EP3688223B1 - Paper support, security document which comprises same and manufacturing process - Google Patents
Paper support, security document which comprises same and manufacturing process Download PDFInfo
- Publication number
- EP3688223B1 EP3688223B1 EP18782358.8A EP18782358A EP3688223B1 EP 3688223 B1 EP3688223 B1 EP 3688223B1 EP 18782358 A EP18782358 A EP 18782358A EP 3688223 B1 EP3688223 B1 EP 3688223B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper medium
- paper
- agent
- structural reinforcement
- dry state
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000002209 hydrophobic effect Effects 0.000 claims description 20
- 229920003043 Cellulose fiber Polymers 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000002671 adjuvant Substances 0.000 claims description 15
- 238000007639 printing Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- -1 i.e. Substances 0.000 claims description 10
- 239000010702 perfluoropolyether Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000004902 Softening Agent Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 238000007754 air knife coating Methods 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920006317 cationic polymer Polymers 0.000 claims description 3
- 238000007766 curtain coating Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims 10
- 238000007493 shaping process Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 239000012744 reinforcing agent Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 15
- 230000035699 permeability Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000976 ink Substances 0.000 description 10
- 239000011436 cob Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
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- 230000006378 damage Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000003746 surface roughness Effects 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 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 210000002615 epidermis Anatomy 0.000 description 1
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- 239000002979 fabric softener Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 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 1
- 239000004816 latex Substances 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
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- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- SKIVFJLNDNKQPD-UHFFFAOYSA-N sulfacetamide Chemical compound CC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 SKIVFJLNDNKQPD-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910000648 terne Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002023 wood 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
- 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
- D21H17/33—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
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- 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
- D21H17/53—Polyethers; Polyesters
-
- 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
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
Definitions
- the invention relates to a high-durability paper support for printing a security document, in particular a banknote.
- the invention also relates to a method of manufacturing this paper medium and a security document made from such a paper medium.
- Security documents and in particular banknotes are subject to numerous stresses during their circulation. These may be of a mechanical nature, for example folds, creases and other manipulations which may lead to more or less marked deterioration of the fibers or even tearing of the latter.
- Banknotes made of plastic material are also known, for example those produced on bi-oriented polypropylene (BOPP), presented as products ensuring a high longevity and other hybrid products comprising both parts of paper and other plastic based on polyamides or polyesters.
- BOPP bi-oriented polypropylene
- the central banks responsible for the issue, circulation and withdrawal of banknotes have budgetary constraints which force them to seek an increase in the longevity of banknotes, in order to reduce the cost of the cycle of cash, which makes them legitimately turn to the aforementioned solutions.
- the varnishing of the support is mandatory to guarantee a minimum hold over time.
- the reinforcing agent consists of additional fibers of a different nature, which are added to the cellulose fibers already usually present in the structure of the paper.
- the document describes WO 2007/000177 a process for the manufacture of two-ply toilet paper in which, before bringing these two layers together, a softening composition providing a pleasant contact for the epidermis is applied to at least one surface of the outer sheet.
- the present invention relates to a high-durability paper support for printing a security document, in particular a banknote, comprising cellulose fibers, in a proportion of at least 50% by mass relative to the total mass of the paper support in the dry state, additives and adjuvants, at least one binder, and which also comprises at least one oleophobic and hydrophobic agent based on an organic compound containing perfluoropolyether (PFPE) groups, in a concentration greater than 0% and less than or equal to 5% by mass in the dry state relative to the total mass of the paper support in the dry state,
- PFPE perfluoropolyether
- This support also comprises at least one non-fibrous structural reinforcing agent from the family of softening agents, that is to say agents increasing the flexibility of cellulose fibers, in an amount of between 0.5% and 15% by mass relative to the total mass of the paper support in the dry state.
- the invention also relates to a security document which comprises a support according to one of the preceding characteristics.
- said document is a banknote.
- the structural reinforcing agents and the oleophobic and hydrophobic agents are applied offline, separately or as a mixture, by coating, dipping, impregnation, surfacing, spraying, air knife coating, curtain coating, pencil coating, roller coating engraved, appointed or by transfer, type "size press", “film press”, without this list being exhaustive
- the high durability properties are obtained by a surface treatment which does not require modification of the fibrous composition of the substrate.
- the air permeability obtained is not zero, contrary to the permeability of the majority of high-durability supports currently known on the market.
- the Cobb bonding value obtained that is to say the water absorption capacity of the support, is normal and comparable to that of standard banknote paper, which reinforces its printability. Its printing is therefore facilitated.
- the support as described by the invention retains its barrier properties after crumpling, with in particular permeability and Cobb values which remain relatively low, unlike untreated paper. These characteristics constitute important parameters which enable the support to better resist mechanical stresses when it is in circulation in the field.
- the support as described by the invention has increased resistance to bending while retaining normal overall stiffness comparable to standard paper.
- the fibers used in the composition of the paper support are mainly cellulose fibers.
- these cellulose fibers are chosen from fibers derived from deciduous wood, softwood, seasonal plants such as cotton, hemp or linen, for example. These different fibers can be used alone or in a mixture.
- the cellulose fibers used are cotton fibers. This fiber is used for its good physical and mechanical characteristics. Indeed, the long cotton fibers can measure up to 40 mm long, which gives the paper obtained a very good resistance to folding.
- the paper support in accordance with the invention also comprises non-fibrous additives and adjuvants, preferably chosen from anti-foam compounds, mineral fillers, wet strength agents and sizing agents used alone or in combination. mixture of at least two of them.
- the antifoam compounds are, for example, agents such as silicones, silicone emulsions, polyethylene glycols, derivatives of polyethylene glycols, synthetic polyalcohols, derivatives of polyalcohols, amide-based antifoams, ester base; surfactants such as oligomers, ethylene oxides (EtO), polypropylene oxides (PPOx); hydrophobic agents such as hydrocarbon waxes, polyethylene waxes, fatty alcohols, fatty acids, fatty esters, ethylene bis(steramide) (EBS), hydrophobic silicas.
- agents such as silicones, silicone emulsions, polyethylene glycols, derivatives of polyethylene glycols, synthetic polyalcohols, derivatives of polyalcohols, amide-based antifoams, ester base
- surfactants such as oligomers, ethylene oxides (EtO), polypropylene oxides (PPOx)
- hydrophobic agents such as hydrocarbon waxes,
- anti-foam compounds will be added during the preparation of the paper pulp as well as in the wet end of the paper machine, in order to avoid the formation of foam, or even to destroy it and thus improve the formation of the sheet.
- the mineral fillers are chosen from colloidal silica, sodium silicates, sodium aluminosilicates, natural or precipitated calcium carbonates, talc, natural or calcined kaolin, alumina hydrate, titanium and barium sulphate, alone or as a mixture of at least two of them.
- These mineral fillers are added to modify the optical properties of the paper obtained, such as its whiteness, its shine or its opacity, but also its surface properties. Some of these fillers are less expensive than fibers and are therefore added to reduce manufacturing costs.
- Wet strength agents are thermosetting polymers that are added while the paper is still wet and which crosslink in the paper during its passage through the dryer section. They act as a water barrier once the paper is made.
- mainly polymers are used which ensure the bonding of the fibers together, such as urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, resins based on polyamidoamine-epichlorohydrin (PAA-E ), glyoxal resins, metal ion complexes alone or as a mixture.
- UF urea-formaldehyde
- MF melamine-formaldehyde
- PAA-E polyamidoamine-epichlorohydrin
- glyoxal resins metal ion complexes alone or as a mixture.
- Sizing agents retard the penetration of liquids into the paper. They are implemented either when the paper is still in the wet state (sizing in the mass of the paper), or at the level of the size press (sizing on the surface).
- natural products are used, such as modified natural resins (resin-based glues), starch or modified starch or synthetic products, such as alkyl ketene dimer (AKD), alkenile succinic anhydride (ASA) and other polymers (eg copolymers based on esters of acrylic acid and maleic acid, acrylonitrile and styrene).
- AKD alkyl ketene dimer
- ASA alkenile succinic anhydride
- other polymers eg copolymers based on esters of acrylic acid and maleic acid, acrylonitrile and styrene.
