EP3938575B1 - Increased paper strength by surface treatment - Google Patents
Increased paper strength by surface treatment Download PDFInfo
- Publication number
- EP3938575B1 EP3938575B1 EP20709236.2A EP20709236A EP3938575B1 EP 3938575 B1 EP3938575 B1 EP 3938575B1 EP 20709236 A EP20709236 A EP 20709236A EP 3938575 B1 EP3938575 B1 EP 3938575B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salts
- starches
- paper
- water
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004381 surface treatment Methods 0.000 title 1
- 229920002472 Starch Polymers 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 43
- 235000019698 starch Nutrition 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 239000008107 starch Substances 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 27
- 125000000129 anionic group Chemical group 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 150000004676 glycans Chemical class 0.000 claims description 10
- 229920001282 polysaccharide Polymers 0.000 claims description 10
- 239000005017 polysaccharide Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 239000007900 aqueous suspension Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019426 modified starch Nutrition 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229920000945 Amylopectin Polymers 0.000 claims description 2
- 229920000856 Amylose Polymers 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 229920006320 anionic starch Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 4
- 239000011707 mineral Substances 0.000 claims 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 239000000123 paper Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 methallyl sulphonic acid Chemical compound 0.000 description 9
- 239000000654 additive Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229940100445 wheat starch Drugs 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000011111 cardboard Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DNHDSWZXBHTLDP-UHFFFAOYSA-N 3-(2-ethenylpyridin-1-ium-1-yl)propane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1C=C DNHDSWZXBHTLDP-UHFFFAOYSA-N 0.000 description 2
- CIQSWDLWSDYUFD-UHFFFAOYSA-N CCCC=C(C)C(N)=O.CN(C)CCCS(O)(=O)=O Chemical compound CCCC=C(C)C(N)=O.CN(C)CCCS(O)(=O)=O CIQSWDLWSDYUFD-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- QQZXAODFGRZKJT-UHFFFAOYSA-N n-tert-butyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC(C)(C)C QQZXAODFGRZKJT-UHFFFAOYSA-N 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- AIUAMYPYEUQVEM-UHFFFAOYSA-N trimethyl(2-prop-2-enoyloxyethyl)azanium Chemical compound C[N+](C)(C)CCOC(=O)C=C AIUAMYPYEUQVEM-UHFFFAOYSA-N 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BLGRSDRGCZQJMW-UHFFFAOYSA-N 3-(dimethylamino)propane-1-sulfonic acid ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C.CN(C)CCCS(O)(=O)=O BLGRSDRGCZQJMW-UHFFFAOYSA-N 0.000 description 1
- GYJNVSAUBGJVLV-UHFFFAOYSA-N 3-(dimethylazaniumyl)propane-1-sulfonate Chemical compound CN(C)CCCS(O)(=O)=O GYJNVSAUBGJVLV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UFEOXCGSEROQQN-UHFFFAOYSA-N C(C(=C)C)(=O)OCC.C(C)[N+](C)(C)C Chemical compound C(C(=C)C)(=O)OCC.C(C)[N+](C)(C)C UFEOXCGSEROQQN-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SCQOZUUUCTYPPY-UHFFFAOYSA-N dimethyl-[(prop-2-enoylamino)methyl]-propylazanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CNC(=O)C=C SCQOZUUUCTYPPY-UHFFFAOYSA-N 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 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
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical group 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012549 training Methods 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
- D21H23/34—Knife or blade type coaters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
- D21H23/48—Curtain coaters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
- D21H23/56—Rolls
-
- 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
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/0005—Processes or apparatus specially adapted for applying liquids or other fluent materials to finished paper or board, e.g. impregnating, coating
- D21H5/0047—Processes or apparatus specially adapted for applying liquids or other fluent materials to finished paper or board, e.g. impregnating, coating by spraying or projecting
Definitions
- the invention relates to a process for treating the surface of paper to improve its mechanical strength.
- starches such as corn starch, wheat starch, potato starch or chemically modified starches were used as layer bonding agents. The practice was to drop/spray the starch slurry onto the wet paper and then promote the gelatinization of the starch during the drying process to improve the adhesive strength.
- the starch grains need high temperature, water and time to “burst/explode” and therefore for the starch to gelatinize. It is the gelatinized starch which provides the mechanical properties. If the water in the slurry deposited on the surface is eliminated too quickly by too violent a drying section profile, or by too rapid absorption of water within the paper, the grains dry as they are, without gelatinizing, and therefore without bringing any performance.
- a polyacrylamide (PAM) dry strength agent has been used in combination with starch. Thanks to synthetic macromolecules of the PAM type, it became possible to minimize the problems linked to the use of an aqueous solution of starch, such as, for example, the increase in the COD (Chemical Oxygen Demand), the formation of moulds/ bacteria from natural substances such as starch, heavy and necessary maintenance of spray nozzles. This also limited starch losses within the paper as well as in the water circuit. However, until now, all dry strength agents tested in combination with starch have been water-soluble polymers.
- the Applicant has discovered, surprisingly, that by applying to the surface of the paper and/or at least one of its layers a mixture of a polysaccharide and an aqueous dispersion comprising (a) particles of at least one polymer anionic water-swellable material and (b) at least one compound chosen from an inorganic salt, an organic salt, a dispersing organic polymer and mixtures thereof, the mechanical properties of delamination are higher.
- the water-holding capacity of the water-swellable polymer gives the starch grains a moist atmosphere that is more resilient to drastic drying conditions, improving the gelatinization of the starch.
- wet paper is understood to mean the paper resulting from the manufacturing process before passing through the dryer section.
- the aqueous suspension S i contains between 0.5 and 30% by mass of polysaccharide in water, and even more advantageously between 5 and 20% by mass.
- the polysaccharide is chosen from native starch, amylose, amylopectin, cellulose and compounds derived from cellulose, modified starches such as enzymatically treated starches, hydrolyzed starches, heated starches, cationic starches, such as those resulting from the reaction of a starch with a tertiary amine to form a quaternary ammonium salt, anionic starches, amphoteric starches; and any combination thereof.
- modified starches such as enzymatically treated starches, hydrolyzed starches, heated starches, cationic starches, such as those resulting from the reaction of a starch with a tertiary amine to form a quaternary ammonium salt, anionic starches, amphoteric starches; and any combination thereof.
- the polysaccharide is native starch.
- Native starch is the product of starch extraction without further modification.
- the water-swellable polymer P used in step ii) of the process of the invention is also known as a super-absorbent polymer. Generally, it has a water absorption capacity greater than 10 times its volume. In a particularly advantageous manner for the process according to the invention, within the dispersion, the water-swellable polymer is not or only slightly water-swelled. Low water swell means that it retains a water absorption capacity greater than 10 times its volume.
- the water-swellable polymer P used in step ii) of the process of the invention is anionic, which means that its resulting charge is negative.
- This polymer can be prepared from various water-soluble monomers, in particular from at least one water-soluble monomer comprising at least one ethylenic double bond. It can thus be prepared from at least one anionic monomer, from at least one nonionic monomer, from at least one cationic monomer or even from at least one zwitterionic monomer, alone or in blend.
- the water-swellable polymers P used in the process of the invention are obtained by crosslinking and therefore form three-dimensional networks.
