好適には１〜６個、好適には１〜４個、通常１〜２個の炭素原子を有するアルキルであり、Ａ２はＯ又はＮＨであり、Ｂ２は２〜８個の炭素原子、好適には２〜４個の炭素原子のアルキレン基、又はヒドロキシプロピレン基であり、又はＡ及びＢは両方とも何もなく、それによりＣとＮの間に単結合がある（Ｏ＝Ｃ−ＮＲ５Ｒ６））により表されるモノマーが挙げられる。この型の好適な共重合性モノマーの例として、アクリルアミド、メタクリルアミド；Ｎ−アルキルアクリルアミド、Ｎ−アルキルメタクリルアミド及びＮ，Ｎ−ジアルキルアクリルアミド、Ｎ，Ｎ−ジアルキルメタクリルアミドのようなアクリルアミドをベースとするモノマー、例えば、Ｎ−ｎ−プロピルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ−ｎ−ブチルアクリルアミド、Ｎ−ｎ−ブチルメタクリルアミド、Ｎ−イソブチルアクリルアミド、Ｎ−イソブチルメタクリルアミド及びＮ−ｔ−ブチルアクリルアミド、Ｎ−ｔ−ブチルメタクリルアミド；並びにジアルキルアミノアルキルアクリルアミド、ジアルキルアミノアルキルメタクリルアミド、例えば、ジメチルアミノエチルアクリルアミド、ジメチルアミノエチルメタクリルアミド、ジエチルアミノエチルアクリルアミド、ジエチルアミノエチルメタクリルアミド、ジメチルアミノプロピルアクリルアミド、ジメチルアミノプロピルメタクリルアミド及びジエチルアミノプロピルアクリルアミド、ジエチルアミノプロピルメタクリルアミド；ジアルキルアミノアルキルアクリレート、ジアルキルアミノアルキルメタクリレートのようなアクリレートをベースとするモノマー、例えば、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、ｔ−ブチルアミノエチルアクリレート、ｔ−ブチルアミノエチルメタクリレート及びジメチルアミノヒドロキシプロピルアクリレート；並びにビニルアミド、例えば、Ｎ−ビニルホルムアミド及びＮ−ビニルアセトアミドが挙げられる。好ましい共重合性ノニオンモノマーとして、アクリルアミド及びメタクリルアミド、即ち、アクリルアミド、メタクリルアミドが挙げられ、主ポリマーはアクリルアミドをベースとするポリマーであることが好ましい。
好適な共重合性陽イオンモノマーとして、一般式（ＩＶ）：
【００３２】
【化２２】
（式中、Ｒ７はＨ又はＣＨ３であり、Ｒ８、Ｒ９及びＲ１０は夫々Ｈ又は好ましくは炭化水素基、好適には１〜３個の炭素原子、通常１〜２個の炭素原子を有するアルキルであり、Ａ３はＯ又はＮＨであり、Ｂ３は２〜４個の炭素原子、好適には２〜４個の炭素原子のアルキレン基、又はヒドロキシプロピレン基であり、かつＸ−は陰イオン対イオン、通常メチルスルフェート又は塩化物のようなハライドである）
により表されるモノマーが挙げられる。好適な陽イオン共重合性モノマーの例として、通常ＨＣｌ、Ｈ２ＳＯ４等のような酸、又は塩化メチル、ジメチル硫酸等のような四級化剤を使用して調製された、上記ジアルキルアミノアルキルアクリレート、ジアルキルアミノアルキルメタクリレート及びジアルキルアミノアルキルアクリルアミド、ジアルキルアミノアルキルメタクリルアミドの酸付加塩及び四級アンモニウム塩；並びにジアリルジメチルアンモニウムクロリドが挙げられる。好ましい共重合性陽イオンモノマーとして、ジメチルアミノエチルアクリレートメチルクロリド四級塩、ジメチルアミノエチルメタクリレートメチルクロリド四級塩及びジアリルジメチルアンモニウムクロリドが挙げられる。アクリル酸、メタクリル酸、種々のスルホン化ビニル付加モノマー等のような共重合性陰イオンモノマーがまた好ましくは少量で使用し得る。
【００３４】
前記陽イオンビニル付加モノマーは一般に１〜９９モル％、好適には２〜５０モル％、好ましくは５〜２０モル％の好ましくは一般式（ＩＩ）により表される、芳香族基を有する陽イオンモノマー、及び９９〜１モル％、好適には９８〜５０モル％、好ましくは９５〜８０モル％のその他の共重合性モノマー（これは好ましくはアクリルアミド又はメタクリルアミドを含む）を含むモノマー混合物から調製でき、モノマー混合物は好適には９８〜５０モル％、好ましくは９５〜８０モル％のアクリルアミド又はメタクリルアミドを含み、％の合計は１００である。
【００３５】
前記陽イオンポリマーはまた芳香族基を含む一種以上のモノマーの縮合反応により調製されたポリマーから選ばれてもよい。このようなモノマーの例として、トルエンジイソシアネート、ビスフェノールＡ、フタル酸、無水フタル酸等が挙げられ、これらは陽イオンポリウレタン、陽イオンポリアミドアミン等の調製に使用し得る。
【００３６】
また、有機ポリマーは芳香族基を含む薬剤を使用する芳香族変性にかけられたポリマーであってもよい。この型の好適な変性剤として、塩化ベンジル、臭化ベンジル、Ｎ−（３−クロロ−２−ヒドロキシプロピル）−Ｎ−ベンジル−Ｎ，Ｎ−ジメチルアンモニウムクロリド、及びＮ−（３−クロロ−２−ヒドロキシプロピル）ピリジニウムクロリドが挙げられる。このような芳香族変性に適したポリマーとして、ビニル付加ポリマーが挙げられる。ポリマーが変性剤により四級化し得る三級窒素を含む場合、このような薬剤の使用は通常ポリマーが陽イオンにされることをもたらす。また、芳香族変性にかけられるポリマーは陽イオン、例えば、陽イオンビニル付加ポリマーであってもよい。
【００３７】
通常、ビニル付加ポリマーの電荷密度は乾燥ポリマー１ｇ当り０．１〜６．０ミリ当量、好適には０．２〜４．０ミリ当量、好ましくは０．５〜３．０ミリ当量の範囲内である。合成ポリマーの重量平均分子量は通常少なくとも約５００，０００、好適には約１，０００，０００以上、好ましくは約２，０００，０００以上である。上限は重要ではない。それは約５０，０００，０００、通常３０，０００，０００、好適には２５，０００，０００であってもよい。
【００３８】
一つ以上の芳香族基を有する陰イオンポリマー
前記サイジング促進剤中に含まれる芳香族基を有する陰イオンポリマー（また必要により本発明のサイジング分散液中に含まれてもよい）は段階成長ポリマー、多糖又は天然産芳香族ポリマーである。本明細書に使用される“段階成長ポリマー”という用語は、段階成長重合により得られたポリマーを表し、これらはまた夫々段階反応ポリマー及び段階反応重合と称される。該促進剤中に含まれる陰イオンポリマーは段階成長ポリマー、多糖又は天然産芳香族ポリマーであることが好ましいが、陰イオンポリマーはメラミンスルホン酸縮合ポリマーではないことを条件とする。陰イオンポリマーは段階成長ポリマー又は天然産芳香族ポリマーであってもよい。本発明の陰イオンポリマーは線状、分岐又は架橋であってもよい。陰イオンポリマーは普通水溶性又は水分散性である。陰イオンポリマーは有機であることが好ましい。好ましい陰イオン芳香族ポリマーは縮合ナフタレンスルホネートのようなナフタレンスルホネート縮合ポリマー、及び変性リグニンポリマー、例えば、リグニンスルホネートである。
【００３９】
前記陰イオンポリマーの芳香族基はポリマー主鎖又はポリマー主鎖に結合されている置換基中に存在し得る。好適な芳香族基の例として、アリール基、アラルキル基及びアルカリール基並びにこれらの誘導体、例えば、フェニル、トリル、ナフチル、フェニレン、キシリレン、ベンジル、フェニルエチル及びこれらの基の誘導体が挙げられる。陰イオンポリマー並びに陰イオンポリマーを調製するのに使用されるモノマー中に存在し得る陰イオンに荷電された基の例として、陰イオン電荷を有する基及び水に溶解又は分散された場合に陰イオン電荷を有する酸基（本明細書中でこれらの基は集約して陰イオン基と称される）、例えば、ホスフェート、ホスホネート、スルフェート、スルホン酸、スルホネート、カルボン酸、カルボキシレート、アルコキシド及びフェノール基、即ち、ヒドロキシ置換フェニル及びヒドロキシ置換ナフチルが挙げられる。陰イオン電荷を有する基は通常アルカリ金属、アルカリ土類金属又はアンモニアの塩である。
【００４０】
本発明の好適な陰イオン段階成長重合生成物の例として、縮合ポリマー、即ち、段階成長縮合重合により得られたポリマー、例えば、ホルムアルデヒドの如きアルデヒドと一つ以上の陰イオン基を含む一種以上の芳香族化合物、詳しくは縮合ナフタレンスルホネート型ポリマー、及び尿素の如き縮合重合に有益な任意のその他のコモノマーの縮合物が挙げられる。陰イオン基を含む好適な芳香族化合物の例として、フェノール化合物及びナフトール化合物、例えば、フェノール、ナフトール、レゾルシノール及びこれらの誘導体、芳香族酸及びこれらの塩、例えば、フェニル、フェノール、ナフチル及びナフトールの酸及び塩、通常スルホン酸及びスルホン酸塩、例えば、ベンゼンスルホン酸及びベンゼンスルホン酸塩、キシレンスルホン酸及びキシレンスルホン酸塩、ナフタレンスルホン酸及びナフタレンスルホン酸塩、フェノールスルホン酸及びフェノールスルホン酸塩が挙げられる。
【００４１】
本発明の更に好適な陰イオン段階成長重合生成物の例として、付加ポリマー、即ち、段階成長付加重合により得られたポリマー、例えば、芳香族イソシアネート及び／又は芳香族アルコールを含むモノマー混合物から調製された陰イオンポリウレタンが挙げられる。好適な芳香族イソシアネートの例として、ジイソシアネート、例えば、トルエン−２，４−ジイソシアネート及びトルエン−２，６−ジイソシアネート並びにジフェニルメタン−４，４’−ジイソシアネートが挙げられる。好適な芳香族アルコールの例として、２価アルコール、即ち、ジオール、例えば、ビスフェノールＡ、フェニルジエタノールアミン、グリセロールモノテレフタレート及びトリメチロールプロパンモノテレフタレートが挙げられる。フェノール及びこれらの誘導体の如き１価芳香族アルコールがまた使用されてもよい。モノマー混合物はまた非芳香族のイソシアネート及び／又はアルコール、通常ジイソシアネート及びジオール、例えば、ポリウレタンの調製に有益であると知られているもののいずれかを含んでもよい。陰イオン基を含む好適なモノマーの例として、トリオール、例えば、トリメチロールエタン、トリメチロールプロパン及びグリセロールと、ジカルボン酸又はこれらの酸無水物、例えば、コハク酸及び無水コハク酸、テレフタル酸及び無水テレフタル酸のモノエステル反応生成物、例えば、グリセロールモノスクシネート、グリセロールモノテレフタレート、トリメチロールプロパンモノスクシネート、トリメチロールプロパンモノテレフタレート、Ｎ，Ｎ−ビス−（ヒドロキシエチル）−グリシン、ジ−（ヒドロキシメチル）プロピオン酸、Ｎ，Ｎ−ビス−（ヒドロキシエチル）−２−アミノエタンスルホン酸等が挙げられ、必要により、また通常、塩基、例えば、アルカリ金属及びアルカリ土類金属の水酸化物、例えば、水酸化ナトリウム、アンモニア又はアミン、例えば、トリエチルアミンとの反応と組み合わされ、それによりアルカリ金属、アルカリ土類金属又はアンモニウム対イオンを生成する。