- paraffin wax and polyethylene waxes are examples of polyethylene waxes.
- the fibers, additives and adjuvants are mixed and are bonded together by the use of at least one binder.
- This binder makes it possible to improve the resistance of the paper in the dry state.
- the binder is chosen from polyvinyl alcohols, starch, starches, latex, hemicelluloses, CMCs (carboxymethylcelluloses), galactomannans, gelatins or polyamide-epichlorohydrin resins, taken alone or as a mixture of at least two of them.
- the paper support also comprises an oleophobic and hydrophobic agent.
- This oleophobic and hydrophobic agent is preferably introduced in the form of an aqueous dispersion based on perfluoro-polyethers (PFPE), having in their chemical formulas the basic fragments -(CF 2 CF 2 O) m -(CF 2 O) n - where m and n are integers.
- PFPE perfluoro-polyethers
- This agent can for example be chosen from the Fluorolink ® PFPE range marketed by Solvay. Mention may be made, for example, of the aqueous-based commercial product “Fluorolink P56”.
- At least one non-fibrous structural reinforcing agent from the family of softeners is added to the fibers, additives, adjuvants and binders mentioned above.
- the structural reinforcing agent is chosen from surfactants such as cationic surfactants, in particular from quaternary ammonium compounds and cationic polymers.
- the amount of structural reinforcing agent which can be described as a softening agent, is preferably between 1 and 30% by weight relative to the total weight of the softening composition.
- the softening agent solution contains water - between 20 and 90%, preferably between 60 and 90%.
- It may also contain low molecular weight organic solvents such as polyethylene glycol, ethanol, isopropanol, n-propanol, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, glycerine, used alone or in combination.
- organic solvents such as polyethylene glycol, ethanol, isopropanol, n-propanol, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, glycerine, used alone or in combination.
- the amount of these solvents can be between 0 and 30%, preferably between 3 and 15%.
- This softening agent can be chosen, for example, from the Aquence FiberPlus® range marketed by the company Henkel. Mention may be made, for example, of the commercial product “Aquence FiberPlus Ultra” or else “Aquence FiberPlus Natural”.
- Cellulose fibers are suspended in water. The mixture is then refined to generate small fibrous elements which will allow the fibers to intertwine more easily and the sheet to have excellent mechanical resistance.
- the various additives, adjuvants and binders are added to the fibrous suspension.
- the structural reinforcing agent can be added at this stage, alone or mixed with the oleophobic and hydrophobic agent.
- the fibrous suspension is finally purified by gravity to eliminate the impurities, and by filtration to eliminate the agglomerates of fibers which could harm the homogeneity of the sheet.
- the oleophobic and hydrophobic sizing agent(s) containing the perfluoropolyether groups and the structural reinforcing agent can be integrated into the paper support by coating, dipping, impregnating, surfacing, spraying, coating with air knife, curtain coating, pencil coating, coating by engraved rolls, attendants or by transfer, type "size press", “film press", in line or off line, alone or in combination.
- the formation of the sheet constituting the paper support can be done with a round-form machine, with or without the addition of a pre-coat under pressure (commonly called in the fiduciary industry "short former"), or with a flat table single or twin jet.
- a watermark, a security thread, security fibers, hilites, boards, or markers may be integrated into the paper support during its formation.
- the structural reinforcing agents as well as the oleophobic and hydrophobic bonding agents can be applied in line or offline and separately, namely that the first product is dried before applying the second product.
- the order of application can be reversed.
- the structural reinforcing agents and the oleophobic and hydrophobic bonding agents can be added as a mixture either with the various additives, adjuvants and binders in the fibrous suspension, or by the various coating techniques mentioned above, in line or offline.
- the paper support thus formed is printable and transformable by all known printing and transformation processes and in particular those usually used in the fiduciary industry (offset, screen printing, intaglio, hot deposition, flexography, typography, etc.). It is also possible to varnish it before or after printing.
- Hydrophobicity is characterized as the resistance to water penetration and is measured using the Cobb test (60 s), according to ISO 535. This is the amount of water absorbed by the substrate in g/m 2 thanks to a cylindrical impregnation template, during a lapse of time of 60 seconds. This is a test that is also common in the paper industry to characterize the absorption of paper.
- the results can give an indication of the printability of the support. Indeed, if the Cobb value is very low, we can expect a refusal of ink from the support. Conversely, with a value that is too high, it may be difficult to achieve the desired rendering in terms of color intensity.
- the standard values for a banknote are between 40 and 80 g/m 2 .
- the creasing was carried out once, on the dry sample of dimensions 6.7 ⁇ 6.7 cm using a device allowing the creasing developed by the "National Bureau of Standards" and marketed by IGT Testing Systems, a device commonly used in the fiduciary field.
- the sample is wrapped around a fork before being slid in a tube with a cap.
- This tube is then engaged in a vertical sleeve fitted with a solid rod.
- the tube must then be pushed in until the counterweight of the IGT apparatus detaches, thus applying a force of 100N to the sample.
- the crumpled sample is then removed by opening the cap. Finally, the sample is delicately smoothed manually.
- Oleophobia is measured using a test of exposure to fatty substances.
- the method used called "Kit Test", uses a mixture of castor oil (fatty substance) and solvents with a high boiling point, namely toluene (aromatic solvent) and n-heptane (aliphatic solvent ).
- composition whose viscosity and surface tension vary inversely to its aggressiveness, that is to say its impregnation capacity.
- composition rich in castor oil is at the bottom of the scale, while a composition rich in heavy solvents is at the top of this same scale.
- the stiffness of the support was also evaluated by the Kodak stiffness measurement according to the ISO 5629 standard.
- Table 1 shows that the air permeability after crumpling (x8) of the solution according to the invention is more than twice lower than the untreated paper, which unambiguously indicates a destructuring well bottom of the bracket.
- the solution according to the invention also increases water resistance by two to three times (depending on the face considered), even after crumpling (crumpling x1) compared to the untreated support.
- the treatment applied therefore retains a significant barrier effect even after the support has been crumpled.
- the surface roughness of the solution is higher, from 40 to 60% depending on the face considered, than the untreated support. This roughness value can be reduced by calendering if necessary.
- the oil resistance is significantly improved with a score of 8 obtained in the Kit test on both sides.
- the results of the double ply test of the solution according to the invention are more than three times superior to untreated Vellum paper thanks to the structural reinforcing agent which provides flexibility to the fibers.
- the adhesion of the inks to the paper support according to the invention was evaluated for three types of printing characteristic of the manufacture of banknotes: offset, intaglio and typography.
- the resistance of these inks has been evaluated by a series of chemical (soaking in different chemicals) and mechanical tests.
- crumpling or crumpling test which assesses the resistance to creasing of the paper support and the inks printed on it in the dry and wet state.
- disappearance of the elements is meant the total disappearance of the printing, so that it is no longer visible on the ticket.
- the hold of the inks is good with results equivalent to those obtained on papers without treatment according to the invention.
- for fluorescent offset it is common to have scores of 0 or 1 in hot water and lye tests on standard untreated paper.
- Example 2 the treatment as described by the invention is applied by a roll-to-roll coating machine with an air knife of width 1300 mm (product A then product B in line), on 100 mm vellum paper. % cotton.
- the machine run speed during coating was 60 m/min.
- Product A is dried with hot air ovens before applying product B itself dried by hot air oven.
- the creased air permeability (x8) of Example 2 is more than four times lower than the untreated paper.
- the resistance to water after crumpling (crumpling x1) is also improved: water absorption is twice lower with the support according to the invention than with the untreated support.
- Example 1 the treatment applied retains its barrier effect even after the support has been crumpled.
- Oil resistance is improved by five points on the front and back compared to untreated paper. This result is lower than that obtained in Example 1, a result which can be attributed on the one hand to the difference in application technique ("bar coating” in one case and air knife coating in the other) and, on the other hand, to the roughness values of the treated support which are higher than those obtained in example 1.
- the surface roughness of the support can have an impact on the oil resistance. Note that it is possible to reduce the roughness by calendering the support after coating and drying of the latter.