- the water-swellable polymer P can be a copolymer prepared from the monomers described above or from the monomers described above and at least one other monomer chosen from the monomers hydrophobic, for example styrene, alkyl-acrylates, alkyl-methacrylates, aryl-acrylates, aryl-methacrylates, hydrophobic derivatives of acrylamide; amphiphilic monomers, for example dodecyl poly(oxyethylene) methacrylate, behenyl poly(oxyethylene) methacrylate; or from natural polymers such as, for example, cellulose derivatives, polysaccharides, clays, for example these natural polymers can be grafted onto the water-swellable polymers of the invention to form another family of water-swellable polymers according to the invention.
- the water-swellable polymer P is a copolymer of at least one nonionic monomer and of at least one anionic monomer.
- the anionic water-swellable polymer P is derived from at least 1 mol% of at least one water-soluble anionic monomer comprising an ethylenic double bond and at least one carboxylic or sulphonic acid function and from at least 5 mol% of at least a nonionic monomer chosen from acrylamide, methacrylamide and their derivatives, vinylformamide and N-vinylpyrrolidone.
- the water-swellable polymer P contains between 1 and 40 mol% of at least one water-soluble anionic monomer comprising an ethylenic double bond and at least one carboxylic or sulphonic acid function and between 60 and 99 mol% of at least one nonionic monomer chosen from acrylamide, methacrylamide and their derivatives, vinylformamide and N-vinylpyrrolidone.
- the water-soluble anionic monomer is chosen from acrylic acid, methacrylic acid and their salts, 2-acrylamido-2-methylpropane sulphonic acid and its salts, itaconic acid and its salts, allyl sulphonic acid and its salts, methallyl sulphonic acid and its salts.
- the water-swellable anionic polymer P is a copolymer of acrylamide and sodium acrylate.
- the aqueous dispersion D comprises from 5 to 60% by dry weight, and even more preferably from 15 to 35% by dry weight, of water-swellable polymer P.
- the particles of water-swellable polymer P advantageously have a diameter allowing them to be dispersed.
- the particles have an average diameter ranging from 0.1 and 1000 ⁇ m, more preferentially ranging from 0.1 and 200 ⁇ m, even more preferentially ranging from 0.1 and 20 ⁇ m.
- the average diameter of the particles can be determined by any method known to those skilled in the art, for example by binocular microscopy.
- the aqueous dispersion D comprises a compound (b) which has a balancing agent function. It is a water-soluble or water-miscible compound. Within the dispersion according to the invention, it makes it possible to totally or partially inhibit the hydroswelling capacity of the polymer P. Thus, within this aqueous dispersion, in the presence of this compound (b), the hydroswellable polymer ( P ) is present in the form of particles and is not or only slightly in the hydroswollen state.
- dispersion D comprises, as compound (b), from 8 to 27% by mass of inorganic salt or organic salt and from 5 to 20% by dry mass of dispersing organic polymer.
- the dispersion D can also comprise at least one additive chosen from polyfunctional alcohols, for example glycerol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol.
- the additive is present in an amount by mass of dispersion ranging from 0.001 to 20% by weight, preferably from 0.5 to 10%
- the mixture M of the suspension S and of the dispersion D is advantageously carried out with stirring by adding the dispersion D to the suspension S, so that the concentration of the polymer P in M is between 0.001 and 10% by mass dried.
- the application of the mixture M ( S + D ) to the surface of the paper and/or at least one of its layers, also called coating of the paper can be carried out by any means of coating.
- this coating means is a coater or a spray bar.
- coaters size presses
- roller coaters blade coaters
- rotary bar coaters curtain coaters
- vacuum coaters vacuum coaters
- step iv) of the process of the invention which consists in applying the mixture M, is carried out at a temperature of between 10 and 100°C and even more preferably between 30°C and 100°C.
- the mixture M advantageously makes it possible to improve the mechanical strength of the paper.
- the present invention relates to a process for improving the mechanical strength of paper comprising the application to the surface of the paper and/or of at least one of its layers of the mixture M according to the invention.
- the present invention also relates to the use of a water-swellable polymer P according to the invention for the treatment of paper, in particular the use of a water-swellable polymer P in combination with a polysaccharide, for the treatment of paper, in particular to improve the mechanical strength of the paper.
- the present invention also relates to the use of the mixture M for the treatment of paper, in particular for improving the mechanical strength of the paper.
- the paper forms are made with an automatic dynamic form.
- the paper pulp is prepared by disintegrating, for 25 minutes, 90 grams of recycled cardboard fibers in 2 liters of hot water (neutral pH pulp composed of 100% recycled fibers).
- the paste thus obtained is then diluted in water to a volume of 6 liters. Once the consistency has been precisely measured, the necessary quantity of this paste is removed so as to finally obtain a sheet with a basis weight of 90 g/m 2 .
- the paste is then introduced into the vat of the dynamic former, diluted to a consistency of 0.5% and stirred moderately with a mechanical stirrer in order to homogenize the aqueous suspension.
- a blotter and the training cloth are placed in the bowl of the dynamic former before starting the rotation of the bowl at 1000 revolutions per minute and building the water wall.
- the sheet is then produced by 23 round trips of the nozzle projecting the paste into the wall of water.
- the forming fabric, with the formed fiber network is removed from the bowl of the dynamic former and placed on a table.
- a dry blotter is laid on the side of the wet fiber mat and is pressed once with a roller. The whole is turned over and the canvas is delicately separated from the fibrous mattress.
- a second dry blotter is placed before turning the assembly over and removing the first waterlogged blotter.
- An aqueous suspension of uncooked native starch, with or without additives of polymer according to the invention, is then applied in the form of a spray (gun, bar, nebulizer, etc.), so as to uniformly deposit a dry quantity of the order of 1 g/m 2 .
- the wet sheet is then folded in two on the treated side, pressed between two rollers under 4 bars of pressure, then after renewing the blotter, dried on a dryer stretched for 10 minutes at 117°C.
- the blotter is then removed and the sheet thus formed is conditioned for a minimum of 12 hours in a room with controlled humidity and temperature (50% relative humidity and 23° C. temperature).
- Industrial flat cardboard is used on which an aqueous suspension S of uncooked native starch with or without additives of dispersion D of polymer is deposited using a threaded bar (the suspension S with additives corresponds to the mixture M ).
- This sheet is then folded in two on the treated side, placed in a blotter, pressed between two rollers under 4 bars of pressure, then dried on a dryer stretched for 10 minutes at 117°C.
- the blotter is then removed and the sheet thus formed is conditioned for a minimum of 12 hours in a room with controlled humidity and temperature (50% relative humidity and 23° C. temperature).
- the equipment used for the application on a dry sheet is a laboratory coater of the Multicoater K 303 type from RK Print Coat Instruments.
- the burst is measured with a Messmer Buchel M 405 burst tester (average over 12 values), according to the TAPPI T403 om-02 standard. The result is expressed in kPa.
- the burst index (Burst Index), expressed in kPa.m 2 /g, is determined by dividing this value by the grammage of the sheet.
- the internal cohesion test is carried out with a Scott Bond type apparatus (average over 5 values) according to the TAPPI T569 pm-00 procedure. The result is expressed in ft.lbs/in 2 .