【００４２】
本発明の好適な陰イオン鎖成長重合生成物の例として、芳香族基を有する少なくとも一種のモノマー及び通常ノニオンモノマー、例えば、アクリレートをベースとするモノマー及びアクリルアミドをベースとするモノマーと共重合される、陰イオン基を有する少なくとも一種のモノマーを含むビニルモノマー又はエチレン性不飽和モノマーの混合物から得られた陰イオンビニル付加ポリマーが挙げられる。好適な陰イオンモノマーの例として、アクリル酸、メタクリル酸及びパラビニルフェノール（ヒドロキシスチレン）が挙げられる。
【００４３】
好適な陰イオン多糖の例として、澱粉、グアーゴム、セルロース、キチン、キトサン、グリカン、ガラクタン、グルカン、キサンタンゴム、ペクチン、マンナン、デキストリン、好ましくは澱粉、グアーゴム及びセルロース誘導体が挙げられ、好適な澱粉として、ジャガイモ、トウモロコシ、小麦、タピオカ、米、ワックス状トウモロコシ及び大麦、好ましくはジャガイモが挙げられる。多糖中の陰イオン基は生来のものであってもよく、かつ／又は化学処理により導入されてもよい。多糖中の芳香族基は当業界で知られている化学方法により導入し得る。
【００４４】
本発明の好適な（変性）天然産芳香族陰イオンポリマーの例として、クラフトリグニン、例えば、ホルムアルデヒドと共重合されたリグニン付加物及びスルホン化リグニンのような変性リグニンポリマー、例えば、リグニンスルホネート及びタンニン抽出物、即ち、幾つかの木材種の樹皮の有機抽出物中に存在する天然産ポリフェノール物質が挙げられる。
【００４５】
芳香族基を有する陰イオンポリマーは段階成長ポリマー、多糖及び天然産芳香族ポリマーから選ばれることが好適である。縮合ナフタレンスルホネートのような縮合ナフタレンスルホネート型ポリマー及び変性リグニンポリマー、例えば、リグニンスルホネートが好ましい。
【００４６】
前記陰イオンポリマーの重量平均分子量は、とりわけ、使用されるポリマーの型に依存して広い制限内で変化することができ、通常それは少なくとも約５００、好適には約２，０００以上、好ましくは約５，０００以上である。この上限は重要ではない。それは約２００，０００，０００、通常１５０，０００，０００、好適には１００，０００，０００、好ましくは１，０００，０００であってもよい。
【００４７】
前記陰イオンポリマーは、とりわけ、使用されるポリマーの型に依存して広範囲にわたって変化する陰イオン置換度（ＤＳＡ）を有し得る。ＤＳＡは通常０．０１〜２．０、好適には０．０２〜１．８、好ましくは０．０２５〜１．５であり、芳香族置換度（ＤＳＱ）は０．００１〜１．０、通常０．０１〜０．８、好適には０．０２〜０．７、好ましくは０．０２５〜０．５であってもよい。陰イオンポリマーが陽イオン基を含む場合、陽イオン置換度（ＤＳＣ）は、例えば、０〜０．２、好適には０〜０．１、好ましくは０〜０．０５であってもよく、その陰イオンポリマーは全体として陰イオン電荷を有する。通常、陰イオンポリマーの陰イオン電荷密度は乾燥ポリマー１ｇ当り０．１〜６．０ミリ当量、好適には０．５〜５．０ミリ当量、好ましくは１．０〜４．０ミリ当量の範囲内である。
【００４８】
芳香族基を有する陽イオン有機ポリマー及びサイジング促進剤の芳香族基を有する陰イオンポリマーはサイジング分散液の添加とは別々に、かつ、とりわけ、原料の型、塩含量、塩の型、てん料含量、てん料の型、添加の時点等に応じて広い制限内で変化し得る量であらゆる順序で水性懸濁液（原料）に添加し得る。一般に、これらのポリマーはそれらを添加しない場合に得られるよりも良好なサイジングを与える量で添加され、通常陽イオン有機ポリマーは陰イオンポリマーを添加する前に原料に添加される。陽イオンポリマーは乾燥原料物質を基準として少なくとも０．００１重量％、しばしば少なくとも０．００５重量％の量で通常添加されるが、その上限は通常３重量％、好適には２．０重量％である。陰イオンポリマーは乾燥原料物質を基準として少なくとも０．００１重量％、しばしば少なくとも０．００５重量％の量で通常添加されるが、その上限は通常３重量％、好適には１．５重量％である。
【００４９】
前記陽イオン有機ポリマー及び陰イオンポリマーとは別に、サイジング促進剤はサイジング効率を改良するその他の化合物、例えば、陰イオン微粒状材料、例えば、シリカをベースとする粒子及びスメクタイト型のクレー、低分子量陽イオン有機ポリマー、ミョウバン、アルミン酸塩、塩化アルミニウム、硝酸アルミニウムのようなアルミニウム化合物、及びポリアルミニウム化合物、例えば、ポリ塩化アルミニウム、ポリ硫酸アルミニウム、塩化物イオン及び硫酸イオンの両方を含むポリアルミニウム化合物、ポリケイ酸硫酸アルミニウム及びこれらの混合物、陰イオンビニル付加ポリマー並びにこれらの組み合わせを含んでもよい。
【００５０】
本発明の方法は高導電率を有する、セルロース繊維、及び任意のてん料を含む懸濁液からの紙の製造に使用されることが好ましい。通常、原料の導電率は少なくとも０．２０ｍＳ／ｃｍ、好適には少なくとも０．５ｍＳ／ｃｍ、好ましくは少なくとも３．５ｍＳ／ｃｍである。非常に良好なサイジング結果が５．０ｍＳ／ｃｍ以上、更には７．５ｍＳ／ｃｍ以上の導電率レベルで観察された。導電率は通常の装置、例えば、クリスチャン・バーナーにより供給されるＷＴＷ ＬＦ ５３９装置により測定し得る。上記値は抄紙機のヘッドボックスに供給され、もしくはその中に存在するセルロース懸濁液の導電率を測定することにより、又は懸濁液を脱水することにより得られた白水の導電率を測定することにより測定されることが好適である。高導電率レベルは塩（電解質）の高含量を意味し、この場合、種々の塩はアルカリ金属、例えば、Ｎａ＋及びＫ＋、アルカリ土類金属、例えば、Ｃａ２＋及びＭｇ２＋、アルミニウムイオン、例えば、Ａｌ３＋、Ａｌ（ＯＨ）２＋及びポリアルミニウムイオンのような１価、２価及び多価の陽イオン、並びにハライド、例えば、Ｃｌ−、硫酸イオン、例えば、ＳＯ４ ２−及びＨＳＯ４ −、炭酸イオン、例えば、ＣＯ３ ２−及びＨＣＯ３ −、ケイ酸イオン及び低級有機酸のような１価、２価及び多価の陰イオンをベースとし得る。本発明は高含量の２価及び多価の陽イオンの塩を有する原料からの紙の製造に特に有益であり、通常、陽イオン含量は少なくとも２００ｐｐｍ、好適には少なくとも３００ｐｐｍ、好ましくは少なくとも４００ｐｐｍである。塩は特に総合工場で原料を生成するのに使用されるセルロース繊維及びてん料に由来することがあり、この場合、パルプ工場からの濃縮された水性繊維懸濁液が通常水と混合されて製紙工場における紙製造に適した希薄な懸濁液を生成する。塩はまた原料に導入された種々の添加剤、その方法に供給される新鮮な水に由来することがあり、又は随時添加等されてもよい。更に、塩の含量は白水が徹底的に循環される方法で通常高く、これはその方法で循環している水中の塩のかなりの蓄積をもたらし得る。
【００５１】
更に、本発明は白水が徹底的に、即ち、高い白水密閉度で循環される場合、例えば、０〜３０トンの新鮮な水が製造される乾燥紙１トン当り使用され、通常２０トン未満、好適には１５トン未満、好ましくは１０トン未満、特別には５トン未満の新鮮な水／紙１トンが使用される場合の製紙方法を含む。その方法で得られた白水の循環は白水をセルロース繊維及び／又は任意のてん料と混合してサイジングされる懸濁液を生成することを含むことが好適である。それは白水をセルロース繊維、及び任意のてん料を含む懸濁液と混合することを含み、その後に懸濁液がサイジングのためのフォーミングワイヤに入ることが好ましい。
【００５２】
製紙に通常である更なる添加剤、例えば、付加的な乾燥強度増強剤、湿潤強度増強剤が本発明の添加剤と組み合わせて勿論使用し得る。セルロース懸濁液、又は原料はまた通常の型の無機てん料、例えば、カオリン、チャイナクレー、二酸化チタン、石膏、タルク並びに天然炭酸カルシウム及び合成炭酸カルシウム、例えば、チョーク、粉砕大理石及び沈降炭酸カルシウムを含んでもよい。
【００５３】
本発明の方法は紙の製造に使用される。本明細書に使用される“紙”という用語は、勿論、紙及びその製品だけでなく、その他のシート又はウェブのような製品、例えば、ボード及び板紙、並びにこれらの製品を含む。その方法はセルロースを含む繊維の異なる型の懸濁液からの紙の製造に使用でき、懸濁液は乾燥物質を基準として少なくとも２５重量％、好ましくは少なくとも５０重量％のこのような繊維を含むことが好適である。これらの懸濁液はケミカルパルプ、例えば、硫酸パルプ、亜硫酸パルプ及び有機溶剤パルプ、メカニカルパルプ、例えば、サーモメカニカルパルプ、ケモ−サーモメカニカルパルプ、リファイナパルプ及び砕木パルプ（広葉樹及び針葉樹の両方から）からの繊維をベースとすることができ、また必要により脱インキパルプからのリサイクル繊維、及びこれらの混合物をベースとし得る。本発明はリサイクル繊維及び脱インキパルプを含むパルプをベースとする懸濁液からの紙の製造に特に有益であり、このような源のセルロース繊維の含量は１００％まで、好適には２０％〜１００％であってもよい。
【００５４】
本発明が以下の実施例で更に説明されるが、これらは本発明を限定することを目的とするものではない。部数及び％は、特にことわらない限り、夫々重量部及び重量％に関する。
【００５５】
以下の全ての実施例において、サイジング分散液及びサイジング促進剤はセルロース懸濁液に別々に添加された。更に、前記促進剤が芳香族基を有する一種より多いポリマーを含んだ場合、これらのポリマーは互いに対し、かつ分散液に対し懸濁液に別々に添加された。
【００５６】
（実施例）
実施例１
ｃｏｂｂ６０試験を使用することにより、この方法のサイジング性能を評価した。アルキルケテン二量体、縮合ナフタレンスルホネート及びジ（水添牛脂）ジメチルアンモニウムクロリドを含む陰イオンサイジング分散液を調製した。このサイジング分散液は３０％のＡＫＤ含量を有し、ＡＫＤを基準として４％のジ（水添牛脂）ジメチルアンモニウムクロリド及び６％の縮合ナフタレンスルホネートを含んでいた。このサイジング分散液を５ｋｇ ＡＫＤ／乾燥原料１トンの量で原料に添加した。
【００５７】
試験２において、サイジング促進剤は縮合ナフタレンスルホネート（商標名タモール（登録商標）として入手し得る）及び窒素含有ベンジル基に関して０．０６５の陽イオン置換度ＤＳを有する陽イオン澱粉を含んでいた。試験１において、０．０６５の陽イオン置換を有する芳香族基を含まない陽イオン澱粉及びゾルとして用意された陰イオン無機シリカ粒子、即ち、陰イオン非芳香族ポリマーを完成紙料に添加した。
【００５８】
使用した完成紙料は８０重量％の漂白カバ／マツ（６０／４０）硫酸パルプ及び２０重量％のＣａＣＯ３をベースとし、２００ＣＳＦまで精製され、原料１リットル当り０．３ｇのＮａ２ＳＯ４を含み、４６１μＳ／ｃｍの導電率及び８．１のｐＨを有していた。
【００５９】
【表１】
実施例２