- the adhesion of the inks was evaluated on the paper thus produced for three types of printing characteristic of the manufacture of banknotes: offset, intaglio and typography.
- example 1 The conclusions of example 1 are confirmed with in particular good resistance to crumpling even after 40 dry crumplings.
- the treatment applied does not disturb the adhesion of the inks to the paper.
- the treatment is compatible with various Vellum papers.
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- Chemical & Material Sciences (AREA)
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- Paper (AREA)
Description
L'invention concerne un support papier à haute durabilité pour l'impression d'un document de sécurité, notamment un billet de banque.The invention relates to a high-durability paper support for printing a security document, in particular a banknote.
L'invention concerne également un procédé de fabrication de ce support papier et un document de sécurité réalisé à partir d'un tel support papier.The invention also relates to a method of manufacturing this paper medium and a security document made from such a paper medium.
Les documents de sécurité et notamment les billets de banque sont soumis à de nombreuses sollicitations pendant leur mise en circulation. Celles-ci peuvent être de nature mécanique par exemple des plis, des froissements et autres manipulations pouvant conduire à des détériorations plus ou moins marquées des fibres voire des déchirures de ces dernières.Security documents and in particular banknotes are subject to numerous stresses during their circulation. These may be of a mechanical nature, for example folds, creases and other manipulations which may lead to more or less marked deterioration of the fibers or even tearing of the latter.
A cela, il faut ajouter les contraintes environnementales auxquelles sont soumis les documents de sécurité, et on peut ainsi indiquer les expositions au rayonnement ultraviolet ou la sécheresse et surtout l'humidité relative, qui peut contribuer à modifier le comportement du billet. En effet, une exposition à un environnement humide peut engendrer un gonflement du papier, c'est-à-dire une augmentation de son grammage et de son épaisseur, accompagnée d'une baisse de la rigidité du papier. A l'inverse, un environnement trop sec peut entraîner une baisse d'humidité du papier et donc un comportement cassant de ses fibres.To this must be added the environmental constraints to which the security documents are subjected, and it is thus possible to indicate exposure to ultraviolet radiation or drought and above all the relative humidity, which can contribute to modifying the behavior of the banknote. Indeed, exposure to a humid environment can cause the paper to swell, that is to say an increase in its basis weight and thickness, accompanied by a decrease in the stiffness of the paper. Conversely, an environment that is too dry can cause a drop in the humidity of the paper and therefore a brittle behavior of its fibres.
Il est donc primordial pour un papier qu'il conserve ses propriétés originales de rigidité mais également de résistance mécanique générale au cours de sa vie sur le terrain.It is therefore essential for a paper that it retains its original properties of rigidity but also of general mechanical resistance during its life in the field.
Enfin, il faut noter que parmi les salissures généralement présentes sur les billets, on trouve une combinaison de corps gras issus généralement du sébum et des matières grasses à usage culinaire véhiculés par l'homme et transférés depuis les porteurs successifs jusqu'au billet. L'accumulation de ces corps gras sur la surface du billet et plus encore leur pénétration au sein des fibres si la surface du papier est détériorée, contribue au caractère poisseux du billet et au sentiment désagréable qui en découle.Finally, it should be noted that among the dirt generally present on the banknotes, there is a combination of fatty substances generally resulting from sebum and fatty substances for culinary use conveyed by man and transferred from the successive wearers to the banknote. The accumulation of these fatty substances on the surface of the banknote and even more their penetration within the fibers if the surface of the paper is damaged, contributes to the stickiness of the note and the unpleasant feeling that results from it.
Ainsi, il existe un besoin de protéger la surface du papier, pour éviter l'accumulation de salissures mais également le cœur du papier (les fibres) afin de ralentir sa déstructuration et donc la progression des agresseurs externes si toutefois la protection de surface venait à se fragiliser, voire à disparaître.Thus, there is a need to protect the surface of the paper, to avoid the accumulation of dirt but also the heart of the paper (the fibers) in order to slow down its destructuring and therefore the progression of external aggressors if, however, the surface protection were to weaken or even disappear.
Ce phénomène est particulièrement visible aux endroits des plis notamment où les fibres sont sollicitées en flexion. Dans ces zones, où la protection de surface va rompre sous l'effet du pli, il existe un besoin d'améliorer la résistance de la fibre et plus particulièrement sa résistance à la flexion pour éviter que celle-ci ne casse. On ralentit ainsi le risque de rupture ou de déchirure du papier dans ces zones de fragilisation.This phenomenon is particularly visible at the places of the folds, in particular where the fibers are stressed in bending. In these zones, where the surface protection will break under the effect of the fold, there is a need to improve the strength of the fiber and more particularly its resistance to bending to prevent it from breaking. This slows down the risk of breaking or tearing the paper in these areas of weakness.
Afin de remédier à ce problème, on connaît déjà dans l'état de la technique, différents procédés permettant d'améliorer la résistance à la salissure et aux déchirures des billets de banque.In order to remedy this problem, various methods are already known in the state of the art which make it possible to improve the resistance to soiling and tearing of banknotes.
On connaît ainsi par exemple d'après le document
On connaît également d'après l'état de la technique, des papiers à résistance améliorée, dans lesquels sont ajoutés à la pulpe de fibre de cellulose, des matériaux tels que des polyamides, des polyesters ou du polypropylène. On citera par exemple le document
On connaît également des billets de banque en matière plastique, par exemple ceux réalisés sur polypropylène bi-orienté (BOPP), présentés comme des produits assurant une forte longévité et d'autres produits hybrides comprenant à la fois des parties de papier et d'autres en plastique à base de polyamides ou polyesters.Banknotes made of plastic material are also known, for example those produced on bi-oriented polypropylene (BOPP), presented as products ensuring a high longevity and other hybrid products comprising both parts of paper and other plastic based on polyamides or polyesters.
Les banques centrales responsables de l'émission, de la circulation et du retrait des billets de banque ont des contraintes budgétaires qui les contraignent à rechercher l'augmentation de la longévité des billets, et ce, afin de diminuer le coût du cycle de l'argent liquide, ce qui les fait se tourner légitimement vers les solutions précitées.The central banks responsible for the issue, circulation and withdrawal of banknotes have budgetary constraints which force them to seek an increase in the longevity of banknotes, in order to reduce the cost of the cycle of cash, which makes them legitimately turn to the aforementioned solutions.
Toutefois, les substrats obtenus avec les techniques identifiées ci-dessus présentent divers inconvénients :
- Etre difficilement imprimables de par la nature très fermée des supports. Les encres pénètrent difficilement dans le support et ainsi leur séchage et leur adhésion sur le substrat peuvent en être perturbées ; il en résulte des difficultés certaines lors de la production des billets et parfois une faible tenue des encres dans le temps. De plus des couleurs ternes peuvent résulter de ces impressions.
- Etre difficilement mis en oeuvre au cours du procédé de formation de la feuille à l'état humide. En effet, l'ajout de fibres synthétiques peut perturber voire empêcher la création de liaisons entre les fibres et donc déstructurer complètement la feuille de papier.
- Be difficult to print due to the very closed nature of the supports. The inks have difficulty penetrating into the support and thus their drying and their adhesion to the substrate may be disturbed; this results in certain difficulties during the production of banknotes and sometimes poor ink retention over time. Additionally, dull colors may result from these prints.
- Be difficult to operate during the wet sheet forming process. Indeed, the addition of synthetic fibers can disrupt or even prevent the creation of bonds between the fibers and therefore completely destructure the sheet of paper.
Enfin, dans certains cas, le vernissage du support est obligatoire pour garantir une tenue minimum dans le temps.Finally, in some cases, the varnishing of the support is mandatory to guarantee a minimum hold over time.
A titre d'état de la technique, on peut également citer le document
En pratique, l'agent de renfort est constitué par des fibres additionnelles et de nature différente, qui viennent s'ajouter aux fibres de cellulose déjà habituellement présentes dans la structure du papier.In practice, the reinforcing agent consists of additional fibers of a different nature, which are added to the cellulose fibers already usually present in the structure of the paper.