- compositions used in the following examples are compositions used in the following examples:
- Composition Description E (Example) Aqueous dispersion containing 20% by mass of a water-swellable polymer P1 of acrylamide and crosslinked sodium acrylate, with a particle size of less than 50 ⁇ m. This aqueous dispersion contains a total of 43% by weight of dry matter, including in particular the water-swellable polymer, ammonium sulphate and dispersant polymers.
- C (Counterexample) Aqueous dispersion containing 20% by mass of a water-soluble polymer P2 of acrylamide and sodium acrylate, with a particle size of less than 50 ⁇ m. This aqueous dispersion contains a total of 43% by mass of dry matter, including in particular the water-soluble polymer, ammonium sulphate and dispersant polymers.
- compositions E and C Differentiation of compositions E and C : The compositions are diluted at 5 g/L in deionized water.
- a turbid suspension is obtained which is left to settle in a tube until an opalescent deposit at the bottom of the tube and a clear supernatant are obtained.
- the opalescent deposit represents the accumulation of particles of water-swellable polymer P1.
- composition C For composition C, dilution to 5 g/L leads directly to a clear and viscous solution. The polymer P2 is completely dissolved.
- a 110 g/m 2 industrial flat cardboard is used, the mechanical performance of which corresponds to the “white” test when it is not treated.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Description
L'invention concerne un procédé de traitement de surface du papier pour améliorer sa résistance mécanique.The invention relates to a process for treating the surface of paper to improve its mechanical strength.
Dans le cas de papiers et/ou cartons obtenus en superposant les couches de papier, il est important d'avoir une force adhésive entre les couches pour améliorer la cohésion du papier dans son épaisseur. Autrefois, des amidons tels que l'amidon de maïs, l'amidon de blé, l'amidon de pomme de terre ou les amidons modifiés chimiquement étaient utilisés en tant qu'agents renforçant la liaison des couches. La pratique était de déposer/pulvériser la suspension d'amidon sur le papier humide, puis de favoriser la gélatinisation de l'amidon pendant le processus de séchage pour améliorer la force adhésive.In the case of papers and/or cardboards obtained by superimposing the layers of paper, it is important to have an adhesive force between the layers to improve the cohesion of the paper in its thickness. In the past, starches such as corn starch, wheat starch, potato starch or chemically modified starches were used as layer bonding agents. The practice was to drop/spray the starch slurry onto the wet paper and then promote the gelatinization of the starch during the drying process to improve the adhesive strength.
Une baisse des performances mécaniques du papier est toutefois observée lorsque le profil de sécherie est trop violent car cela engendre une élimination rapide de l'eau du slurry d'amidon déposé en surface du papier.A drop in the mechanical performance of the paper is however observed when the drying section profile is too violent because this leads to rapid elimination of the water from the starch slurry deposited on the surface of the paper.
En effet, les grains d'amidon ont besoin de haute température, d'eau et de temps pour « éclater/exploser » et donc pour que l'amidon gélatinise. C'est l'amidon gélatinisé qui apporte les propriétés mécaniques. Si l'eau du slurry déposé en surface est éliminée trop rapidement par un profil de sécherie trop violent, ou par une absorption d'eau au sein du papier trop rapide, les grains sèchent en l'état, sans gélatiniser, donc sans apporter de performances.Indeed, the starch grains need high temperature, water and time to “burst/explode” and therefore for the starch to gelatinize. It is the gelatinized starch which provides the mechanical properties. If the water in the slurry deposited on the surface is eliminated too quickly by too violent a drying section profile, or by too rapid absorption of water within the paper, the grains dry as they are, without gelatinizing, and therefore without bringing any performance.
Plus récemment, un agent de résistance à sec de type polyacrylamide (PAM) a été utilisé en combinaison avec l'amidon. Grâce aux macromolécules synthétiques de type PAM, il devint possible de minimiser les problèmes liés à l'utilisation d'une solution aqueuse d'amidon, comme par exemple l'augmentation de la DCO (Demande Chimique en Oxygène), la formation de moisissures / bactéries provenant des substances naturelles telles que l'amidon, la maintenance lourde et nécessaire des buses de spray. Cela limitait également les pertes d'amidon au sein du papier ainsi que dans le circuit d'eau. Néanmoins, jusqu'à maintenant, tous les agents de résistance à sec testés en combinaison avec l'amidon étaient des polymères hydrosolubles.More recently, a polyacrylamide (PAM) dry strength agent has been used in combination with starch. Thanks to synthetic macromolecules of the PAM type, it became possible to minimize the problems linked to the use of an aqueous solution of starch, such as, for example, the increase in the COD (Chemical Oxygen Demand), the formation of moulds/ bacteria from natural substances such as starch, heavy and necessary maintenance of spray nozzles. This also limited starch losses within the paper as well as in the water circuit. However, until now, all dry strength agents tested in combination with starch have been water-soluble polymers.
La Demanderesse a découvert de manière surprenante qu'en appliquant en surface du papier et/ou d'au moins une de ses couches un mélange d'un polysaccharide et d'une dispersion aqueuse comprenant (a) des particules d'au moins un polymère hydrogonflable anionique et (b) au moins un composé choisi parmi un sel minéral, un sel organique, un polymère organique dispersant et leurs mélanges, les propriétés mécaniques de délamination sont plus élevées. Sans être lié à une quelconque théorie, il semble que la capacité de rétention d'eau du polymère hydrogonflable confère aux grains d'amidon une atmosphère humide plus résiliente aux conditions de sécherie drastiques, améliorant la gélatinisation de l'amidon.The Applicant has discovered, surprisingly, that by applying to the surface of the paper and/or at least one of its layers a mixture of a polysaccharide and an aqueous dispersion comprising (a) particles of at least one polymer anionic water-swellable material and (b) at least one compound chosen from an inorganic salt, an organic salt, a dispersing organic polymer and mixtures thereof, the mechanical properties of delamination are higher. Without being bound by any theory, it seems that the water-holding capacity of the water-swellable polymer gives the starch grains a moist atmosphere that is more resilient to drastic drying conditions, improving the gelatinization of the starch.
L'invention concerne donc un procédé de traitement de la surface du papier, et/ou d'au moins une de ses couches, comprenant les étapes successives suivantes :
- i) Fournir une suspension aqueuse S de polysaccharide,
- ii) Fournir d'une dispersion aqueuse D comprenant (a) des particules d'au moins un polymère hydrogonflable anionique P et (b) au moins un composé choisi parmi un sel minéral, un sel organique, un polymère organique dispersant et leurs mélanges,
- iii) Mélanger la suspension S et la dispersion D pour obtenir un mélange M,
- iv) Appliquer le mélange M en surface du papier, et/ou d'au moins une de ses couches.
- i) Provide an aqueous suspension S of polysaccharide,
- ii) Providing an aqueous dispersion D comprising (a) particles of at least one anionic water-swellable polymer P and (b) at least one compound chosen from an inorganic salt, an organic salt, a dispersing organic polymer and mixtures thereof,
- iii) Mix the suspension S and the dispersion D to obtain a mixture M,
- iv) Apply the mixture M to the surface of the paper, and/or at least one of its layers.
Le procédé de l'invention peut être mis en oeuvre sur du papier humide ou sec, de préférence humide. Dans le cadre de l'invention, on entend par papier humide le papier issu du processus de fabrication avant passage en sécherie.The method of the invention can be carried out on wet or dry, preferably wet, paper. In the context of the invention, wet paper is understood to mean the paper resulting from the manufacturing process before passing through the dryer section.