実施例１に記載されたのと同じ陰イオンサイジング分散液並びに窒素含有ベンジル基に関して０．０６５の陽イオン置換ＤＳを有する陽イオン澱粉及び陰イオン無機シリカ粒子を含むサイジング促進剤（試験１）；及び縮合ナフタレンスルホネート（商標名タモール（登録商標）として入手し得る）及び窒素含有ベンジル基に関して０．０６５の陽イオン置換ＤＳを有する陽イオン澱粉を含む促進剤（試験２）を添加することにより、その方法のサイジング性能を評価した（ｃｏｂｂ６０試験）。しかしながら、塩化カルシウムを完成紙料に添加して導電率を５０００μＳ／ｃｍに調節し、それにより高導電率を有する完成紙料を模擬した。
【００６１】
【表２】
実施例３
１５％のアルキルケテン二量体、２％の陽イオン澱粉、及びＡＫＤ（サイジング剤）を基準として０．６％のナトリウムリグノスルホネートを含む陽イオンサイジング分散液を使用してサイジング性能を評価した。サイジング促進剤中に含まれた成分及び成分の添加量（表３から明らかである）は、縮合ナフタレンスルホネート、０．０６５のＤＳを有する芳香族基を含まない陽イオン澱粉、０．０６５のＤＳを有する芳香族基を含む陽イオン澱粉及びゾルとして用意された陰イオン無機シリカ粒子を含んでいた。使用した原料は原料への塩化カルシウムの添加により８．１のｐＨ及び５０００μＳ／ｃｍの導電率を有する実施例２の原料であった。
【００６３】
【表３】
実施例４
８．９％の市販のアルキルケテン二量体、０．８９％のベンジル基を含む０．０６５のＤＳを有する芳香族置換陽イオン澱粉、及び０．２２％の商標名タモール（登録商標）として入手し得る縮合ナフタレンスルホネートを含む陰イオンサイジング分散液を調製した。その陰イオン分散液をケテン二量体を基準として０．０１１５％（乾燥ベース）の量で３０％のマツ、３０％のビー（Ｂｅｅ）、４０％のユーカリ、及び１５％の沈降ＣａＣＯ３を含むセルロース懸濁液（乾燥ベース）に添加した。懸濁液の導電率は５００μＳ／ｃｍであった。その懸濁液にまた０．０６５のＤＳを有するベンジル置換澱粉及び商標名タモール（登録商標）として入手し得る縮合ナフタレンスルホネートを含むサイジング促進剤を添加した（試験２）。
同じ懸濁液にまた同じ陰イオン分散液を添加した。しかしながら、この懸濁液に添加されたサイジング促進剤は芳香族ポリマーを含んでいなかった。このサイジング促進剤は芳香族基を有しない０．０６５のＤＳを有する陽イオン澱粉及びゾルとして用意された陰イオン無機シリカ粒子を含んでいた（試験１）。促進剤のポリマー及び分散液のサイジング剤（ＡＫＤ）の量を表４に示す。
【００６５】
【表４】
実施例５
この実施例において、懸濁液の導電率が５０００μＳ／ｃｍであった以外は実施例２と同じ分散液及びサイジング促進剤を使用した。この促進剤のポリマー及び分散液のサイジング剤（ＡＫＤ）の量を表５に示す。
【００６７】
【表５】
実施例６
Ｃｏｂｂ６０試験を使用することにより、この方法のサイジング性能を評価した。アルキルケテン二量体、縮合ナフタレンスルホネート及びジ（水添牛脂）ジメチルアンモニウムクロリドを含む陰イオンサイジング分散液を調製した。このサイジング分散液は３０％のＡＫＤ含量を有し、ＡＫＤを基準として４％のジ（水添牛脂）ジメチルアンモニウムクロリド及び６％の縮合ナフタレンスルホネートを含んでいた。このサイジング分散液を乾燥原料１トン当り０．３ｋｇのＡＫＤの量で添加した。
【００６９】
窒素含有ベンジル基に関して０．０６５の陽イオン置換ＤＳを有する陽イオン澱粉及び０．０６５の陽イオン置換ＤＳを有する澱粉を夫々縮合ナフタレンスルホネート及びメラミンスルホネートと組み合わせて使用した。
【００７０】
使用した完成紙料は８０％のカバ／マツ（６０／４０）硫酸パルプ及び２０重量％のＣａＣＯ３をベースとし、２００ＣＳＦまで精製され、原料１リットル当り０．３ｇを含み、５５５μＳ／ｃｍの導電率及びｐＨ８．２２を示した。
【００７１】
【表６】
(Technical field)
The present invention relates to anionic or cationic sizing dispersions, and cationic organic polymers with one or more aromatic groups, and step-grown polymers, polysaccharides and natural Adding a sizing accelerator comprising an anionic polymer having one or more aromatic groups that are aromatic polymers produced, forming the resulting suspension, including dewatering, the sizing dispersion and The present invention relates to a paper sizing method, wherein a sizing accelerator is separately added to an aqueous suspension.
[0002]
(Background technology)
Sizing agent dispersions or emulsions are used in papermaking to provide paper and paperboard with improved resistance to wetting and penetration by various liquids. The sizing dispersion is usually added to an aqueous suspension containing cellulose fibers, optional fillers and various additives. The aqueous suspension is fed to a headbox which discharges the suspension onto a wire, where a wet web of paper is formed. To the suspension are further added compounds such as ordinary starch and finely divided material, which promote the dewatering of the suspension on the wire. Water dewatered from the wire (called white water) is usually partially circulated in a papermaking process. Cellulose suspensions contain certain amounts of non-fibrous materials such as fillers, charged polymers, sizing agents and various charged contaminants, ie, anionic debris, electrolytes, colloidal materials, and the like. Non-fibrous materials have an effect on sizing efficiency and usually impair sizing efficiency. Large amounts of charged compounds, such as high contents of salts in the suspension, make the suspension increasingly difficult to size, ie to obtain paper with satisfactory sizing properties. Other compounds included in suspensions that impair sizing are various lipophilic wood extracts, which may be derived from recycled fibers and mechanical pulp. Increased amounts of added sizing agent often improve sizing, but result in increased accumulation of sizing agent in white water as well as high cost. Accumulation of non-fibrous materials as well as any other components present in the suspension will be even more pronounced in factories where white water is thoroughly circulated with only a small amount of fresh water introduced into the papermaking process. Thus, it is an object of the present invention to further improve sizing. Another object of the present invention is to improve sizing when sizing aqueous cellulose-containing suspensions having high conductivity and / or high amounts of lipophilic wood extract. Further objects will become apparent hereinafter.
[0003]
U.S. Pat. No. 6,011,166 refers to an aqueous alkyldiketene dispersion containing a cationic starch and an anionic dispersant, such as ligninsulfonic acid, a condensate of naphthalenesulfonic acid and formaldehyde.
[0004]
WO 0023651 relates to anionic and cationic sizing dispersions comprising a ketene dimer and at least an anionic dispersant.