Par ailleurs et dans un tout autre domaine technique que celui de la présente invention, on décrit dans le document
En tout état de cause, il existe à ce jour un besoin de disposer d'un support papier destiné à la fabrication et à l'impression d'un document de sécurité, notamment un billet de banque, qui présente des caractéristiques de "haute durabilité", à savoir des propriétés barrières élevées ainsi qu'une résistance aux sollicitations mécaniques élevée sans modifier le process papetier, plus précisément sans ajout de fibres différentes des fibres de cellulose habituellement utilisées pour la fabrication d'un tel papier, ni perturber l'impression du support final. Plus exactement, on cherche d'une part à augmenter la flexibilité des fibres, tout en conservant une rigidité relative du support papier, de manière à augmenter sa résistance au pliage et d'autre part à augmenter sa résistance à l'eau et à l'huile pour éviter une détérioration du support par l'eau et les corps gras qui sont susceptibles de se déposer à sa surface.In any event, there currently exists a need to have a paper support intended for the manufacture and printing of a security document, in particular a banknote, which has characteristics of "high durability ", namely high barrier properties as well as high resistance to mechanical stress without modifying the papermaking process, more precisely without adding fibers different from the cellulose fibers usually used for the manufacture of such paper, nor disturbing the printing end support. More exactly, one seeks on the one hand to increase the flexibility of the fibers, while preserving a relative rigidity of the paper support, so as to increase its resistance to folding and on the other hand to increase its resistance to water and to the oil to prevent deterioration of the support by water and fatty substances which are likely to deposit on its surface.
Ainsi, la présente invention se rapporte à un support papier à haute durabilité pour l'impression d'un document de sécurité, notamment un billet de banque, comprenant des fibres de cellulose, selon une proportion d'au moins 50 % en masse par rapport à la masse totale du support papier à l'état sec, des additifs et adjuvants, au moins un liant, et qui comprend en outre au moins un agent oléophobe et hydrophobe à base d'un composé organique contenant des groupements perfluoropolyéthers (PFPE), selon une concentration supérieure à 0 % et inférieure ou égale à 5 % en masse à l'état sec par rapport à la masse totale du support papier à l'état sec,Thus, the present invention relates to a high-durability paper support for printing a security document, in particular a banknote, comprising cellulose fibers, in a proportion of at least 50% by mass relative to the total mass of the paper support in the dry state, additives and adjuvants, at least one binder, and which also comprises at least one oleophobic and hydrophobic agent based on an organic compound containing perfluoropolyether (PFPE) groups, in a concentration greater than 0% and less than or equal to 5% by mass in the dry state relative to the total mass of the paper support in the dry state,
Ce support comprend par ailleurs au moins un agent de renfort structurel non fibreux de la famille des agents assouplissants, c'est à dire des agents augmentant la flexibilité des fibres de cellulose, selon une quantité comprise entre 0,5 % et 15 % en masse par rapport à la masse totale du support papier à l'état sec.This support also comprises at least one non-fibrous structural reinforcing agent from the family of softening agents, that is to say agents increasing the flexibility of cellulose fibers, in an amount of between 0.5% and 15% by mass relative to the total mass of the paper support in the dry state.
Par ailleurs, selon d'autres caractéristiques non limitatives et avantageuses de ce support :
- le module d'Young dudit support, mesuré selon la norme ISO 1924 est inférieur d'au moins 30 %, de préférence de 50 à 60 %, à celui d'un support papier dépourvu dudit agent de renfort structurel ;
- il présente une valeur moyenne SM/ST de résistance au double pli supérieure de 100 %, et de préférence de 200 %, à celle d'un support papier dépourvu dudit agent de renfort structurel ;
- la concentration en fibres de cellulose est supérieure ou égale à 85% et inférieure à 100% en masse à l'état sec par rapport à la masse totale dudit support papier à l'état sec ;
- les additifs et adjuvants et liant sont présents selon une concentration supérieure à 0 % et inférieure ou égale à 15 % en masse à l'état sec par rapport à la masse totale dudit support papier à l'état sec ;
- l'agent de renfort structurel est choisi parmi les tensioactifs ;
- ledit agent de renfort structurel est choisi parmi les tensioactifs cationiques, notamment parmi les composés ammonium quaternaire et les polymères cationiques ;
- ledit agent de renfort structurel est choisi parmi les tensioactifs non ioniques, notamment dans le groupe constitué par le polybutylène, les acides gras à longue chaîne, c'est à dire ayant une longueur de chaîne supérieure ou égale à 10 atomes de carbone, et les acides aminés gras éthoxylés ;
- ledit agent de renfort structurel est choisi parmi les tensioactifs anioniques ; et
- les groupements perfluoropolyéthers possèdent dans leurs formules chimiques les fragments de base -(CF2CF2O)m-(CF2O)n- où m et n sont des entiers.
- the Young's modulus of said support, measured according to the ISO 1924 standard, is lower by at least 30%, preferably by 50 to 60%, than that of a paper support devoid of said structural reinforcing agent;
- it has an average SM/ST value of resistance to double folding that is 100%, and preferably 200%, higher than that of a paper support without said structural reinforcing agent;
- the concentration of cellulose fibers is greater than or equal to 85% and less than 100% by mass in the dry state relative to the total mass of said paper support in the dry state;
- the additives and adjuvants and binder are present in a concentration greater than 0% and less than or equal to 15% by mass in the dry state relative to the total mass of said paper support in the dry state;
- the structural reinforcing agent is chosen from surfactants;
- said structural reinforcing agent is chosen from cationic surfactants, in particular from quaternary ammonium compounds and cationic polymers;
- said structural reinforcing agent is chosen from nonionic surfactants, in particular from the group consisting of polybutylene, long-chain fatty acids, that is to say having a chain length greater than or equal to 10 carbon atoms, and ethoxylated fatty amino acids;
- said structural reinforcing agent is chosen from anionic surfactants; and
- the perfluoropolyether groups have in their chemical formulas the basic fragments -(CF2CF2O)m-(CF2O)n- where m and n are integers.
L'invention se rapporte également à un document de sécurité qui comprend un support selon l'une des caractéristiques précédentes.The invention also relates to a security document which comprises a support according to one of the preceding characteristics.
Avantageusement, ledit document est un billet de banque.Advantageously, said document is a banknote.
Enfin, elle se rapporte à un procédé de fabrication d'un tel support papier qui comprend les étapes suivantes :
- a) mise en suspension dans l'eau des fibres de cellulose,
- b) raffinage du mélange,
- c) ajout des additifs, adjuvants et liant,
- d) épuration et filtration de la suspension fibreuse,
- e) mise en forme du support papier,
- f) pressage,
- g) pré séchage,
- h) enduction du support papier,
- i) post séchage,
- lorsqu'ils sont ajoutés seuls, c'est à dire individuellement :
- l'agent de renfort structurel est ajouté à l'étape c) et l'agent oléophobe et hydrophobe à l'étape h), ou inversement ; ou
- les deux agents sont appliqués l'un après l'autre à l'étape h) en ligne sur la machine à papier, le premier d'entre eux étant séché par air chaud ou rayonnement infrarouge, avant d'appliquer le deuxième, lui-même séché par air chaud ou rayonnement infrarouge,
- lorsqu'ils sont ajoutés en mélange, cet ajout est réalisé pendant l'étape c) ou pendant l'étape h).
- a) suspending the cellulose fibers in water,
- b) refining the mixture,
- c) addition of additives, adjuvants and binder,
- d) purification and filtration of the fibrous suspension,
- e) formatting of the paper support,
- f) pressing,
- g) pre-drying,
- h) coating of the paper support,
- i) post-drying,
- when they are added alone, i.e. individually :
- the structural reinforcing agent is added in step c) and the oleophobic and hydrophobic agent in step h), or vice versa; Where
- the two agents are applied one after the other in step h) in line on the paper machine, the first of them being dried by hot air or infrared radiation, before to apply the second, itself dried by hot air or infrared radiation,
- when they are added as a mixture , this addition is carried out during step c) or during step h).