Avantageusement la suspension aqueuse S, contient entre 0,5 et 30% massique de polysaccharide dans l'eau, et encore plus avantageusement entre 5 et 20 % massique.Advantageously, the aqueous suspension S i contains between 0.5 and 30% by mass of polysaccharide in water, and even more advantageously between 5 and 20% by mass.
Préférentiellement le polysaccaride est choisi parmi l'amidon natif, l'amylose, l'amylopectine, la cellulose et les composés dérivés de la cellulose, les amidons modifiés tels que les amidons traités par voie enzymatique, les amidons hydrolysés, les amidons chauffés, les amidons cationiques, tels que ceux résultant de la réaction d'un amidon avec une amine tertiaire pour former un sel d'ammonium quaternaire, les amidons anioniques, les amidons amphotères; et toute combinaison de ceux-ci.Preferably, the polysaccharide is chosen from native starch, amylose, amylopectin, cellulose and compounds derived from cellulose, modified starches such as enzymatically treated starches, hydrolyzed starches, heated starches, cationic starches, such as those resulting from the reaction of a starch with a tertiary amine to form a quaternary ammonium salt, anionic starches, amphoteric starches; and any combination thereof.
De préférence, le polysaccharide est l'amidon natif. L'amidon natif est le produit de l'extraction de l'amidon sans modification ultérieure.Preferably, the polysaccharide is native starch. Native starch is the product of starch extraction without further modification.
Le polymère hydrogonflable P, utilisé dans l'étape ii) du procédé de l'invention est également connu comme polymère super-absorbant. Généralement, il a une capacité d'absorption d'eau supérieure à 10 fois son volume. De manière particulièrement avantageuse pour le procédé selon l'invention, au sein de la dispersion, le polymère hydrogonflable n'est pas ou peu hydrogonflé. Peu hydrogonflé signifie qu'il garde une capacité d'absorption d'eau supérieure à 10 fois son volume.The water-swellable polymer P , used in step ii) of the process of the invention is also known as a super-absorbent polymer. Generally, it has a water absorption capacity greater than 10 times its volume. In a particularly advantageous manner for the process according to the invention, within the dispersion, the water-swellable polymer is not or only slightly water-swelled. Low water swell means that it retains a water absorption capacity greater than 10 times its volume.
Le polymère hydrogonflable P utilisé dans l'étape ii) du procédé de l'invention est anionique, ce qui signifie que sa charge résultante est négative. Ce polymère peut être préparé à partir de différents monomères hydrosolubles, en particulier à partir d'au moins un monomère hydrosoluble comprenant au moins une double liaison éthylénique. Il peut ainsi être préparé à partir d'au moins un monomère anionique, à partir d'au moins un monomère non ionique, à partir d'au moins un monomère cationique ou encore à partir d'au moins un monomère zwitterionique, seuls ou en mélange. De façon générale, les polymères hydrogonflables P utilisés dans le procédé de l'invention sont obtenus par réticulation et forment donc des réseaux tridimensionnels.The water-swellable polymer P used in step ii) of the process of the invention is anionic, which means that its resulting charge is negative. This polymer can be prepared from various water-soluble monomers, in particular from at least one water-soluble monomer comprising at least one ethylenic double bond. It can thus be prepared from at least one anionic monomer, from at least one nonionic monomer, from at least one cationic monomer or even from at least one zwitterionic monomer, alone or in blend. In general, the water-swellable polymers P used in the process of the invention are obtained by crosslinking and therefore form three-dimensional networks.
Comme exemples de monomères anioniques, on utilise avantageusement au moins un monomère choisi parmi :
- les monomères comprenant au moins une fonction carboxylique, par exemple acide acrylique, acide méthacrylique, acide itaconique et leurs sels ;
- les monomères comprenant au moins une fonction acide sulfonique, par exemple l'acide 2-acrylamido-2-méthylpropane sulfonique (AMPS), l'acide allyl sulfonique et, l'acide methallyl sulfonique et leurs sels.
- monomers comprising at least one carboxylic function, for example acrylic acid, methacrylic acid, itaconic acid and their salts;
- the monomers comprising at least one sulphonic acid function, for example 2-acrylamido-2-methylpropane sulphonic acid (AMPS), allyl sulphonic acid and methallyl sulphonic acid and their salts.
Comme exemples de monomères non ioniques, on utilise avantageusement au moins un monomère choisi parmi :
- l'acrylamide et ses dérivés, notamment les N-alkylacrylamides, par exemple le Nisopropylacrylamide, le N-tert-butylacrylamide ; les N,N-dialkylacrylamides, par exemple le N,N-diméthylacrylamide et le N-méthylolacrylamide;
- le méthacrylamide et ses dérivés, notamment les N-alkylméthacrylamides, par exemple le N-isopropylméthacrylamide, le N-tert-butylméthacrylamide ; les N,Ndialkylméthacrylamides, par exemple le NN-diméthylméthacrylamide et le N-méthylolméthacrylamide ;
- la vinylformamide, la N-vinylpyridine, la N-vinylpyrrolidone, les hydroxyalkylacrylates, les hydroxyalkyl méthacrylates, les acrylates portant des chaînes alkoxy; les méthacrylates portant des chaînes alkoxy.
- acrylamide and its derivatives, in particular N-alkylacrylamides, for example Nisopropylacrylamide, N-tert-butylacrylamide; N,N-dialkylacrylamides, for example N,N-dimethylacrylamide and N-methylolacrylamide;
- methacrylamide and its derivatives, in particular N-alkylmethacrylamides, for example N-isopropylmethacrylamide, N-tert-butylmethacrylamide; N,N-dialkylmethacrylamides, for example N-N-dimethylmethacrylamide and N-methylolmethacrylamide;
- vinylformamide, N-vinylpyridine, N-vinylpyrrolidone, hydroxyalkylacrylates, hydroxyalkyl methacrylates, acrylates carrying alkoxy chains; methacrylates bearing alkoxy chains.
Comme exemples de monomères cationiques, on utilise avantageusement au moins un monomère choisi parmi :
- les sels de diallyldialkyl ammonium, par exemple le chlorure de diallyl dimethyl ammonium (DADMAC) ;
- les acrylates de dialkylaminoalkyle, les méthacrylates de dialkylaminoalkyle, en particulier l'acrylate de dialkylaminoalkyle de dialkylaminoéthyle (ADAME) et le méthacrylate de dialkylaminoéthyle (MADAME), ainsi que leurs formes acidifiées ou quaternisées, par exemple le chlorure de [2-(acryloyloxy)ethyl]triméthylammonium ; les dialkyl-aminoalkylacrylamides, les dialkyl-methacrylamides, ainsi que leurs formes acidifiées ou quaternisées, par exemple le chlorure d'acrylamido-propyl triméthyl ammonium.
- diallyldialkyl ammonium salts, for example diallyl dimethyl ammonium chloride (DADMAC);
- dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, in particular dialkylaminoethyl dialkylaminoalkyl acrylate (ADAME) and dialkylaminoethyl methacrylate (MADAME), as well as their acidified or quaternized forms, for example [2-(acryloyloxy) ethyl]trimethylammonium; dialkyl-aminoalkylacrylamides, dialkyl-methacrylamides, as well as their acidified or quaternized forms, for example acrylamido-propyl trimethyl ammonium chloride.