EP '984101 sizing comprises ketene dimer or anhydride and a complexing agent selected from aminopolycarboxylic acids, N-bis- or tris-((1,2-dicarboxylethoxy) ethyl) amine and phosphonic acids. A composition is disclosed.
[0005]
U.S. Patent No. 5,972,094 relates to a sizing composition comprising a thermoplastic resin selected from the group consisting of thermoplastic rosin, thermoplastic hydrocarbon resin, thermoplastic polyamide and thermoplastic amide wax.
U.S. Pat. No. 5,595,629 discloses a papermaking process that produces an aqueous cellulose papermaking slurry and adds a cationic polymer and an anionic polymer to the slurry to increase retention and / or dewatering. The anionic polymer comprises a formaldehyde condensate of a naphthalene sulfonate.
[0006]
(Disclosure of the Invention)
It has been found that the claimed invention surprisingly solves the problems outlined in the present application. More specifically, the present invention relates to an aqueous or suspension comprising cellulose fibers and optional fillers, anionic or cationic sizing dispersions, and cationic organic polymers and step-grown polymers having one or more aromatic groups. Adding a sizing accelerator comprising an anionic polymer having one or more aromatic groups that is a polysaccharide or a naturally occurring aromatic polymer, forming the resulting suspension, dehydrating, The present invention relates to a paper sizing method, wherein a sizing dispersion and a sizing accelerator are separately added to an aqueous suspension.
[0007]
Sizing dispersion
The sizing agent contained in the anionic or cationic sizing dispersion used in the method of the present invention may be any sizing agent, rosin, such as fortified rosin and / or esterification, which provides the paper or paperboard with resistance to wetting and penetration of the liquid. Suitably, it is a non-cellulose-reactive agent comprising rosin, wax, fatty acid and resin acid derivatives, for example fatty amides and fatty esters, for example glycerol triesters of natural fatty acids, and / or cellulose-reactive agents. This sizing dispersion preferably contains a cellulose-reactive sizing agent. The cellulose-reactive sizing agent contained in the sizing dispersion is selected from any cellulose-reactive agent known in the art. The sizing agent is suitably selected from hydrophobic ketene dimers, ketene multimers, acid anhydrides, organic isocyanates, carbamoyl chlorides and mixtures thereof, preferably ketene dimers and / or acid anhydrides. The ketene dimer preferably has the following general formula (I):1And R2Represents a saturated or unsaturated hydrocarbon group, usually a saturated hydrocarbon group, and the hydrocarbon group preferably has 8 to 36 carbon atoms, and usually has a straight chain having 12 to 20 carbon atoms. Or a branched-chain alkyl group such as a hexadecyl group and an octadecyl group. The ketene dimer may be liquid at ambient temperature, ie at 25 ° C, preferably at 20 ° C. Usually, the acid anhydride is characterized by the following general formula (II):3And R4May be the same or different and preferably represent a saturated or unsaturated hydrocarbon group containing 8 to 30 carbon atoms, or R3And R4Can form a 5- to 6-membered ring together with the -CO-C- moiety and may be further substituted by a hydrocarbon group containing up to 30 carbon atoms as needed. Examples of commercially available acid anhydrides include alkyl succinic anhydrides and alkenyl succinic anhydrides, and especially isooctadecenyl succinic anhydride.
[0008]
Embedded image
[0009]
The method of the present invention involves adding an anionic or cationic aqueous sizing dispersion to a suspension containing cellulosic fibers, i.e., the dispersant and / or stabilizer present in the dispersion, which can be referred to as a dispersion, Each has an overall anionic or cationic charge. The dispersion may include any agent that promotes the formation of a dispersion or emulsion, for example, dispersants and / or stabilizers exemplified by polyelectrolytes, surfactants and electrolytes. The anionic aqueous sizing dispersion may be a cationic compound, i.e., a cationic polyelectrolyte (cationic or amphoteric polyelectrolyte with an overall cationic charge) and / or a cationic surfactant and / or known to those skilled in the art. Any other cationic compound may be included, provided that the overall charge of the dispersion is anionic. On the other hand, the cationic aqueous sizing dispersion may be an anionic compound, ie, an anionic polyelectrolyte (anionic or amphoteric polyelectrolyte having an anionic charge as a whole) and / or an anionic surfactant and / or those skilled in the art. May be included, provided that the overall charge of the dispersion is anionic. Anionic charge or cationic charge of the sizing dispersion can be measured by Zetamaster S version PCS.
[0010]
(Best Mode for Carrying Out the Invention)
According to a preferred embodiment of the present invention, the anionic or cationic sizing dispersion comprises a cationic organic polymer having one or more aromatic groups and / or an anionic polymer having one or more aromatic groups. . The cationic organic polymer and anionic polymer may be any of those described below that are included in the sizing accelerator.
[0011]
The anionic or cationic sizing dispersion added to the suspension may have a sizing agent content of 0.1 to 50% by weight, preferably 20% by weight or more, based on the total dispersion / emulsion. The dispersion containing the ketene dimer sizing agent may have a ketene dimer content of 5 to 50% by weight, preferably 10 to 35% by weight, based on the total dispersion. The dispersion or emulsion containing the anhydride sizing agent may have an anhydride content of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total dispersion / emulsion. The dispersion containing the non-cellulose reactive sizing agent suitably has a sizing agent content of 5 to 50% by weight, preferably 10 to 35% by weight. When the anionic and / or cationic polymers having one or more aromatic groups are included in the sizing dispersion, they are present in an amount from about 0.1% to about 15% by weight, based on the sizing agent. It is preferred to do so.
[0012]
The amount of sizing agent added to the aqueous suspension containing the cellulose fibers is 0.01 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the dry weight of the cellulose fibers and any filler. Where the dose depends on the quality of the pulp or paper being sized, the sizing agent and the level of sizing.
[0013]
According to the present invention, an anionic or cationic sizing dispersion and a cationic organic polymer having one or more aromatic groups and a step-growth polymer, one or more aromatic groups that are polysaccharides or naturally occurring aromatic polymers. A sizing accelerator containing an anionic polymer is separately added to the aqueous suspension. Although the sizing dispersion may contain the same polymers as those contained in the sizing accelerator, significant improvements in sizing are only observed when the sizing accelerator and the sizing dispersion are added separately to the cellulosic suspension. You. Separate additions may include the sizing dispersion (which may include any of the polymers of the sizing accelerator) and the sizing accelerator at different or substantially the same locations in the cellulose suspension (concentrated stock solution). Means that they are added separately in time. Furthermore, it is preferred that the cationic organic polymer and the anionic polymer which form the sizing accelerator are also added separately. Preferably, the anionic polymer is added to the suspension after both the sizing dispersion and the cationic organic polymer.
[0014]
According to a preferred embodiment of the present invention, a method of sizing paper comprises adding an aqueous suspension comprising cellulose fibers and optional filler to a sizing agent and one or more of a step-grown polymer, a polysaccharide or a naturally occurring aromatic polymer. Anionic or cationic sizing dispersion containing an anionic polymer having an aromatic group (the amount of sizing agent added to the suspension is from about 0.01% to about 5.0% by weight, based on dry fiber) And cationic polymers having one or more aromatic groups, which are preferably cationic polysaccharides or cationic vinyl addition polymers, and one or more which are step-grown polymers, polysaccharides or naturally occurring aromatic polymers. A sizing accelerator containing an anionic polymer having an aromatic group (the amount of the cationic polymer added to the suspension is about 0.001 wt. % To about 3.0% by weight, and the amount of anionic polymer added to the suspension is from about 0.001% to about 3.0% by weight, based on dry fiber) And forming the resulting suspension and dewatering, adding the sizing dispersion and the sizing accelerator separately to the aqueous suspension.
[0015]
According to yet another preferred embodiment of the present invention, the anionic or cationic sizing dispersion is a sizing agent, a cationic organic polymer having one or more aromatic groups, such as a cationic polysaccharide or a cationic vinyl addition polymer. And an anionic polymer having one or more aromatic groups that is a step-grown polymer, a polysaccharide or a naturally occurring aromatic polymer, wherein the anionic polymer is preferably a step-grown polymer or a naturally occurring aromatic polymer .
Cationic polymers having one or more aromatic groups have the structural formula (I):
[0016]
Embedded image
A cationic polysaccharide having the general formula (II):
[0017]
Embedded image
Is preferably a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer. Cationic polymers having one or more aromatic groups have the structural formula (I):
[0018]
Embedded image
More preferably, it is a cationic polysaccharide having
[0019]
Cationic organic polymers with one or more aromatic groups
The cationic organic polymer of the sizing accelerator (and preferably present in the sizing dispersion) can be derived from natural or synthetic sources and may be linear, branched or crosslinked. The cationic polymer is preferably water-soluble or water-dispersible. Examples of suitable cationic polymers include cationic polysaccharides such as starch, guar gum, cellulose, chitin, chitosan, glycan, galactan, glucan, xanthan gum, pectin, mannan, dextrin, preferably starch and guar gum (suitable starches are (Including potato, corn, wheat, tapioca, rice, waxy corn, barley, etc.); cationic synthetic organic polymers such as cationic chain growing polymers such as polymers based on acrylates, acrylamides and vinylamides. Ionic vinyl addition polymers, and cationic step-growth polymers, such as cationic polyurethanes. Particularly preferred are cationic organic polymers selected from polysaccharides, ie, starch, and cationic vinyl addition polymers such as polymers based on acrylamides having aromatic groups.
[0020]
The aromatic groups of the cationic organic polymer may be present in the polymer backbone or in a substituent attached to the polymer backbone, preferably in the substituent. Examples of suitable aromatic groups include aryl, aralkyl and alkaryl groups such as phenyl, phenylene, naphthyl, xylylene, benzyl and phenylethyl, preferably benzyl, nitrogen-containing aromatic ( Aryl) groups such as pyridinium and quinolinium, and derivatives of these groups. Examples of cationically charged groups that may be present in cationic polymers and monomers used to prepare the cationic polymers include quaternary ammonium groups, tertiary amino groups, and acid addition salts thereof. .