Avantageusement, les agents de renfort structurel et les agents oléophobes et hydrophobes sont appliqués hors ligne, séparément ou en mélange, par enduction, trempage, imprégnation, surfaçage, pulvérisation, couchage à lame d'air, couchage rideau, couchage crayon, couchage par rouleaux gravés, préposés ou par transfert, type « size press », « film press », sans que cette énumération soit limitativeAdvantageously, the structural reinforcing agents and the oleophobic and hydrophobic agents are applied offline, separately or as a mixture, by coating, dipping, impregnation, surfacing, spraying, air knife coating, curtain coating, pencil coating, roller coating engraved, appointed or by transfer, type "size press", "film press", without this list being exhaustive
Ainsi qu'on le montre dans la suite de la description, les propriétés de haute durabilité sont obtenues par un traitement de surface qui ne nécessite pas de modification de la composition fibreuse du substrat. De plus, la perméabilité à l'air obtenue n'est pas nulle, contrairement aux perméabilités de la majorité des supports de haute durabilité connus actuellement sur le marché. En outre, la valeur de collage Cobb obtenue, c'est-à-dire la capacité d'absorption d'eau du support est normale et comparable à celle d'un papier standard pour billet de banque, ce qui conforte son caractère imprimable. Son impression est donc facilitée.As shown in the remainder of the description, the high durability properties are obtained by a surface treatment which does not require modification of the fibrous composition of the substrate. Moreover, the air permeability obtained is not zero, contrary to the permeability of the majority of high-durability supports currently known on the market. In addition, the Cobb bonding value obtained, that is to say the water absorption capacity of the support, is normal and comparable to that of standard banknote paper, which reinforces its printability. Its printing is therefore facilitated.
Par ailleurs, le support tel que décrit par l'invention conserve ses propriétés barrière après froissement, avec notamment des valeurs de perméabilité et de Cobb qui restent relativement faibles, contrairement à un papier non traité. Ces caractéristiques constituent des paramètres importants qui permettent au support de mieux résister aux sollicitations mécaniques lorsqu'il est en circulation sur le terrain.Furthermore, the support as described by the invention retains its barrier properties after crumpling, with in particular permeability and Cobb values which remain relatively low, unlike untreated paper. These characteristics constitute important parameters which enable the support to better resist mechanical stresses when it is in circulation in the field.
Enfin, le support tel que décrit par l'invention présente une résistance à la flexion augmentée tout en conservant une rigidité globale normale et comparable à un papier standard.Finally, the support as described by the invention has increased resistance to bending while retaining normal overall stiffness comparable to standard paper.
Les fibres entrant dans la composition du support papier sont principalement des fibres de cellulose.The fibers used in the composition of the paper support are mainly cellulose fibers.
De façon avantageuse, ces fibres de cellulose sont choisies parmi les fibres issues de bois de feuillus, de bois de résineux, de plantes saisonnières telles que le coton, le chanvre ou le lin, par exemple. Ces différentes fibres peuvent être utilisées seules ou en mélange.Advantageously, these cellulose fibers are chosen from fibers derived from deciduous wood, softwood, seasonal plants such as cotton, hemp or linen, for example. These different fibers can be used alone or in a mixture.
De préférence toutefois, les fibres de cellulose utilisées sont des fibres de coton. Cette fibre est utilisée pour ses bonnes caractéristiques physiques et mécaniques. En effet, les fibres longues de coton peuvent mesurer jusqu'à 40 mm de long, ce qui confère au papier obtenu une très bonne résistance au pliage.Preferably, however, the cellulose fibers used are cotton fibers. This fiber is used for its good physical and mechanical characteristics. Indeed, the long cotton fibers can measure up to 40 mm long, which gives the paper obtained a very good resistance to folding.
Le support papier conforme à l'invention comprend également des additifs et adjuvants, non fibreux, choisis de préférence parmi les composés anti-mousse, les charges minérales, les agents de résistance à l'état humide et les agents de collage utilisés seuls ou en mélange d'au moins deux d'entre eux.The paper support in accordance with the invention also comprises non-fibrous additives and adjuvants, preferably chosen from anti-foam compounds, mineral fillers, wet strength agents and sizing agents used alone or in combination. mixture of at least two of them.
Les composés anti-mousse sont par exemple des agents tels que les silicones, les émulsions de silicone, les polyéthylènes glycol, les dérivés de polyéthylènes glycol, les polyalcools synthétiques, les dérivés de polyalcools, les anti-mousses à base d'amide, à base d'ester ; des tensio-actifs tels que des oligomères, des oxydes d'éthylène (EtO), des oxydes de polypropylènes (PPOx) ; des agents hydrophobiques tels que des cires d'hydrocarbures, des cires de polyéthylène, des alcools gras, des acides gras, des esters gras, des éthylènesbis(stéramide) (EBS), des silices hydrophobiques.The antifoam compounds are, for example, agents such as silicones, silicone emulsions, polyethylene glycols, derivatives of polyethylene glycols, synthetic polyalcohols, derivatives of polyalcohols, amide-based antifoams, ester base; surfactants such as oligomers, ethylene oxides (EtO), polypropylene oxides (PPOx); hydrophobic agents such as hydrocarbon waxes, polyethylene waxes, fatty alcohols, fatty acids, fatty esters, ethylene bis(steramide) (EBS), hydrophobic silicas.
Ces composés anti-mousse seront ajoutés lors de la préparation de la pâte à papier ainsi que dans la partie humide de la machine à papier, afin d'éviter la formation de mousse, voire de la détruire et ainsi améliorer la formation de la feuille.These anti-foam compounds will be added during the preparation of the paper pulp as well as in the wet end of the paper machine, in order to avoid the formation of foam, or even to destroy it and thus improve the formation of the sheet.
De préférence, les charges minérales sont choisies parmi la silice colloïdale, les silicates de sodium, les aluminosilicates de sodium, les carbonates de calcium naturels ou précipités, le talc, le kaolin naturel ou calciné, l'hydrate d'alumine, le dioxyde de titane et le sulfate de baryum, seuls ou en mélange d'au moins deux d'entre eux.Preferably, the mineral fillers are chosen from colloidal silica, sodium silicates, sodium aluminosilicates, natural or precipitated calcium carbonates, talc, natural or calcined kaolin, alumina hydrate, titanium and barium sulphate, alone or as a mixture of at least two of them.
Ces charges minérales sont ajoutées pour modifier les propriétés optiques du papier obtenu, telles que sa blancheur, sa brillance ou son opacité, mais également ses propriétés de surface. Certaines de ces charges sont moins coûteuses que les fibres et sont donc ajoutées pour diminuer les coûts de fabrication.These mineral fillers are added to modify the optical properties of the paper obtained, such as its whiteness, its shine or its opacity, but also its surface properties. Some of these fillers are less expensive than fibers and are therefore added to reduce manufacturing costs.
Les agents de résistance à l'état humide sont des polymères thermodurcissables qui sont ajoutés quand le papier est encore à l'état humide et qui réticulent dans le papier lors de son passage en sécherie. Ils jouent un rôle de barrière à l'eau une fois le papier fabriqué.Wet strength agents are thermosetting polymers that are added while the paper is still wet and which crosslink in the paper during its passage through the dryer section. They act as a water barrier once the paper is made.
On utilise, de préférence, principalement des polymères qui assurent la liaison des fibres entre elles, tels que les résines urée-formaldéhyde (UF), les résines mélamine-formaldéhyde (MF), les résines à base de polyamidoamine-épichlorhydrine (PAA-E), les résines de glyoxal, les complexes ions métalliques seuls ou en mélange.Preferably, mainly polymers are used which ensure the bonding of the fibers together, such as urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, resins based on polyamidoamine-epichlorohydrin (PAA-E ), glyoxal resins, metal ion complexes alone or as a mixture.
Les agents de collage retardent la pénétration des liquides dans le papier. Ils sont mis en oeuvre soit lorsque le papier est encore à l'état humide (encollage dans la masse du papier), soit au niveau de la presse encolleuse (encollage en surface).Sizing agents retard the penetration of liquids into the paper. They are implemented either when the paper is still in the wet state (sizing in the mass of the paper), or at the level of the size press (sizing on the surface).