Comme exemples de monomères zwitterioniques, on utilise avantageusement au moins un monomère choisi parmi :
- les monomères sulfobétaïnes comme le sulfopropyl diméthylammonium éthyl méthacrylate, le sulfopropyl diméthylammonium propylméthacrylamide, le sulfopropyl 2-vinylpyridinium ;
- les monomères phosphobétaïnes, comme le phosphato éthyl triméthylammonium éthyl méthacrylate les monomères carboxybétaïnes.
- sulfobetaine monomers such as sulfopropyl dimethylammonium ethyl methacrylate, sulfopropyl dimethylammonium propylmethacrylamide, sulfopropyl 2-vinylpyridinium;
- phosphobetaine monomers, such as phosphato ethyl trimethylammonium ethyl methacrylate carboxybetaine monomers.
De manière avantageuse à l'étape ii) du procédé de l'invention, le polymère hydrogonflable P peut être un copolymère préparé à partir des monomères précédemment décrits ou à partir des monomères précédemment décrits et d'au moins un autre monomère choisi parmi les monomères hydrophobes, par exemple le styrène, les alkyl-acrylates, les alkyl-méthacrylates, les aryl-acrylates, les aryl-méthacrylates, les dérivés hydrophobes d'acrylamide; les monomères amphiphiles, par exemple le méthacrylate de dodécyl poly(oxyéthylène), le méthacrylate de béhényl poly(oxyéthylène); ou à partir de polymères naturels tels que par exemples, les dérivés cellulosiques, les polysaccharides, les argiles, par exemple ces polymères naturels peuvent être greffés sur les polymères hydrogonflables de l'invention pour former une autre famille de polymères hydrogonflables selon l'invention.Advantageously in step ii) of the process of the invention, the water-swellable polymer P can be a copolymer prepared from the monomers described above or from the monomers described above and at least one other monomer chosen from the monomers hydrophobic, for example styrene, alkyl-acrylates, alkyl-methacrylates, aryl-acrylates, aryl-methacrylates, hydrophobic derivatives of acrylamide; amphiphilic monomers, for example dodecyl poly(oxyethylene) methacrylate, behenyl poly(oxyethylene) methacrylate; or from natural polymers such as, for example, cellulose derivatives, polysaccharides, clays, for example these natural polymers can be grafted onto the water-swellable polymers of the invention to form another family of water-swellable polymers according to the invention.
Avantageusement, le polymère hydrogonflable P est un copolymère d'au moins un monomère non-ionique et d'au moins un monomère anionique. Préférentiellement, le polymère hydrogonflable anionique P est issu d'au moins 1 mol% d'au moins un monomère anionique hydrosoluble comprenant une double liaison éthylénique et au moins une fonction acide carboxylique ou sulfonique et d'au moins 5 mol % d'au moins un monomère non ionique choisi parmi l'acrylamide, le méthacrylamide et leurs dérivés, la vinylformamide et la N-vinylpyrrolidone.Advantageously, the water-swellable polymer P is a copolymer of at least one nonionic monomer and of at least one anionic monomer. Preferably, the anionic water-swellable polymer P is derived from at least 1 mol% of at least one water-soluble anionic monomer comprising an ethylenic double bond and at least one carboxylic or sulphonic acid function and from at least 5 mol% of at least a nonionic monomer chosen from acrylamide, methacrylamide and their derivatives, vinylformamide and N-vinylpyrrolidone.
Préférentiellement, le polymère hydrogonflable P contient entre 1 et 40 mol % d'au moins un monomère anionique hydrosoluble comprenant une double liaison éthylénique et au moins une fonction acide carboxylique ou sulfonique et entre 60 et 99 mol% d'au moins un monomère non ionique choisi parmi l'acrylamide, le méthacrylamide et leurs dérivés, la vinylformamide et la N-vinylpyrrolidone.Preferably, the water-swellable polymer P contains between 1 and 40 mol% of at least one water-soluble anionic monomer comprising an ethylenic double bond and at least one carboxylic or sulphonic acid function and between 60 and 99 mol% of at least one nonionic monomer chosen from acrylamide, methacrylamide and their derivatives, vinylformamide and N-vinylpyrrolidone.
Selon un mode de réalisation préféré, le monomère anionique hydrosoluble est choisi parmi l'acide acrylique, l'acide méthacrylique et leurs sels, l'acide 2-acrylamido-2-méthylpropane sulfonique et ses sels, l'acide itaconique et ses sels, l'acide allyl sulfonique et ses sels, l'acide methallyl sulfonique et ses sels.According to a preferred embodiment, the water-soluble anionic monomer is chosen from acrylic acid, methacrylic acid and their salts, 2-acrylamido-2-methylpropane sulphonic acid and its salts, itaconic acid and its salts, allyl sulphonic acid and its salts, methallyl sulphonic acid and its salts.
De manière encore plus préférentielle, le polymère anionique hydrogonflable P est un copolymère d'acrylamide et d'acrylate de sodium.Even more preferably, the water-swellable anionic polymer P is a copolymer of acrylamide and sodium acrylate.
Selon un mode de réalisation préféré, pour le procédé de l'invention, la dispersion aqueuse D comprend de 5 à 60 % en poids sec, et encore plus préférentiellement de 15 à 35 % en poids sec, de polymère hydrogonflable P. According to a preferred embodiment, for the process of the invention, the aqueous dispersion D comprises from 5 to 60% by dry weight, and even more preferably from 15 to 35% by dry weight, of water-swellable polymer P.
Pour le procédé selon l'invention, les particules de polymère hydrogonflable P ont de façon avantageuse un diamètre permettant leur dispersion. De préférence, les particules présentent un diamètre moyen allant de 0,1 et 1 000 µm, plus préférentiellement allant de 0,1 et 200 µm, encore plus préférentiellement allant de 0,1 et 20 µm. Le diamètre moyen des particules peut être déterminé par toute méthode connue de l'homme du métier, par exemple par microscopie binoculaire.For the process according to the invention, the particles of water-swellable polymer P advantageously have a diameter allowing them to be dispersed. Preferably, the particles have an average diameter ranging from 0.1 and 1000 μm, more preferentially ranging from 0.1 and 200 μm, even more preferentially ranging from 0.1 and 20 μm. The average diameter of the particles can be determined by any method known to those skilled in the art, for example by binocular microscopy.
Outre le polymère hydrogonflable P, la dispersion aqueuse D comprend un composé (b) qui a une fonction d'agent d'équilibrage. Il s'agit d'un composé hydrosoluble ou miscible à l'eau. Au sein de la dispersion selon l'invention, il permet d'inhiber totalement ou partiellement la capacité d'hydrogonflage du polymère P. Ainsi, au sein de cette dispersion aqueuse, en présence de ce composé (b), le polymère hydrogonflable (P) est présent sous forme de particules et n'est pas ou peu à l'état hydrogonflé.Besides the water-swellable polymer P , the aqueous dispersion D comprises a compound (b) which has a balancing agent function. It is a water-soluble or water-miscible compound. Within the dispersion according to the invention, it makes it possible to totally or partially inhibit the hydroswelling capacity of the polymer P. Thus, within this aqueous dispersion, in the presence of this compound (b), the hydroswellable polymer ( P ) is present in the form of particles and is not or only slightly in the hydroswollen state.