[0021]
According to a preferred embodiment, the cationic organic polymer having aromatic groups is selected from cationic polysaccharides. The aromatic group of the polysaccharide may be attached to a heteroatom such as nitrogen or oxygen present in the polysaccharide, and the heteroatom may be optionally charged, for example, if it is nitrogen. Aromatic groups may also be attached to groups containing heteroatoms, such as amides, esters or ethers, and these groups may be attached to the polysaccharide backbone, for example, via a chain of atoms. Examples of suitable aromatic groups and groups containing aromatic groups include aryl and aralkyl groups such as phenyl, phenylene, naphthyl, phenylene, xylylene, benzyl and phenylethyl; nitrogen-containing aromatic (aryl) groups such as When pyridinium and quinolinium, and one or more substituents attached to the aromatic group are selected from hydroxyl, halide, e.g., chloride, nitro, and hydrocarbon groups having 1 to 4 carbon atoms. Derivatives of these groups are mentioned.
The cationic organic polymer has the general structural formula (I):
[0022]
Embedded image
Is preferably selected from cationic polysaccharides having
[0023]
The aromatic group-modified cationic polysaccharide can have a widely varying degree of substitution. Degree of cation substitution (DSc) May be from 0.01 to 0.5, suitably from 0.02 to 0.3, preferably from 0.025 to 0.2, and the degree of aromatic substitution (DSAr) May be from 0.01 to 0.5, suitably from 0.02 to 0.3, preferably from 0.025 to 0.2, and the degree of anion substitution (DSA) May be 0-0.2, suitably 0-0.1, preferably 0-0.05.
[0024]
The polysaccharide may be subjected to cation and aromatic modification of the polysaccharide in a known manner using one or more agents containing cationic and / or aromatic groups, for example, to convert the agent to an alkaline substance, such as an alkali. It can be prepared by reacting with a polysaccharide in the presence of a metal or alkaline earth metal hydroxide. The polysaccharide subjected to cation and aromatic modification may be nonionic, anionic, amphoteric or cation. Suitable modifiers include nonionic agents, such as aralkyl halides, such as benzyl chloride and benzyl bromide; reaction products of epichlorohydrin and dialkylamines having at least one substituent containing an aromatic group as defined above. (Including 3-dialkylamino-1,2-epoxypropane); and cationic agents such as tertiary amines having epichlorohydrin and at least one substituent containing an aromatic group as defined above ( Reaction products of alkaryl dialkylamines, including, for example, dimethylbenzylamine); arylamines, such as pyridine and quinoline. Suitable cationic agents of this type include 2,3-epoxypropyltrialkylammonium halides and halohydroxypropyltrialkylammonium halides, such as N- (3-chloro-2-hydroxypropyl) -N- (hydrophobic alkyl ) -N, N-di (lower alkyl) ammonium chloride and N-glycidyl-N- (hydrophobic alkyl) -N, N-di (lower alkyl) ammonium chloride (aromatic groups are as defined above) And the hydrophobic alkyls are especially octyl, decyl and dodecyl, and the lower alkyls are methyl or ethyl); and halohydroxypropyl-N, N-dialkyl-N-alkaryl ammonium halides and N-glycidyl-N- (Alkaryl) -N, N-dialkylammonium A chloride such as N- (3-chloro-2-hydroxypropyl) -N- (alkaryl) -N, N-di (lower alkyl) ammonium chloride (alkaryl and lower alkyl groups are as defined above) And N- (3-chloro-2-hydroxypropyl) -N-benzyl-N, N-dimethylammonium chloride; and N- (3-chloro-2-hydroxypropyl) pyridinium chloride. In general, when using a nonionic aromatic drug, it is preferred that the polysaccharide be cationized before and after hydrophobic modification by using any of the cationic drugs known in the art. For examples of suitable cationic and / or aromatic modifiers, aromatic group-modified polysaccharides and methods for their preparation, see US Pat. Nos. 4,687,519 and 5,463,127; WO 94/24169, European Patent Application No. 189935; P. Patel, R .; G. FIG. Patel and V.S. S. Patel, Starch / Starke, 41 (1989), no. 5, pp. 192-196, the teachings of which are incorporated herein by reference.
[0025]
According to yet another preferred embodiment, the cationic organic polymer is selected from homopolymers and copolymers prepared from at least one monomer having an aromatic group, preferably one or more monomers including ethylenically unsaturated monomers. . Cationic polymers may be linear or branched. The aromatic group of the synthetic polymer may be present in the polymer backbone, or preferably it may be a pendant group attached to or extending from the polymer backbone, or attached to the polymer backbone, or It may be in a pendant group extending therefrom. Suitable aromatic (aryl) groups include those that include an optionally substituted phenyl group, an optionally substituted phenylene group, and an optionally substituted naphthyl group, For example, the general formula -C6H5, -C6H4-, -C6H3-And -C6H2-Having a group such as phenylene (-C6H4-), Xylylene (-CH2-C6H4-CH2-), Phenyl (-C6H5), Benzyl (-CH2-C6H5), Phenethyl (-CH2CH2-C6H5), And substituted phenyl (eg, -C6H4-Y, -C6H3Y2, And -C6H2Y3Wherein one or more substituents (Y) attached to the phenyl ring may be selected from hydroxyl, halide, for example chloride, nitro, and hydrocarbon groups having 1 to 4 carbon atoms. Good).
[0026]
Preferably, the cationic polymer is a vinyl addition polymer. The term "vinyl addition polymer" as used herein refers to the addition polymerization of one or more vinyl monomers or ethylenically unsaturated monomers, including, for example, acrylamide-based monomers and acrylate-based monomers. Represents a polymer prepared by This cationic polymer has the general formula (II):
[0027]
Embedded image
(Where R1Is H or CH3And R2And R3Is preferably an alkyl group having preferably 1 to 3 carbon atoms, usually 1 to 2 carbon atoms;1Is O or NH;1Is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, or a hydroxypropylene group, and Q is an aromatic group, preferably a phenyl group or a substituent containing a substituted phenyl group. (This can usually be attached to the nitrogen by an alkylene group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms), and preferably Q is a benzyl group (-CH2-C6H5) And X−Is an anion counter ion, usually a halide such as chloride)
Is preferably selected from cationic vinyl addition polymers obtained by polymerizing a cationic monomer represented by the following formula or a monomer mixture containing the cationic monomer. Examples of suitable monomers represented by the general formula (II) include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and dimethylaminohydroxypropyl Acrylate, dimethylaminohydroxypropyl methacrylate, and dialkylaminoalkyl acrylamide, dialkylaminoalkyl methacrylamide, for example, dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide, dimethyl Mino methacrylamide, and diethylaminopropyl acrylamide, quaternary monomers obtained by a diethylaminopropyl methacrylamide treatment with benzyl chloride. Preferred cationic monomers of the general formula (II) include dimethylaminoethyl acrylate benzyl chloride quaternary salt and dimethylaminoethyl methacrylate benzyl chloride quaternary salt.
[0029]
The cationic vinyl addition (synthetic cation) polymer may be a homopolymer prepared from a cation monomer having an aromatic group or a monomer mixture containing a cation monomer having an aromatic group and one or more copolymerizable monomers. May also be used. Suitable copolymerizable nonionic monomers include compounds of the general formula (III):
[0030]
Embedded image
(Where R4Is H or CH3And R5And R6Is H or a hydrocarbon group, respectively, preferably an alkyl having 1 to 6, preferably 1 to 4, usually 1 to 2 carbon atoms;2Is O or NH;2Is an alkylene group of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, or a hydroxypropylene group, or A and B are both absent, whereby a single between C and N There is a bond (O = C-NR5R6)). Examples of suitable copolymerizable monomers of this type are based on acrylamide, methacrylamide; acrylamide such as N-alkylacrylamide, N-alkylmethacrylamide and N, N-dialkylacrylamide, N, N-dialkylmethacrylamide. Monomers such as Nn-propylacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-butylacrylamide, Nn-butylmethacrylamide, N-isobutylacrylamide, N-isobutylmethacrylamide and N -T-butylacrylamide, Nt-butylmethacrylamide; and dialkylaminoalkylacrylamide, dialkylaminoalkylmethacrylamide, for example, dimethylaminoethylacrylic acid. Amides, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl acrylamide, diethylaminopropyl methacrylamide; acrylates such as dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate Based on e.g. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, t-butylaminoethyl acrylate, t-butylaminoethyl methacrylate and dimethylaminohydroxypropyl acrylate ; And vinylamides, for example, N- vinylformamide and N- vinylacetamide. Preferred copolymerizable nonionic monomers include acrylamide and methacrylamide, ie, acrylamide, methacrylamide, and the main polymer is preferably an acrylamide-based polymer.
Suitable copolymerizable cationic monomers include those of the general formula (IV):
[0032]
Embedded image
(Where R7Is H or CH3And R8, R9And R10Is each H or preferably a hydrocarbon group, suitably an alkyl having 1 to 3 carbon atoms, usually 1 to 2 carbon atoms;3Is O or NH;3Is an alkylene group of 2 to 4 carbon atoms, preferably 2 to 4 carbon atoms, or a hydroxypropylene group, and X−Is an anion counterion, usually a halide such as methyl sulfate or chloride)
And a monomer represented by the following formula: Examples of suitable cationic copolymerizable monomers are usually HCl, H2SO4Prepared using an acid such as, or a quaternizing agent such as methyl chloride, dimethyl sulfate, etc., of the above dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate and dialkylaminoalkyl acrylamide, dialkylaminoalkyl methacrylamide. Acid addition salts and quaternary ammonium salts; and diallyldimethylammonium chloride. Preferred copolymerizable cationic monomers include dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, and diallyl dimethyl ammonium chloride. Copolymerizable anionic monomers such as acrylic acid, methacrylic acid, various sulfonated vinyl addition monomers, and the like can also be used, preferably in small amounts.
[0034]
The cationic vinyl addition monomer is generally 1 to 99 mol%, suitably 2 to 50 mol%, preferably 5 to 20 mol%, preferably a cation having an aromatic group represented by the general formula (II) Prepared from a monomer mixture comprising monomers and from 99 to 1 mol%, suitably from 98 to 50 mol%, preferably from 95 to 80 mol% of other copolymerizable monomers, which preferably comprise acrylamide or methacrylamide. The monomer mixture suitably comprises 98 to 50 mol%, preferably 95 to 80 mol%, of acrylamide or methacrylamide, the sum of the percentages being 100.