De préférence, on utilise des produits naturels, tels que des résines naturelles modifiées (colles à base de résine), de l'amidon ou de l'amidon modifié ou des produits synthétiques, tels que le dimère d'alkyle cétène (AKD), l'alcénile succinique anhydride (ASA) et d'autres polymères (par exemple les copolymères à base d'esters d'acide acrylique et d'acide maléique, d'acrylonitrile et de styrène). L'AKD est le produit chimique de collage le plus couramment utilisé et il doit être employé de préférence lorsque les spécifications du produit le permettent. Il est également possible d'utiliser de la cire de paraffine et des cires de polyéthylène. Ces différents produits peuvent être utilisés seuls ou en mélange.Preferably, natural products are used, such as modified natural resins (resin-based glues), starch or modified starch or synthetic products, such as alkyl ketene dimer (AKD), alkenile succinic anhydride (ASA) and other polymers (eg copolymers based on esters of acrylic acid and maleic acid, acrylonitrile and styrene). AKD is the most commonly used bonding chemical and should preferably be used where product specifications permit. It is also possible to use paraffin wax and polyethylene waxes. These various products can be used alone or as a mixture.
Comme cela sera décrit ultérieurement, les fibres, additifs et adjuvants sont mélangés et sont liés entre eux par l'emploi d'au moins un liant.As will be described later, the fibers, additives and adjuvants are mixed and are bonded together by the use of at least one binder.
Ce liant permet d'améliorer la résistance du papier à l'état sec.This binder makes it possible to improve the resistance of the paper in the dry state.
De façon avantageuse, le liant est choisi parmi les alcools polyvinyliques, l'amidon, les fécules, le latex, les hémicelluloses, les CMC (carboxyméthylcelluloses), les galactomannanes, les gélatines ou les résines polyamide-épichlorhydrine, pris seuls ou en mélange d'au moins deux d'entre eux.Advantageously, the binder is chosen from polyvinyl alcohols, starch, starches, latex, hemicelluloses, CMCs (carboxymethylcelluloses), galactomannans, gelatins or polyamide-epichlorohydrin resins, taken alone or as a mixture of at least two of them.
Conformément à l'invention, le support papier comprend également un agent oléophobe et hydrophobe.In accordance with the invention, the paper support also comprises an oleophobic and hydrophobic agent.
Cet agent oléophobe et hydrophobe est introduit de préférence sous forme d'une dispersion aqueuse à base de perfluoro-polyéthers (PFPE), possédant dans leurs formules chimiques les fragments de base -(CF2CF2O)m-(CF2O)n- ou m et n sont des entiers. Cet agent peut par exemple être choisi dans la gamme Fluorolink® PFPE commercialisée par la société Solvay. On peut citer par exemple le produit commercial « Fluorolink P56 » à base aqueuse.This oleophobic and hydrophobic agent is preferably introduced in the form of an aqueous dispersion based on perfluoro-polyethers (PFPE), having in their chemical formulas the basic fragments -(CF 2 CF 2 O) m -(CF 2 O) n - where m and n are integers. This agent can for example be chosen from the Fluorolink ® PFPE range marketed by Solvay. Mention may be made, for example, of the aqueous-based commercial product “Fluorolink P56”.
Conformément à l'invention, on ajoute aux fibres, additifs, adjuvants et liants précités, au moins un agent de renfort structurel non fibreux de la famille des assouplissants. On entend, dans l'ensemble de la présente demande, un agent qui permet d'augmenter la flexibilité des fibres de cellulose du papier. Autrement dit, le module d'Young de ces fibres est diminué et leur allongement à la rupture est augmenté.In accordance with the invention, at least one non-fibrous structural reinforcing agent from the family of softeners is added to the fibers, additives, adjuvants and binders mentioned above. Throughout the present application, we mean an agent which makes it possible to increase the flexibility of the cellulose fibers of the paper. In other words, the Young's modulus of these fibers is reduced and their elongation at break is increased.
De préférence, l'agent de renfort structurel est choisi parmi les tensioactifs tels que les tensioactifs cationiques, notamment parmi les composés d'ammonium quaternaire et les polymères cationiques.Preferably, the structural reinforcing agent is chosen from surfactants such as cationic surfactants, in particular from quaternary ammonium compounds and cationic polymers.
Mais il peut être choisi aussi parmi :
- les tensioactifs non ioniques, notamment dans le groupe constitué par le polybutylène, les acides gras à longue chaîne, c'est à dire comportant au moins 10 atomes de carbone, et les acides aminés gras éthoxylés ;
- les tensioactifs anioniques.
- nonionic surfactants, in particular from the group consisting of polybutylene, long-chain fatty acids, ie containing at least 10 carbon atoms, and ethoxylated fatty amino acids;
- anionic surfactants.
La quantité d'agent de renfort structurel, que l'on peut qualifier d'agent assouplissant est de préférence comprise entre 1 et 30% en poids par rapport au poids total de la composition assouplissante.The amount of structural reinforcing agent, which can be described as a softening agent, is preferably between 1 and 30% by weight relative to the total weight of the softening composition.
De préférence, la solution d'agent assouplissant contient de l'eau - entre 20 et 90%, de préférence entre 60 et 90%.Preferably, the softening agent solution contains water - between 20 and 90%, preferably between 60 and 90%.
Elle peut également contenir des solvants organiques à faible poids moléculaires tel que le polyéthylène glycol, l'éthanol, l'isopropanol, le n-propanol, l'acétone, le méthyl éthyl cétone l'éthylène glycol, le propylène glycol, la glycérine, utilisés seuls ou en mélange. La quantité de ces solvants peut être comprise entre 0 et 30%, de préférence entre 3 et 15%.It may also contain low molecular weight organic solvents such as polyethylene glycol, ethanol, isopropanol, n-propanol, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, glycerine, used alone or in combination. The amount of these solvents can be between 0 and 30%, preferably between 3 and 15%.
Cet agent assouplissant peut être choisi par exemple dans la gamme Aquence FiberPlus® commercialisé par la société Henkel. On peut citer par exemple le produit commercial « Aquence FiberPlus Ultra » ou encore « Aquence FiberPlus Natural ».This softening agent can be chosen, for example, from the Aquence FiberPlus® range marketed by the company Henkel. Mention may be made, for example, of the commercial product “Aquence FiberPlus Ultra” or else “Aquence FiberPlus Natural”.
Conformément à l'invention, les produits précédemment cités sont introduits dans les concentrations suivantes :
- Fibres de cellulose : supérieur ou égal à 85% et inférieur à 100%, de préférence compris entre 88 à 92% ;
- Additifs, adjuvants et liants : supérieur à 0% et inférieur ou égal à 15%, de préférence compris entre 8% et 12% ;
- Agent de renfort structurel : supérieur à 0% et inférieur ou égal à 15%, de préférence compris entre 0.5% et 3% ;
- Agent oléophobe et hydrophobe : supérieur à 0% et inférieur ou égal à 5%, de préférence compris entre 0,5 et 2% ;
- Cellulose fibers: greater than or equal to 85% and less than 100%, preferably between 88 to 92%;
- Additives, adjuvants and binders: greater than 0% and less than or equal to 15%, preferably between 8% and 12%;
- Structural reinforcing agent: greater than 0% and less than or equal to 15%, preferably between 0.5% and 3%;
- Oleophobic and hydrophobic agent: greater than 0% and less than or equal to 5%, preferably between 0.5 and 2%;
Ces pourcentages sont donnés en masse sèche d'un produit donné, rapportée à la masse totale à l'état sec de l'échantillon considéré dudit support papier.These percentages are given as dry mass of a given product, relative to the total mass in the dry state of the sample in question of said paper medium.
Un exemple de réalisation du procédé de fabrication du support papier est décrit plus en détail ci-après.An exemplary embodiment of the method of manufacturing the paper support is described in more detail below.
Les fibres de cellulose sont mises en suspension dans l'eau. Le mélange est ensuite raffiné pour générer des éléments fibreux de petite taille qui permettront aux fibres de s'entrelacer plus facilement et à la feuille d'avoir une excellente résistance mécanique.Cellulose fibers are suspended in water. The mixture is then refined to generate small fibrous elements which will allow the fibers to intertwine more easily and the sheet to have excellent mechanical resistance.