De manière préférée, la dispersion aqueuse comprend au moins un composé (b) choisi parmi :
- les sels minéraux ou organiques comprenant au moins un anion choisi parmi les sulfates, les dihydrogénophosphates, les phosphates, les halogénures ;
- les sels minéraux ou organiques comprenant au moins un cation choisi parmi le sodium, le potassium, l'ammonium, le magnésium, le calcium, l'aluminium ;
- les mélanges d'au moins deux de ces sels ;
- les polymères organiques dispersants choisis parmi les polymères ou les copolymères à base d'acide acrylique, d'acide 2-acrylamido-2-méthylpropane sulfonique et leurs sels et d'acrylamide de poids moléculaire allant de 1000 à 30 000 g.mol-1.
- inorganic or organic salts comprising at least one anion chosen from sulfates, dihydrogen phosphates, phosphates, halides;
- inorganic or organic salts comprising at least one cation chosen from sodium, potassium, ammonium, magnesium, calcium, aluminium;
- mixtures of at least two of these salts;
- dispersant organic polymers chosen from polymers or copolymers based on acrylic acid, 2-acrylamido-2-methylpropane sulphonic acid and their salts and acrylamide with a molecular weight ranging from 1000 to 30,000 g.mol -1 .
De manière préférée, la dispersion D comprend, comme composé (b), de 8 à 27 % en masse de sel minéral ou de sel organique et de 5 à 20 % en masse sèche de polymère organique dispersant.Preferably, dispersion D comprises, as compound (b), from 8 to 27% by mass of inorganic salt or organic salt and from 5 to 20% by dry mass of dispersing organic polymer.
Selon l'invention, la dispersion D peut également comprendre au moins un additif choisi parmi les alcools polyfonctionnels, par exemple le glycérol, les polyalkylèneglycols tels que le polyéthylèneglycol et le polypropylèneglycol. Avantageusement, l'additif est présent en une quantité en masse de dispersion allant de 0,001 à 20 % en poids, préférentiellement de 0,5 à 10%According to the invention, the dispersion D can also comprise at least one additive chosen from polyfunctional alcohols, for example glycerol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Advantageously, the additive is present in an amount by mass of dispersion ranging from 0.001 to 20% by weight, preferably from 0.5 to 10%
Le mélange M de la suspension S et de la dispersion D, est effectué avantageusement sous agitation par ajout de la dispersion D dans la suspension S, de manière à ce que la concentration du polymère P dans M soit comprise entre 0,001 à 10 % en masse sèche.The mixture M of the suspension S and of the dispersion D is advantageously carried out with stirring by adding the dispersion D to the suspension S, so that the concentration of the polymer P in M is between 0.001 and 10% by mass dried.
Pour l'étape iv) du procédé de l'invention, l'application du mélange M (S + D) en surface du papier et/ou d'au moins une de ses couches, aussi appelée enduction du papier, peut être effectuée par tout moyen d'enduction. Préférentiellement, ce moyen d'enduction est une coucheuse ou une barre de spray. Il existe plusieurs types de coucheuses (« size press ») dont les coucheuses à rouleaux, les coucheuses à lame, les coucheuses à barre rotative, les coucheuses rideau et les coucheuses sous vide.For step iv) of the process of the invention, the application of the mixture M ( S + D ) to the surface of the paper and/or at least one of its layers, also called coating of the paper, can be carried out by any means of coating. Preferably, this coating means is a coater or a spray bar. There are several types of coaters (“size presses”) including roller coaters, blade coaters, rotary bar coaters, curtain coaters and vacuum coaters.
Enfin selon une dernière préférence, l'étape iv) du procédé de l'invention qui consiste à appliquer le mélange M, se fait à une température comprise entre 10 et 100°C et encore plus préférentiellement entre 30°C et 100°C.Finally, according to a final preference, step iv) of the process of the invention, which consists in applying the mixture M, is carried out at a temperature of between 10 and 100°C and even more preferably between 30°C and 100°C.
Le mélange M permet avantageusement d'améliorer la résistance mécanique du papier. Ainsi, de préférence, la présente invention concerne un procédé d'amélioration de la résistance mécanique du papier comprenant l'application à la surface du papier et/ou d'au moins une de ses couches du mélange M selon l'invention.The mixture M advantageously makes it possible to improve the mechanical strength of the paper. Thus, preferably, the present invention relates to a process for improving the mechanical strength of paper comprising the application to the surface of the paper and/or of at least one of its layers of the mixture M according to the invention.
La présente invention concerne également l'utilisation d'un polymère hydrogonflable P selon l'invention pour le traitement du papier, notamment l'utilisation d'un polymère hydrogonflable P en combinaison avec un polysaccharide, pour le traitement du papier, notamment pour améliorer la résistance mécanique du papier.The present invention also relates to the use of a water-swellable polymer P according to the invention for the treatment of paper, in particular the use of a water-swellable polymer P in combination with a polysaccharide, for the treatment of paper, in particular to improve the mechanical strength of the paper.
La présente invention concerne également l'utilisation du mélange M pour le traitement du papier, notamment pour améliorer la résistance mécanique du papier.The present invention also relates to the use of the mixture M for the treatment of paper, in particular for improving the mechanical strength of the paper.
L'invention et les avantages qui en résultent ressortiront bien des exemples de réalisation suivants.The invention and the resulting advantages will clearly emerge from the following embodiments.
Les formettes de papier sont réalisées avec une formette dynamique automatique. Tout d'abord, la pâte à papier est préparée en désintégrant, pendant 25 minutes, 90 grammes de fibres de carton recyclé dans 2 litres d'eau chaude (pâte à pH neutre composée de 100% de fibres recyclées). La pâte ainsi obtenue est ensuite diluée dans l'eau jusqu'à un volume de 6 litres. Une fois la consistance mesurée précisément, la quantité nécessaire de cette pâte est prélevée de manière à obtenir finalement une feuille avec un grammage de 90 g/m2.The paper forms are made with an automatic dynamic form. First, the paper pulp is prepared by disintegrating, for 25 minutes, 90 grams of recycled cardboard fibers in 2 liters of hot water (neutral pH pulp composed of 100% recycled fibers). The paste thus obtained is then diluted in water to a volume of 6 liters. Once the consistency has been precisely measured, the necessary quantity of this paste is removed so as to finally obtain a sheet with a basis weight of 90 g/m 2 .
La pâte est alors introduite dans le cuvier de la formette dynamique, diluée jusqu'à une consistance de 0.5% et agitée modérément avec un agitateur mécanique afin d'homogénéiser la suspension aqueuse.The paste is then introduced into the vat of the dynamic former, diluted to a consistency of 0.5% and stirred moderately with a mechanical stirrer in order to homogenize the aqueous suspension.