[0035]
The cationic polymer may also be selected from polymers prepared by the condensation reaction of one or more monomers containing an aromatic group. Examples of such monomers include toluene diisocyanate, bisphenol A, phthalic acid, phthalic anhydride, and the like, which can be used to prepare cationic polyurethanes, cationic polyamidoamines, and the like.
[0036]
The organic polymer may also be a polymer that has been subjected to an aromatic modification using a drug containing an aromatic group. Suitable denaturants of this type include benzyl chloride, benzyl bromide, N- (3-chloro-2-hydroxypropyl) -N-benzyl-N, N-dimethylammonium chloride, and N- (3-chloro-2 -Hydroxypropyl) pyridinium chloride. Suitable polymers for such aromatic modification include vinyl addition polymers. Where the polymer contains a tertiary nitrogen that can be quaternized by a modifier, the use of such an agent usually results in the polymer being made cationic. Also, the polymer subjected to aromatic modification may be a cation, for example, a cationic vinyl addition polymer.
[0037]
Usually, the charge density of the vinyl addition polymer is in the range of 0.1-6.0 meq, suitably 0.2-4.0 meq / g, preferably 0.5-3.0 meq / g of dry polymer. It is. The weight average molecular weight of the synthetic polymer is usually at least about 500,000, suitably about 1,000,000 or more, preferably about 2,000,000 or more. The upper limit is not important. It may be about 50,000,000, usually 30,000,000, preferably 25,000,000.
[0038]
Anionic polymer having one or more aromatic groups
The anionic polymer having an aromatic group contained in the sizing accelerator (and may optionally be contained in the sizing dispersion of the present invention) is a step growth polymer, a polysaccharide or a naturally occurring aromatic polymer. As used herein, the term "step-growth polymer" refers to polymers obtained by step-growth polymerization, which are also referred to as step-reaction polymer and step-reaction polymerization, respectively. Preferably, the anionic polymer contained in the accelerator is a step growth polymer, a polysaccharide or a naturally occurring aromatic polymer, provided that the anionic polymer is not a melamine sulfonic acid condensation polymer. The anionic polymer may be a step-grown polymer or a naturally occurring aromatic polymer. The anionic polymer of the present invention may be linear, branched or crosslinked. Anionic polymers are usually water-soluble or water-dispersible. Preferably, the anionic polymer is organic. Preferred anionic aromatic polymers are naphthalene sulfonate condensed polymers, such as condensed naphthalene sulfonates, and modified lignin polymers, for example, lignin sulfonates.
[0039]
The aromatic groups of the anionic polymer may be present in the polymer backbone or in substituents attached to the polymer backbone. Examples of suitable aromatic groups include aryl, aralkyl and alkaryl groups and derivatives thereof, for example, phenyl, tolyl, naphthyl, phenylene, xylylene, benzyl, phenylethyl and derivatives of these groups. Examples of anionic charged groups that may be present in anionic polymers and the monomers used to prepare the anionic polymers include anionic charged groups and anions when dissolved or dispersed in water. Charged acid groups (these groups are collectively referred to herein as anionic groups), for example, phosphate, phosphonate, sulfate, sulfonic acid, sulfonate, carboxylic acid, carboxylate, alkoxide, and phenol groups Ie, hydroxy substituted phenyl and hydroxy substituted naphthyl. Groups having an anionic charge are usually salts of alkali metals, alkaline earth metals or ammonia.
[0040]
Examples of suitable anionic step-growth polymerization products of the present invention include condensation polymers, i.e., polymers obtained by step-growth condensation polymerization, e.g., one or more aldehydes such as formaldehyde and one or more anionic groups. Condensates of aromatic compounds, particularly condensed naphthalene sulfonate-type polymers, and any other comonomer useful for condensation polymerization, such as urea. Examples of suitable aromatic compounds containing anionic groups include phenolic compounds and naphthol compounds, such as phenol, naphthol, resorcinol and derivatives thereof, aromatic acids and salts thereof, such as phenyl, phenol, napthyl and naphthol. Acids and salts, usually sulfonic acids and sulphonates, such as benzene sulphonic acid and benzene sulphonate, xylene sulphonic acid and xylene sulphonate, naphthalene sulphonic acid and naphthalene sulphonate, phenol sulphonic acid and phenol sulphonate. No.
[0041]
Examples of further suitable anionic step-growth polymerization products of the present invention include addition polymers, i.e., polymers obtained by step-growth addition polymerization, such as those prepared from monomer mixtures containing aromatic isocyanates and / or aromatic alcohols. Anionic polyurethane. Examples of suitable aromatic isocyanates include diisocyanates such as toluene-2,4-diisocyanate and toluene-2,6-diisocyanate and diphenylmethane-4,4'-diisocyanate. Examples of suitable aromatic alcohols include dihydric alcohols, ie, diols such as bisphenol A, phenyldiethanolamine, glycerol monoterephthalate and trimethylolpropane monoterephthalate. Monohydric aromatic alcohols such as phenols and their derivatives may also be used. The monomer mixture may also include non-aromatic isocyanates and / or alcohols, usually diisocyanates and diols, such as any of those known to be useful in preparing polyurethanes. Examples of suitable monomers containing anionic groups include triols, such as trimethylolethane, trimethylolpropane and glycerol, and dicarboxylic acids or anhydrides thereof, such as succinic and succinic anhydride, terephthalic acid and terephthalic anhydride. Monoester reaction products of acids, for example, glycerol monosuccinate, glycerol monoterephthalate, trimethylolpropane monosuccinate, trimethylolpropane monoterephthalate, N, N-bis- (hydroxyethyl) -glycine, di- (hydroxymethyl ) Propionic acid, N, N-bis- (hydroxyethyl) -2-aminoethanesulfonic acid and the like, if necessary and usually, a base such as an alkali metal or alkaline earth metal hydroxide, for example, Sodium hydroxide , Ammonia or amines, for example, be combined with reaction with triethylamine, thereby to generate the alkali metal, alkaline earth metal or ammonium counterion.
[0042]
Examples of suitable anionic chain-growth polymerization products of the present invention are copolymerized with at least one monomer having an aromatic group and usually a nonionic monomer, for example, an acrylate-based monomer and an acrylamide-based monomer. And an anionic vinyl addition polymer obtained from a mixture of a vinyl monomer containing at least one monomer having an anionic group or an ethylenically unsaturated monomer. Examples of suitable anionic monomers include acrylic acid, methacrylic acid and paravinylphenol (hydroxystyrene).
[0043]
Examples of suitable anionic polysaccharides include starch, guar gum, cellulose, chitin, chitosan, glycan, galactan, glucan, xanthan gum, pectin, mannan, dextrin, preferably starch, guar gum, and cellulose derivatives. , Potato, corn, wheat, tapioca, rice, waxy corn and barley, preferably potato. The anionic groups in the polysaccharide may be native and / or may be introduced by chemical treatment. Aromatic groups in the polysaccharide can be introduced by chemical methods known in the art.
[0044]
Examples of suitable (modified) naturally occurring aromatic anionic polymers of the present invention include kraft lignin, for example, lignin adducts copolymerized with formaldehyde and modified lignin polymers, such as sulfonated lignin, for example, lignin sulfonate and tannin Extracts, ie, naturally occurring polyphenolic substances present in the organic extracts of the bark of some wood species.
[0045]
Preferably, the anionic polymer having an aromatic group is selected from step-grown polymers, polysaccharides and naturally occurring aromatic polymers. Preferred are condensed naphthalene sulfonate-type polymers such as condensed naphthalene sulfonates and modified lignin polymers, for example lignin sulfonates.
[0046]
The weight average molecular weight of the anionic polymer can vary within wide limits depending, inter alia, on the type of polymer used, usually it is at least about 500, suitably about 2,000 or more, preferably about 5,000 or more. This upper limit is not important. It may be about 200,000,000, usually 150,000,000, suitably 100,000,000, preferably 1,000,000.
[0047]
Said anionic polymers have, inter alia, widely varying degrees of anion substitution (DS) depending on the type of polymer used.A). DSAIs usually 0.01 to 2.0, suitably 0.02 to 1.8, preferably 0.025 to 1.5, and the degree of aromatic substitution (DSQ) May be from 0.001 to 1.0, usually from 0.01 to 0.8, suitably from 0.02 to 0.7, preferably from 0.025 to 0.5. When the anionic polymer contains a cationic group, the degree of cationic substitution (DSC) May be, for example, from 0 to 0.2, suitably from 0 to 0.1, preferably from 0 to 0.05, and the anionic polymer has an anionic charge as a whole. Usually, the anionic charge density of the anionic polymer is between 0.1 and 6.0 milliequivalents per gram of dry polymer, suitably between 0.5 and 5.0 milliequivalents, preferably between 1.0 and 4.0 milliequivalents. Within range.
[0048]
The cationic organic polymer having an aromatic group and the anionic polymer having an aromatic group of the sizing accelerator are separate from the addition of the sizing dispersion and, inter alia, the raw material type, salt content, salt type, filler It can be added to the aqueous suspension (raw material) in any order in amounts which can vary within wide limits depending on the content, type of filler, time of addition and the like. Generally, these polymers are added in amounts that provide better sizing than would otherwise be obtained, and the cationic organic polymer is usually added to the feedstock before adding the anionic polymer. The cationic polymer is usually added in an amount of at least 0.001% by weight, often at least 0.005% by weight, based on the dry raw material, with the upper limit usually being 3% by weight, preferably 2.0% by weight. is there. The anionic polymer is usually added in an amount of at least 0.001% by weight, often at least 0.005% by weight, based on the dry raw material, with the upper limit usually being 3% by weight, preferably 1.5% by weight. is there.
[0049]
Apart from said cationic organic and anionic polymers, sizing accelerators are other compounds which improve the sizing efficiency, such as anionic particulate materials, for example silica-based particles and smectite-type clays, low molecular weight Cationic organic polymers, aluminum compounds such as alum, aluminate, aluminum chloride, aluminum nitrate, and polyaluminum compounds, for example, polyaluminum chloride, polyaluminum sulfate, polyaluminum compounds containing both chloride and sulfate ions , Polyaluminum silicate sulfate and mixtures thereof, anionic vinyl addition polymers and combinations thereof.