Dans un deuxième temps, les différents additifs, adjuvants et les liants sont ajoutés à la suspension fibreuse. L'agent de renfort structurel peut être ajouté à ce stade, seul ou en mélange avec l'agent oléophobe et hydrophobe.In a second step, the various additives, adjuvants and binders are added to the fibrous suspension. The structural reinforcing agent can be added at this stage, alone or mixed with the oleophobic and hydrophobic agent.
La suspension fibreuse est enfin épurée par gravité pour éliminer les impuretés, et par filtration pour éliminer les agglomérats de fibres qui pourraient nuire à l'homogénéité de la feuille.The fibrous suspension is finally purified by gravity to eliminate the impurities, and by filtration to eliminate the agglomerates of fibers which could harm the homogeneity of the sheet.
S'ils ne sont pas ajoutés dans la suspension fibreuse, le ou les agents de collage oléophobe et hydrophobe contenant les groupements perfluoropolyéthers et l'agent de renfort structurel peuvent être intégrés au support papier par enduction, trempage, imprégnation, surfaçage, pulvérisation, couchage à lame d'air, couchage rideau, couchage crayon, couchage par rouleaux gravés, préposés ou par transfert, type « size press », « film press », en ligne ou hors ligne, seuls ou en mélange.If they are not added to the fibrous suspension, the oleophobic and hydrophobic sizing agent(s) containing the perfluoropolyether groups and the structural reinforcing agent can be integrated into the paper support by coating, dipping, impregnating, surfacing, spraying, coating with air knife, curtain coating, pencil coating, coating by engraved rolls, attendants or by transfer, type "size press", "film press", in line or off line, alone or in combination.
La formation de la feuille constituant le support papier peut se faire avec une machine à forme ronde, avec ou sans ajout d'une pré-couche sous pression (communément appelée dans l'industrie fiduciaire "short former"), ou avec une table plate simple ou bi jet.The formation of the sheet constituting the paper support can be done with a round-form machine, with or without the addition of a pre-coat under pressure (commonly called in the fiduciary industry "short former"), or with a flat table single or twin jet.
Un filigrane, un fil de sécurité, des fibres de sécurité, des hilites, des planchettes, ou des marqueurs pourront être intégrés au support papier lors de sa formation.A watermark, a security thread, security fibers, hilites, boards, or markers may be integrated into the paper support during its formation.
Selon une variante, les agents de renfort structurel ainsi que les agents de collage oléophobe et hydrophobe peuvent être appliqués en ligne ou hors ligne et séparément à savoir que le premier produit est séché avant d'appliquer le second produit. L'ordre d'application peut être inversé.According to a variant, the structural reinforcing agents as well as the oleophobic and hydrophobic bonding agents can be applied in line or offline and separately, namely that the first product is dried before applying the second product. The order of application can be reversed.
Selon une autre variante, les agents de renfort structurel et les agents de collage oléophobe et hydrophobe peuvent être ajoutés en mélange soit avec les différents additifs, adjuvants et liants dans la suspension fibreuse, soit par les différentes techniques de couchage précédemment citées, en ligne ou hors ligne.According to another variant, the structural reinforcing agents and the oleophobic and hydrophobic bonding agents can be added as a mixture either with the various additives, adjuvants and binders in the fibrous suspension, or by the various coating techniques mentioned above, in line or offline.
Le support papier ainsi formé est imprimable et transformable par tous les procédés d'impression et de transformation connus et notamment ceux utilisés usuellement dans l'industrie fiduciaire (offset, sérigraphie, taille douce, dépose à chaud, flexographie, typographie...). Il est également possible de le vernir avant ou après impression.The paper support thus formed is printable and transformable by all known printing and transformation processes and in particular those usually used in the fiduciary industry (offset, screen printing, intaglio, hot deposition, flexography, typography, etc.). It is also possible to varnish it before or after printing.
Des travaux ont été menés pour observer les propriétés de durabilité du papier ainsi obtenu.Work has been carried out to observe the durability properties of the paper thus obtained.
L'hydrophobie est caractérisée comme la résistance à la pénétration de l'eau et est mesurée à l'aide du test Cobb (60 s), selon la norme ISO 535. Il s'agit de la quantité d'eau absorbée par le support en g/m2 grâce à un gabarit d'imprégnation cylindrique, durant un laps de temps de 60 secondes. Il s'agit d'un test par ailleurs fréquent dans le domaine papetier pour caractériser l'absorption du papier.Hydrophobicity is characterized as the resistance to water penetration and is measured using the Cobb test (60 s), according to ISO 535. This is the amount of water absorbed by the substrate in g/m 2 thanks to a cylindrical impregnation template, during a lapse of time of 60 seconds. This is a test that is also common in the paper industry to characterize the absorption of paper.
Les résultats peuvent donner une indication sur l'imprimabilité du support. En effet, si la valeur de Cobb est très faible, on peut s'attendre à un refus d'encre de la part du support. A l'inverse, avec une valeur trop élevée, il peut être difficile d'atteindre le rendu souhaité en termes d'intensité des couleurs. Les valeurs standards pour un billet de banque sont comprises entre 40 et 80 g/m2.The results can give an indication of the printability of the support. Indeed, if the Cobb value is very low, we can expect a refusal of ink from the support. Conversely, with a value that is too high, it may be difficult to achieve the desired rendering in terms of color intensity. The standard values for a banknote are between 40 and 80 g/m 2 .
Ce test a également été réalisé après « crumpling sec ×1 » (c'est-à-dire après un froissement du support sec) pour évaluer l'évolution des propriétés barrière du support après froissement.This test was also carried out after “dry crumpling ×1” (that is to say after crumpling the dry support) to evaluate the evolution of the barrier properties of the support after crumpling.
Conformément à ce test, le froissement a été réalisé une fois, sur l'échantillon sec de dimensions 6,7 × 6,7 cm à l'aide d'un appareil permettant le froissage développé par le « National Bureau of Standards » et commercialisé par la société IGT Testing Systems, appareil couramment utilisé dans le domaine fiduciaire. L'échantillon est enroulé autour d'une fourche avant d'être glissé dans un tube muni d'un capuchon. Ce tube est ensuite engagé dans un manchon vertical muni d'une tige pleine. Le tube doit alors être enfoncé jusqu'à obtention d'un décollement du contrepoids de l'appareil IGT appliquant ainsi une force de 100N sur l'échantillon. L'échantillon ainsi froissé est alors retiré en ouvrant le capuchon. Enfin l'échantillon est délicatement défroissé manuellement.In accordance with this test, the creasing was carried out once, on the dry sample of dimensions 6.7 × 6.7 cm using a device allowing the creasing developed by the "National Bureau of Standards" and marketed by IGT Testing Systems, a device commonly used in the fiduciary field. The sample is wrapped around a fork before being slid in a tube with a cap. This tube is then engaged in a vertical sleeve fitted with a solid rod. The tube must then be pushed in until the counterweight of the IGT apparatus detaches, thus applying a force of 100N to the sample. The crumpled sample is then removed by opening the cap. Finally, the sample is delicately smoothed manually.
L'oléophobie est mesurée grâce à un test d'exposition aux corps gras. La méthode utilisée, dénommée « Kit Test », met en oeuvre un mélange d'huile de ricin (corps gras) et de solvants à haut point d'ébullition, à savoir le toluène (solvant aromatique) et le n-heptane (solvant aliphatique).Oleophobia is measured using a test of exposure to fatty substances. The method used, called "Kit Test", uses a mixture of castor oil (fatty substance) and solvents with a high boiling point, namely toluene (aromatic solvent) and n-heptane (aliphatic solvent ).
En fonction des différentes proportions des produits susmentionnés, on obtient une composition dont la viscosité et la tension de surface varient inversement à son agressivité, c'est-à-dire sa capacité d'imprégnation.Depending on the different proportions of the aforementioned products, a composition is obtained whose viscosity and surface tension vary inversely to its aggressiveness, that is to say its impregnation capacity.
Une composition riche en huile de ricin se situe en bas de l'échelle, alors qu'une composition riche en solvants lourds se situe en haut de cette même échelle.A composition rich in castor oil is at the bottom of the scale, while a composition rich in heavy solvents is at the top of this same scale.