Un buvard et la toile de formation sont placés dans le bol de la formette dynamique avant de démarrer la rotation du bol à 1000 tours par minute et de construire le mur d'eau. La feuille est alors réalisée par 23 aller-retours de la buse projetant la pâte dans le mur d'eau. Une fois que l'eau est drainée et que la séquence automatique est terminée, la toile de formation, avec le réseau de fibres formé, est retirée du bol de la formette dynamique et placée sur une table. Un buvard sec est déposé du côté du matelas de fibres humides et est pressé une fois avec un rouleau. L'ensemble est retourné et la toile est délicatement séparée du matelas fibreux. Un second buvard sec est déposé avant de retourner l'ensemble et de retirer le premier buvard gorgé d'eau.A blotter and the training cloth are placed in the bowl of the dynamic former before starting the rotation of the bowl at 1000 revolutions per minute and building the water wall. The sheet is then produced by 23 round trips of the nozzle projecting the paste into the wall of water. Once the water is drained and the automatic sequence is complete, the forming fabric, with the formed fiber network, is removed from the bowl of the dynamic former and placed on a table. A dry blotter is laid on the side of the wet fiber mat and is pressed once with a roller. The whole is turned over and the canvas is delicately separated from the fibrous mattress. A second dry blotter is placed before turning the assembly over and removing the first waterlogged blotter.
On applique ensuite sous forme de spray (pistolet, barre, nébuliseur, ...) une suspension aqueuse d'amidon natif non cuit, additivé ou non de polymère selon l'invention, de manière à déposer uniformément une quantité sèche de l'ordre de 1 g/m2.An aqueous suspension of uncooked native starch, with or without additives of polymer according to the invention, is then applied in the form of a spray (gun, bar, nebulizer, etc.), so as to uniformly deposit a dry quantity of the order of 1 g/m 2 .
La feuille humide est ensuite repliée en deux sur la face traitée, pressée entre deux rouleaux sous 4 bars de pression, puis après avoir renouvelé le buvard, séchée sur un sécheur tendu pendant 10 minutes à 117°C. Le buvard est ensuite retiré et la feuille ainsi formée est conditionnée pendant 12 heures minimum dans une pièce à humidité et température contrôlées (50% d'humidité relative et 23°C de température).The wet sheet is then folded in two on the treated side, pressed between two rollers under 4 bars of pressure, then after renewing the blotter, dried on a dryer stretched for 10 minutes at 117°C. The blotter is then removed and the sheet thus formed is conditioned for a minimum of 12 hours in a room with controlled humidity and temperature (50% relative humidity and 23° C. temperature).
Les propriétés de résistance à sec des différentes feuilles obtenues par cette procédure sont évaluées.The dry strength properties of the different sheets obtained by this procedure are evaluated.
On utilise du carton plat industriel sur lequel on dépose à l'aide d'une barre filetée une suspension aqueuse S d'amidon natif non cuit additivée ou non de dispersion D de polymère (La suspension S additivée correspond au mélange M). Cette feuille est ensuite repliée en deux sur la face traitée, placée dans un buvard, pressée entre deux rouleaux sous 4 bars de pression, puis séchée sur un sécheur tendu pendant 10 minutes à 117°C. Le buvard est ensuite retiré et la feuille ainsi formée est conditionnée pendant 12 heures minimum dans une pièce à humidité et température contrôlées (50% d'humidité relative et 23°C de température).Industrial flat cardboard is used on which an aqueous suspension S of uncooked native starch with or without additives of dispersion D of polymer is deposited using a threaded bar (the suspension S with additives corresponds to the mixture M ). This sheet is then folded in two on the treated side, placed in a blotter, pressed between two rollers under 4 bars of pressure, then dried on a dryer stretched for 10 minutes at 117°C. The blotter is then removed and the sheet thus formed is conditioned for a minimum of 12 hours in a room with controlled humidity and temperature (50% relative humidity and 23° C. temperature).
Les propriétés de résistance à sec des différentes feuilles obtenues par cette procédure sont évaluées.The dry strength properties of the different sheets obtained by this procedure are evaluated.
L'équipement utilisé pour la dépose sur feuille sèche est une coucheuse de laboratoire de type Multicoater K 303 de RK Print Coat Instruments.The equipment used for the application on a dry sheet is a laboratory coater of the Multicoater K 303 type from RK Print Coat Instruments.
L'éclatement est mesuré avec un éclatomètre Messmer Buchel M 405 (moyenne sur 12 valeurs), selon la norme TAPPI T403 om-02. Le résultat est exprimé en kPa. On détermine l'indice d'éclatement (Burst Index), exprimé en kPa.m2/g, en divisant cette valeur par le grammage de la feuille.The burst is measured with a Messmer Buchel M 405 burst tester (average over 12 values), according to the TAPPI T403 om-02 standard. The result is expressed in kPa. The burst index (Burst Index), expressed in kPa.m 2 /g, is determined by dividing this value by the grammage of the sheet.
Le test de cohésion interne est réalisé avec un appareil de type Scott Bond (moyenne sur 5 valeurs) selon la procédure TAPPI T569 pm-00. Le résultat est exprimé en ft.lbs/in2.The internal cohesion test is carried out with a Scott Bond type apparatus (average over 5 values) according to the TAPPI T569 pm-00 procedure. The result is expressed in ft.lbs/in 2 .
Différentiation compositions E et C : Les compositions sont diluées_à 5 g/L dans de l'eau déionisée. Pour la composition E, on obtient une suspension turbide qu'on laisse décanter dans un tube jusqu'à obtenir un dépôt opalescent au fond du tube et un surnageant limpide. Le dépôt opalescent représente l'accumulation des particules de polymère hydrogonflable P1. Differentiation of compositions E and C : The compositions are diluted at 5 g/L in deionized water. For composition E, a turbid suspension is obtained which is left to settle in a tube until an opalescent deposit at the bottom of the tube and a clear supernatant are obtained. The opalescent deposit represents the accumulation of particles of water-swellable polymer P1.
Pour la composition C, la dilution à 5 g/L conduit directement à une solution limpide et visqueuse. Le polymère P2 est complètement dissous.For composition C, dilution to 5 g/L leads directly to a clear and viscous solution. The polymer P2 is completely dissolved.
On utilise un carton plat industriel de 110 g/m2 dont les performances mécaniques correspondent à l'essai « blanc » lorsqu'il n'est pas traité.A 110 g/m 2 industrial flat cardboard is used, the mechanical performance of which corresponds to the “white” test when it is not treated.
Comme essai de référence, on dépose sur celui-ci, grâce à la coucheuse de laboratoire (barre filetée n°3), un lait d'amidon de blé natif à 18% de matière sèche.As a reference test, using the laboratory coater (threaded bar No. 3), a milk of native wheat starch containing 18% dry matter is deposited on it.
On reproduit cette dernière opération, toutes choses étant égales par ailleurs, en préparant au préalable à la dépose, les mélanges lait d'amidon de blé natif/ dispersion de polymère de manière à substituer 5% de la matière sèche de l'amidon par la même quantité en matière sèche de polymère P1 ou P2 (par ajout des quantités respectives requises des compositions E et C).
Le fait d'additiver de l'amidon natif avec des polymères synthétiques apporte un gain indéniable en termes de performances de résistances mécaniques du papier, ici la résistance à la délamination (cohésion interne), ainsi que la résistance à l'éclatement. Mais surtout, on observe clairement ici l'intérêt tout particulier à l'utilisation du polymère hydrogonflable P1 en lieu et place du polymère hydrosoluble P2.The fact of adding native starch with synthetic polymers brings an undeniable gain in terms of performance of mechanical resistance of the paper, here the resistance to delamination (internal cohesion), as well as the resistance to bursting. But above all, the very particular interest in using the water-swellable polymer P1 instead of the water-soluble polymer P2 is clearly observed here.