[0050]
The process of the present invention is preferably used for the production of paper from a suspension having a high electrical conductivity, comprising cellulosic fibers and optional fillers. Usually, the conductivity of the raw material is at least 0.20 mS / cm, suitably at least 0.5 mS / cm, preferably at least 3.5 mS / cm. Very good sizing results were observed at conductivity levels above 5.0 mS / cm, and even above 7.5 mS / cm. Conductivity can be measured by conventional equipment, for example, the WTW LF 539 apparatus supplied by Christian Burner. The above value is supplied to the head box of the paper machine, or by measuring the conductivity of the cellulose suspension present therein, or by measuring the conductivity of white water obtained by dehydrating the suspension. It is preferable to be measured by the following. A high conductivity level means a high content of salts (electrolytes), where the various salts are alkali metals such as Na+And K+, An alkaline earth metal such as Ca2+And Mg2+, Aluminum ions, for example, Al3+, Al (OH)2+And monovalent, divalent and multivalent cations such as polyaluminum ions and halides, for example Cl2−, Sulfate ions such as SO4 2-And HSO4 −, Carbonate ions such as CO3 2-And HCO3 −, Divalent and polyvalent anions such as silicates and lower organic acids. The invention is particularly useful for the production of paper from raw materials having a high content of divalent and polyvalent cation salts, usually with a cation content of at least 200 ppm, suitably at least 300 ppm, preferably at least 400 ppm. is there. Salts may be derived from cellulosic fibers and fillers, used in particular to produce raw materials in general mills, where concentrated aqueous fiber suspensions from pulp mills are usually mixed with water to form paper. Produces a dilute suspension suitable for paper production in factories. The salt may also be derived from various additives introduced into the raw materials, fresh water supplied to the method, or may be added as needed. In addition, the salt content is usually high in a manner in which the white water is exhaustively circulated, which can lead to a considerable accumulation of salts in the water circulating in that way.
[0051]
Further, the present invention is used when white water is circulated thoroughly, i.e. with a high degree of white water tightness, e.g. from 0 to 30 tons of fresh water is used per ton of dry paper, usually less than 20 tons, Suitably less than 15 tonnes, preferably less than 10 tonnes, in particular less than 5 tonnes, including papermaking processes where 1 ton of fresh water / paper is used. Suitably, the circulation of the white water obtained in that way comprises mixing the white water with cellulose fibers and / or any filler to produce a sizing suspension. It involves mixing the white water with a suspension containing the cellulosic fibers and any fillers, after which the suspension preferably enters a forming wire for sizing.
[0052]
Further additives customary for papermaking, such as additional dry strength agents, wet strength agents, may of course be used in combination with the additives of the invention. The cellulosic suspension, or raw material, may also be made of conventional types of inorganic fillers such as kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates, such as chalk, ground marble and precipitated calcium carbonate. May be included.
[0053]
The method according to the invention is used for the production of paper. The term "paper" as used herein, of course, includes not only paper and its products, but also other products such as sheets or webs, such as boards and paperboard, and these products. The method can be used for the production of paper from suspensions of different types of fibers containing cellulose, the suspension comprising at least 25% by weight, preferably at least 50% by weight, based on dry matter, of such fibers. Is preferred. These suspensions include chemical pulp, such as sulfated pulp, sulfite pulp and organic solvent pulp, mechanical pulp such as thermomechanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp (from both hardwood and softwood) And, if desired, recycled fibers from deinked pulp, and mixtures thereof. The invention is particularly useful for the production of paper from pulp-based suspensions, including recycled fibers and deinked pulp, wherein the content of such source cellulose fibers is up to 100%, preferably from 20%. It may be 100%.
[0054]
The present invention is further described in the following examples, which are not intended to limit the invention. Parts and percentages relate to parts by weight and percentage by weight, respectively, unless otherwise stated.
[0055]
In all of the following examples, the sizing dispersion and the sizing accelerator were added separately to the cellulosic suspension. Furthermore, if the accelerator contained more than one polymer with aromatic groups, these polymers were added separately to the suspension to each other and to the dispersion.
[0056]
(Example)
Example 1
The sizing performance of this method was evaluated by using the cobb60 test. An anionic sizing dispersion containing an alkyl ketene dimer, a condensed naphthalene sulfonate and di (hydrogenated tallow) dimethyl ammonium chloride was prepared. The sizing dispersion had an AKD content of 30% and contained, based on AKD, 4% di (hydrogenated tallow) dimethyl ammonium chloride and 6% condensed naphthalene sulfonate. This sizing dispersion was added to the raw material in an amount of 5 kg @ AKD / ton of dry raw material.
[0057]
In Test 2, the sizing accelerator comprised a condensed naphthalene sulfonate (available under the trade name Tamol®) and a cationic starch having a cationic substitution degree DS of 0.065 with respect to the nitrogen-containing benzyl group. In Test 1, a cationic starch having no aromatic group and a cationic substitution of 0.065 and anionic inorganic silica particles prepared as a sol, ie, an anionic non-aromatic polymer, were added to the furnish.
[0058]
The furnish used was 80% by weight bleached birch / pine (60/40) sulfate pulp and 20% by weight CaCO3And purified to 200 CSF, 0.3 g of Na per liter of raw material2SO4And had a conductivity of 461 μS / cm and a pH of 8.1.
[0059]
[Table 1]
Example 2
A sizing accelerator comprising the same anionic sizing dispersion as described in Example 1 and cationic starch and anionic inorganic silica particles having a cationic substitution DS of 0.065 for nitrogen-containing benzyl groups (test 1); By adding a condensed naphthalene sulfonate (available under the trade name Tamol®) and an accelerator comprising a cationic starch having a cationic substitution DS of 0.065 with respect to the nitrogen-containing benzyl group (Test 2). The sizing performance of the method was evaluated (cobb60 test). However, calcium chloride was added to the furnish to adjust the conductivity to 5000 μS / cm, thereby simulating a furnish with high conductivity.
[0061]
[Table 2]
Example 3
Sizing performance was evaluated using a cationic sizing dispersion containing 15% alkyl ketene dimer, 2% cationic starch, and 0.6% sodium lignosulfonate based on AKD (sizing agent). The components contained in the sizing accelerator and the amounts of the components added (as evident from Table 3) are: condensed naphthalene sulfonate, non-aromatic group-free cationic starch having a DS of 0.065, and a DS of 0.065. And a cationic starch containing an aromatic group having the following formula: and anionic inorganic silica particles prepared as a sol. The raw material used was the raw material of Example 2 having a pH of 8.1 and a conductivity of 5000 μS / cm due to the addition of calcium chloride to the raw material.
[0063]
[Table 3]
Example 4
As 8.9% of a commercially available alkyl ketene dimer, an aromatic substituted cationic starch having a DS of 0.065 containing 0.89% of benzyl groups, and 0.22% of a trade name Tamol® An anionic sizing dispersion containing an available condensed naphthalene sulfonate was prepared. The anion dispersion was treated with 30% pine, 30% Bee, 40% eucalyptus, and 15% precipitated CaCO in an amount of 0.0115% (dry basis) based on ketene dimer.3Was added to a cellulose suspension (dry basis) containing The conductivity of the suspension was 500 μS / cm. To the suspension was also added a sizing accelerator comprising a benzyl-substituted starch having a DS of 0.065 and a condensed naphthalene sulfonate available under the trade name Tamol® (Test 2).
The same anion dispersion was also added to the same suspension. However, the sizing accelerator added to this suspension did not contain an aromatic polymer. The sizing accelerator comprised cationic starch having a DS of 0.065 without aromatic groups and anionic inorganic silica particles prepared as a sol (Test 1). Table 4 shows the amount of the polymer of the accelerator and the sizing agent (AKD) of the dispersion.
[0065]
[Table 4]
Example 5
In this example, the same dispersion and sizing accelerator as in Example 2 were used, except that the conductivity of the suspension was 5000 μS / cm. Table 5 shows the amount of the polymer of the accelerator and the sizing agent (AKD) of the dispersion.
[0067]
[Table 5]
Example 6
The sizing performance of this method was evaluated by using the Cobb 60 test. An anionic sizing dispersion containing an alkyl ketene dimer, a condensed naphthalene sulfonate and di (hydrogenated tallow) dimethyl ammonium chloride was prepared. The sizing dispersion had an AKD content of 30% and contained, based on AKD, 4% di (hydrogenated tallow) dimethyl ammonium chloride and 6% condensed naphthalene sulfonate. The sizing dispersion was added in an amount of 0.3 kg AKD per ton of dry material.
[0069]
A cationic starch having a cationically substituted DS of 0.065 with respect to the nitrogen-containing benzyl group and a starch having a cationically substituted DS of 0.065 were used in combination with condensed naphthalene sulfonate and melamine sulfonate, respectively.
[0070]
The furnish used was 80% birch / pine (60/40) sulfate pulp and 20% by weight CaCO3And purified to 200 CSF, containing 0.3 g per liter of raw material and having a conductivity of 555 μS / cm and a pH of 8.22.
[0071]
[Table 6]
Claims (78)
（ｉ）陰イオン又は陽イオンサイジング分散液、及び
（ｉｉ）一つ以上の芳香族基を有する陽イオン有機ポリマー、及び一つ以上の芳香族基を有する段階成長ポリマー、多糖又は天然産芳香族ポリマーである陰イオンポリマーを含むサイジング促進剤
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。To an aqueous suspension containing cellulose fibers, and any filler,
(I) an anionic or cationic sizing dispersion; and (ii) a cationic organic polymer having one or more aromatic groups, and a step-grown polymer, polysaccharide or naturally occurring aromatic having one or more aromatic groups. Adding a sizing accelerator comprising an anionic polymer that is a polymer, forming and dewatering the resulting suspension, adding the sizing dispersion and the sizing accelerator separately to the aqueous suspension A sizing method for paper, characterized in that:
を有する陽イオン多糖、及び／又は一般式（ＩＩ）：
により表される陽イオンモノマー又は陽イオンモノマーを含むモノマー混合物を重合することにより得られたビニル付加ポリマーである請求の範囲第１項記載の方法。The cationic organic polymer has the structural formula (I):
And / or a general formula (II):
The method according to claim 1, which is a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer represented by the following formula:
を有する陽イオン多糖から選ばれる請求の範囲第１項記載の方法。The cationic polymer has the structural formula (I):
The method according to claim 1, which is selected from cationic polysaccharides having the following formula:
（ｉｉ）一つ以上の芳香族基を有する陽イオン有機ポリマー、及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤であって、懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までであり、かつ陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までである、
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。An aqueous suspension comprising cellulosic fibers and optional filler is added to an aqueous suspension comprising (i) an anionic polymer having one or more aromatic groups, which is a sizing agent and a step growth polymer, a polysaccharide or a naturally occurring aromatic polymer. An ionic or cationic sizing dispersion, wherein the amount of sizing dispersion added to the suspension is from about 0.01% to about 5.0% by weight calculated as a sizing agent on a dry fiber basis. And sizing enhancement comprising (ii) a cationic organic polymer having one or more aromatic groups and an anionic polymer having one or more aromatic groups that is a step-grown polymer, a polysaccharide or a naturally occurring aromatic polymer. The amount of cationic polymer added to the suspension is from about 0.001% to about 3% by weight, based on dry fiber, and the amount of anionic polymer The amount is the dry fibers from about 0.001% to about 3% by weight based,
Sizing the resulting suspension, dewatering, and separately adding the sizing dispersion and the sizing accelerator to the aqueous suspension.
を有する陽イオン多糖、又は一般式（ＩＩ）：
により表される陽イオンモノマー又は陽イオンモノマーを含むモノマー混合物を重合することにより得られたビニル付加ポリマーである請求の範囲第１８項記載の方法。The cationic organic polymer has the structural formula (I):
A cationic polysaccharide having the general formula (II):
The method according to claim 18, which is a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer represented by the following formula:
を有する陽イオン多糖である請求の範囲第２０項記載の方法。The cationic organic polymer has the structural formula (I):
21. The method according to claim 20, which is a cationic polysaccharide having:
（ｉｉ）一つ以上の芳香族基を有する陽イオン有機ポリマー、及び段階成長ポリマー、多糖又は天然産芳香族ポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤であって、懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までであり、かつ懸濁液に添加される陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までである、
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。In an aqueous suspension comprising cellulose fibers and optional filler, (i) a sizing agent, a cationic organic polymer having one or more aromatic groups and a step-growth polymer, a polysaccharide or a naturally occurring aromatic polymer. An anionic or cationic sizing dispersion comprising an anionic polymer having one or more aromatic groups, wherein the amount of sizing dispersion added to the suspension is about From 0.01% to about 5.0% by weight, and (ii) a cationic organic polymer having one or more aromatic groups, and one that is a step-grown polymer, a polysaccharide or a naturally occurring aromatic polymer. A sizing accelerator comprising an anionic polymer having an aromatic group as described above, wherein the amount of the cationic polymer added to the suspension is about 0.001 wt. It is from up to about 3 wt%, and the amount of anionic polymer added to the suspension is from about 0.001% by weight, based on the dry fiber up to about 3 wt%,
Sizing the resulting suspension, dewatering, and separately adding the sizing dispersion and the sizing accelerator to the aqueous suspension.
を有する陽イオン多糖、又は一般式（ＩＩ）：
により表される陽イオンモノマー又は陽イオンモノマーを含むモノマー混合物を重合することにより得られたビニル付加ポリマーである請求の範囲第３３項記載の方法。The cationic organic polymer of the sizing dispersion and the sizing accelerator has the structural formula (I):
A cationic polysaccharide having the general formula (II):
34. The method according to claim 33, which is a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer represented by the following formula:
を有する陽イオン多糖である請求の範囲第３５項記載の方法。The cationic organic polymer has the structural formula (I):
The method according to claim 35, which is a cationic polysaccharide having the following formula:
（ｉｉ）陽イオン多糖である一つ以上の芳香族基を有する陽イオン有機ポリマー、及びナフタレンスルホネート縮合ポリマー又は変性リグニンポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤であって、懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までであり、かつ懸濁液に添加される陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までである、
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。An aqueous suspension comprising the cellulose fibers, and any filler, is added to an anion or cation comprising (i) a sizing agent and an anionic polymer having one or more aromatic groups that is a naphthalene sulfonate condensation polymer or a modified lignin polymer. An ion sizing dispersion, wherein the amount of the sizing dispersion added to the suspension is from about 0.01% to about 5.0% by weight, calculated as the sizing agent, based on dry fiber; and (Ii) a sizing accelerator comprising a cationic organic polymer having one or more aromatic groups which is a cationic polysaccharide, and an anionic polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer or a modified lignin polymer Wherein the amount of cationic polymer added to the suspension is from about 0.001% by weight based on dry fiber. 3 is up to wt%, and the amount of anionic polymer added to the suspension is from about 0.001% by weight, based on the dry fiber up to about 3 wt%,
Sizing the resulting suspension, dewatering, and separately adding the sizing dispersion and the sizing accelerator to the aqueous suspension.
を有する陽イオン多糖である請求の範囲第４５項記載の方法。The cationic organic polymer has the structural formula (I):
46. The method according to claim 45, which is a cationic polysaccharide having the following formula:
（ｉｉ）陽イオン多糖である一つ以上の芳香族基を有する陽イオン有機ポリマー、及びナフタレンスルホネート縮合ポリマー又は変性リグニンポリマーである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤であって、懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までであり、かつ懸濁液に添加される陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までである、
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。In an aqueous suspension containing cellulosic fibers and optional fillers, (i) a sizing agent, a cationic organic polymer having one or more aromatic groups that are cationic polysaccharides, and a naphthalene sulfonate condensation polymer or modified lignin polymer An anionic or cationic sizing dispersion comprising an anionic polymer having one or more aromatic groups, wherein the amount of sizing dispersion added to the suspension is calculated as a sizing agent on a dry fiber basis From about 0.01% to about 5.0% by weight, and (ii) a cationic organic polymer having one or more aromatic groups that is a cationic polysaccharide, and a naphthalene sulfonate condensed polymer or modified lignin A sizing accelerator comprising an anionic polymer having one or more aromatic groups that is a polymer, wherein the sizing accelerator is added to a suspension. The amount of cationic polymer is from about 0.001% to about 3% by weight, based on dry fiber, and the amount of anionic polymer added to the suspension is about 0.001%, based on dry fiber. By weight up to about 3% by weight,
Sizing the resulting suspension, dewatering, and separately adding the sizing dispersion and the sizing accelerator to the aqueous suspension.
を有する陽イオン多糖である請求の範囲第５３項記載の方法。The sizing dispersion and the cationic organic polymer of the accelerator have the structural formula (I):
54. The method according to claim 53, which is a cationic polysaccharide having the formula:
（ｉｉ）構造式（Ｉ）：
を有する陽イオン多糖である一つ以上の芳香族基を有する陽イオン有機ポリマー、及び縮合ナフタレンスルホネート又はリグニンスルホネートである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤であって、懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までであり、かつ懸濁液に添加される陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までである、
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。Anionic or cationic sizing, comprising (i) an anionic polymer having one or more aromatic groups, which is a sizing agent and a condensed naphthalene sulfonate or lignin sulfonate, in an aqueous suspension comprising the cellulose fibers and any fillers. The amount of sizing dispersion added to the suspension, from about 0.01% to about 5.0% by weight, calculated as sizing agent, based on dry fiber, and (ii) ) Structural formula (I):
A sizing accelerator comprising a cationic organic polymer having one or more aromatic groups that is a cationic polysaccharide having, and an anionic polymer having one or more aromatic groups that is a condensed naphthalene sulfonate or lignin sulfonate, Wherein the amount of cationic polymer added to the suspension is from about 0.001% to about 3% by weight, based on dry fiber, and the amount of anionic polymer added to the suspension is From about 0.001% to about 3% by weight, based on
Sizing the resulting suspension, dewatering, and separately adding the sizing dispersion and the sizing accelerator to the aqueous suspension.
を有する陽イオン多糖である一つ以上の芳香族基を有する陽イオン有機ポリマー、及び縮合ナフタレンスルホネート又はリグニンスルホネートである一つ以上の芳香族基を有する陰イオンポリマーを含む陰イオン又は陽イオンサイジング分散液であって、懸濁液に添加されるサイジング分散液の量は乾燥繊維を基準としてサイジング剤として計算して約０．０１重量％から約５．０重量％までであり、及び
（ｉｉ）構造式（Ｉ）：
を有する陽イオン多糖である一つ以上の芳香族基を有する陽イオン有機ポリマー、及び縮合ナフタレンスルホネート又はリグニンスルホネートである一つ以上の芳香族基を有する陰イオンポリマーを含むサイジング促進剤であって、懸濁液に添加される陽イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までであり、かつ懸濁液に添加される陰イオンポリマーの量は乾燥繊維を基準として約０．００１重量％から約３重量％までである、
を添加し、得られた懸濁液を地合構成し、脱水することを含み、サイジング分散液及びサイジング促進剤を水性懸濁液に別々に添加することを特徴とする紙のサイジング方法。In an aqueous suspension containing cellulose fibers and any filler, (i) a sizing agent, structural formula (I):
Or cation sizing comprising a cationic organic polymer having one or more aromatic groups, which is a cationic polysaccharide having, and an anionic polymer having one or more aromatic groups, being a condensed naphthalene sulfonate or lignin sulfonate The amount of sizing dispersion added to the suspension, from about 0.01% to about 5.0% by weight, calculated as sizing agent, based on dry fiber, and (ii) ) Structural formula (I):
A sizing accelerator comprising a cationic organic polymer having one or more aromatic groups that is a cationic polysaccharide having, and an anionic polymer having one or more aromatic groups that is a condensed naphthalene sulfonate or lignin sulfonate, Wherein the amount of cationic polymer added to the suspension is from about 0.001% to about 3% by weight, based on dry fiber, and the amount of anionic polymer added to the suspension is From about 0.001% to about 3% by weight, based on
Sizing the resulting suspension, dewatering, and separately adding the sizing dispersion and the sizing accelerator to the aqueous suspension.
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| EP00850135 | 2000-08-07 | ||
| EP00850136 | 2000-08-07 | ||
| EP00850195 | 2000-11-16 | ||
| PCT/SE2001/001699 WO2002012623A1 (en) | 2000-08-07 | 2001-08-02 | Process for sizing paper |
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| JP2002517894A Pending JP2004514796A (en) | 2000-08-07 | 2001-08-02 | How to size paper |
| JP2002517897A Pending JP2004506105A (en) | 2000-08-07 | 2001-08-02 | Paper manufacturing method |
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| EP (4) | EP1309756B1 (en) |
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