On prépare trois feuilles selon la procédure décrite précédemment :
- une première feuille sans traitement (Blanc),
- la deuxième en déposant l'équivalent de 0,38 g/m2 d'amidon de blé natif.
- La troisième en déposant l'équivalent de 0,374 g/m2 d'un mélange amidon de blé natif/P1 (90/10), soit une dépose respective de 0,34 g/m2 + 0,034 g/m2.
- a first sheet without treatment (White),
- the second by depositing the equivalent of 0.38 g/m 2 of native wheat starch.
- The third by depositing the equivalent of 0.374 g/m 2 of a native wheat starch/ P1 (90/10) mixture, ie a respective deposit of 0.34 g/m 2 +0.034 g/m 2 .
Les performances de cohésion interne et d'éclatement sont clairement améliorées en substituant 10% de l'amidon natif par la même quantité de polymère hydrogonflable P1. The internal cohesion and bursting performances are clearly improved by replacing 10% of the native starch with the same quantity of water-swellable polymer P1.
Claims (11)
- A method for treating the surface of paper and/or at least one of the layers thereof, comprising the following successive steps:i) Supplying an aqueous suspension S of polysaccharide;ii) Supplying an aqueous dispersion D comprising (a) particles of at least one anionic water-swellable polymer P and (b) at least one compound selected from a mineral salt, an organic salt, an organic dispersing polymer and the mixtures thereof;iii) Mixing the suspension S and the dispersion D to obtain a mixture M;iv) Applying the mixture M to the surface of the paper and/or to at least one of the layers thereof.
- The method according to claim 1, characterized in that the polysaccharide is selected from among native starch, amylose, amylopectin, cellulose and compounds derived from cellulose, modified starches such as enzymatically treated starches, hydrolysed starches, heated starches, cationic starches such as those resulting from the reaction of a starch with a tertiary amine to form a quaternary ammonium salt, anionic starches, amphoteric starches; and any combination thereof.
- The method according to the preceding claims, characterized in that the anionic water-swellable polymer P is derived from at least 1 mol % of at least one anionic water-soluble monomer comprising an ethylenic double bond and at least one carboxylic or sulfonic acid function and from at least 5 mol % of at least one nonionic monomer selected from among acrylamide, methacrylamide and derivatives thereof, vinylformamide and N-vinylpyrrolidone.
- The method according to the preceding claims, characterized in that the anionic water-soluble monomer is selected from among acrylic acid, methacrylic acid and the salts thereof, 2-acrylamido-2-methylpropane sulfonic acid and the salts thereof, itaconic acid and the salts thereof, allyl sulfonic acid and the salts thereof, methallyl sulfonic acid and the salts thereof.
- The method according to the preceding claims, characterized in that the anionic water-swellable polymer P is a copolymer of acrylamide and sodium acrylate.
- The method according to one of the preceding claims, characterized in that the dispersion D comprises from 5 to 60 weight %, preferably from 15 to 35 weight % of anionic water-swellable polymer P.
- The method according to the preceding claims, characterized in that the particles of aqueous dispersion D have a mean diameter ranging from 0.1 to 1 000 µm, preferably ranging from 0.1 to 200 µm, more preferably ranging from 0.1 to 20 µm.
- The method according to one of the preceding claims, characterized in that the dispersion D comprises at least one compound (b) selected from among:- mineral or organic salts comprising at least one anion selected from among sulfates, dihydrogen phosphates, phosphates, halides; or- mineral or organic salts comprising at least one cation selected from among sodium, potassium, ammonium, magnesium, calcium, aluminium; or- mixtures of at least two of these salts; or- organic dispersing polymers selected from among polymers or copolymers of acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid and the salts thereof and acrylamide having a molecular weight ranging from 1000 to 30 000 g.mol-1.
- The method according to one of the preceding claims in which the dispersion D comprises:- from 8 to 27 weight % of mineral salt or organic salt; or- from 5 to 20 weight % of organic dispersing polymer.
- The method according to one of the preceding claims, characterized in that for step iv), the application to the surface of paper and/or to at least one of the layers thereof is carried out with a size press or spray bar.
- The method according to the preceding claims, characterized in that for step iv) the application to the surface of paper and/or to one of the layers thereof is conducted at a temperature of between 10 and 100 °C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1902634A FR3093738B1 (en) | 2019-03-14 | 2019-03-14 | INCREASED PAPER RESISTANCE BY SURFACE TREATMENT |
| PCT/EP2020/056774 WO2020182977A1 (en) | 2019-03-14 | 2020-03-13 | Increasing paper strength by surface treatment |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP3938575A1 EP3938575A1 (en) | 2022-01-19 |
| EP3938575B1 true EP3938575B1 (en) | 2023-07-05 |
| EP3938575B8 EP3938575B8 (en) | 2023-08-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20709236.2A Active EP3938575B8 (en) | 2019-03-14 | 2020-03-13 | Increased paper strength by surface treatment |
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| Country | Link |
|---|---|
| US (1) | US11781271B2 (en) |
| EP (1) | EP3938575B8 (en) |
| KR (1) | KR20210138605A (en) |
| CN (1) | CN113557331A (en) |
| BR (1) | BR112021018153A2 (en) |
| CA (1) | CA3132084A1 (en) |
| FI (1) | FI3938575T3 (en) |
| FR (1) | FR3093738B1 (en) |
| WO (1) | WO2020182977A1 (en) |
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| US6494990B2 (en) * | 1995-08-25 | 2002-12-17 | Bayer Corporation | Paper or board with surface of carboxylated surface size and polyacrylamide |
| PL205556B1 (en) | 2002-04-09 | 2010-05-31 | Fpinnovations | Swollen starch-latex compositions for use in papermaking |
| US20110091733A1 (en) * | 2008-06-24 | 2011-04-21 | Basf Se | Paper coating composition comprising metal salt pigments and having a content of aqueous dispersions of water-soluble copolymers |
-
2019
- 2019-03-14 FR FR1902634A patent/FR3093738B1/en active Active
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2020
- 2020-03-13 WO PCT/EP2020/056774 patent/WO2020182977A1/en active Application Filing
- 2020-03-13 BR BR112021018153A patent/BR112021018153A2/en unknown
- 2020-03-13 CA CA3132084A patent/CA3132084A1/en active Pending
- 2020-03-13 US US17/437,496 patent/US11781271B2/en active Active
- 2020-03-13 KR KR1020217029481A patent/KR20210138605A/en active Search and Examination
- 2020-03-13 FI FIEP20709236.2T patent/FI3938575T3/en active
- 2020-03-13 CN CN202080020624.3A patent/CN113557331A/en active Pending
- 2020-03-13 EP EP20709236.2A patent/EP3938575B8/en active Active
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|---|---|
| FR3093738B1 (en) | 2021-04-02 |
| BR112021018153A2 (en) | 2021-11-16 |
| EP3938575A1 (en) | 2022-01-19 |
| KR20210138605A (en) | 2021-11-19 |
| FR3093738A1 (en) | 2020-09-18 |
| WO2020182977A1 (en) | 2020-09-17 |
| CN113557331A (en) | 2021-10-26 |
| CA3132084A1 (en) | 2020-09-17 |
| FI3938575T3 (en) | 2023-09-27 |
| US11781271B2 (en) | 2023-10-10 |
| US20220162803A1 (en) | 2022-05-26 |
| EP3938575B8 (en) | 2023-08-09 |
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