Il y a 12 compositions et il est admis qu'une note supérieure ou égale à 5 confère déjà une barrière satisfaisante aux graisses. L'évaluation se fait visuellement. Les résultats sont fortement dépendants de l'état de surface du support. En effet, généralement, plus la rugosité est faible, meilleur est le résultat au kit test. Par exemple, il a été observé qu'après diminution de la rugosité notamment suite à une impression taille douce, les résultats du kit test ont tendance à être améliorés.There are 12 compositions and it is accepted that a score greater than or equal to 5 already confers a satisfactory barrier to grease. The evaluation is done visually. The results are strongly dependent on the surface condition of the support. Indeed, generally, the lower the roughness, the better the result of the test kit. For example, it has been observed that after reducing the roughness, in particular following intaglio printing, the results of the test kit tend to be improved.
La résistance mécanique du support a été évaluée par plusieurs tests bien connus de l'industrie papetière dans les sens « Marche » (longitudinal c'est-à-dire dans le sens des fibres) et « Travers » (transversal c'est-à-dire dans le sens perpendiculaire aux fibres) du papier indiqués respectivement SM et ST:
- Résistance au double pli avec un appareil de marque Frank Prüfgeräte suivant la norme ISO 5626 ;
- Résistance à la déchirure amorcée suivant la norme ISO 1974 ;
- Résistance à la traction sèche et humide suivant la norme ISO 1924-2 ;
- Résistance à l'état humide suivant la norme ISO 3781.
- Double fold resistance with a Frank Prüfgeräte device according to ISO 5626;
- Initiated tear resistance according to ISO 1974 standard;
- Dry and wet tensile strength according to ISO 1924-2;
- Wet strength according to ISO 3781.
La rigidité du support a également été évaluée par la mesure de rigidité Kodak suivant la norme ISO 5629.The stiffness of the support was also evaluated by the Kodak stiffness measurement according to the ISO 5629 standard.
Les propriétés de surface telle que la rugosité Bendsten et la perméabilité à l'air Bendsten ont également été mesurées, respectivement selon les normes ISO 8791-2 et ISO 5636-3 sur les faces recto et verso, donnant ainsi une indication sur l'imprimabilité du support.Surface properties such as Bendsten roughness and Bendsten air permeability were also measured, respectively according to ISO 8791-2 and ISO 5636-3 standards on the front and back sides, thus giving an indication of the printability of the medium.
Tout comme pour le Cobb, la perméabilité à l'air après « crumpling » x8 a été évaluée pour vérifier les propriétés barrières après froissement.As for the Cobb, the air permeability after crumpling x8 was evaluated to check the barrier properties after crumpling.
Les résultats obtenus avec un support papier vélin 100% coton recouvert sur chaque face d'une couche de surfactant cationique (produit A qui constitue donc l'agent de renfort structurel) et d'une couche constituée d'agent oléophobe et hydrophobe à 3% dans l'eau (produit B) (appelé « solution haute performance ») sont donnés dans le tableau 1 ci-dessous. Le couchage a été réalisé en 2 étapes (produit A puis produit B), par tige filetée sur chaque face d'un papier sec déjà formé de grammage 90 g/m2. La solution aqueuse est déposée le long de la tige puis celle-ci est déplacée sur la feuille pour répartir la solution de manière homogène. La tige filetée utilisée dépose une couche humide de 6 µm d'épaisseur. L'épaisseur réelle de matière obtenue est plus faible après évaporation de l'eau durant le séchage. Le grammage sec ainsi déposé d'agent oléophobe et hydrophobe est d'environ 0.5 g/m2 par face. Celui de l'assouplissant est d'environ 4,5 g/m2 par face.The results obtained with a 100% cotton vellum paper backing covered on each side with a layer of cationic surfactant (product A which therefore constitutes the structural reinforcing agent) and a layer consisting of oleophobic and hydrophobic agent at 3% in water (product B) (called "high performance solution") are given in Table 1 below. The coating was carried out in 2 stages (product A then product B), by threaded rod on each face of a dry paper already formed with a basis weight of 90 g/m 2 . The aqueous solution is deposited along the stem then the latter is moved over the leaf to distribute the solution evenly. The threaded rod used deposits a wet layer 6 µm thick. The actual thickness of material obtained is lower after evaporation of the water during drying. The dry basis weight thus deposited of oleophobic and hydrophobic agent is approximately 0.5 g/m 2 per side. That of the fabric softener is approximately 4.5 g/m 2 per side.
Les résultats obtenus avec cette solution haute performance ont été comparés au papier seul, au papier avec seulement le produit A, au papier avec seulement le produit B ainsi qu'à un papier haute durabilité connu dans le domaine de l'impression fiduciaire. Les tests sont effectués en triplicat et les valeurs indiquées sont des moyennes.
L'analyse du tableau 1 ci-dessus montre que la perméabilité à l'air après froissement (x8) de la solution selon l'invention est plus de deux fois plus faible que le papier non traité, ce qui indique sans ambiguïté une déstructuration bien inférieure du support.The analysis of Table 1 above shows that the air permeability after crumpling (x8) of the solution according to the invention is more than twice lower than the untreated paper, which unambiguously indicates a destructuring well bottom of the bracket.
La solution selon l'invention augmente également de deux à trois fois (selon la face considérée) la résistance à l'eau, même après froissement (crumpling x1) par rapport au support non traité.The solution according to the invention also increases water resistance by two to three times (depending on the face considered), even after crumpling (crumpling x1) compared to the untreated support.
Le traitement appliqué conserve donc un effet barrière significatif même après froissement du support.The treatment applied therefore retains a significant barrier effect even after the support has been crumpled.
La rugosité de surface de la solution est plus élevée, de 40 à 60% suivant la face considérée, que le support non traité. Cette valeur de rugosité peut être diminuée par calandrage si nécessaire.The surface roughness of the solution is higher, from 40 to 60% depending on the face considered, than the untreated support. This roughness value can be reduced by calendering if necessary.
La résistance à l'huile est nettement améliorée avec une note obtenue de 8 au Kit test sur les 2 faces.The oil resistance is significantly improved with a score of 8 obtained in the Kit test on both sides.
Concernant les propriétés mécaniques, les résultats du test de double pli de la solution selon l'invention sont plus de trois fois supérieurs au papier Vélin non traité grâce à l'agent de renfort structurel qui apporte de la flexibilité aux fibres.Concerning the mechanical properties, the results of the double ply test of the solution according to the invention are more than three times superior to untreated Vellum paper thanks to the structural reinforcing agent which provides flexibility to the fibers.
Cette amélioration de la flexibilité des fibres est confirmée par la baisse du module d'Young de 58 % en sens marche et de 70 % en sens travers, ainsi que par l'augmentation de l'élongation à la rupture par rapport au papier non traité. Les résultats de rigidité dynamique du support restent proche des valeurs standards avec des résultats peu différents de ceux du papier non traité.This improvement in fiber flexibility is confirmed by the decrease in Young's modulus of 58% in the machine direction and 70% in the cross direction, as well as by the increase in elongation at break compared to untreated paper. . The dynamic stiffness results of the support remain close to the standard values with results not very different from those of the untreated paper.
La résistance à l'état humide est améliorée de 7% aussi bien en sens marche qu'en sens travers. Cette caractéristique est importante pour assurer une tenue des billets en circulation notamment dans les régions humides. En effet, en présence d'eau, les liaisons hydrogènes qui lient les fibres du papier entre elles sont aisément rompues et ceci a pour effet de diminuer fortement la résistance mécanique de la feuille de papier qui va commencer alors à se déstructurer.Wet strength is improved by 7% in both forward and cross direction. This characteristic is important to ensure that banknotes are held in circulation, particularly in humid regions. Indeed, in the presence of water, the hydrogen bonds which link the fibers of the paper together are easily broken and this has the effect of greatly reducing the mechanical strength of the sheet of paper which will then begin to break down.
L'adhésion des encres sur le support papier selon l'invention a été évaluée pour trois types d'impression caractéristiques de la fabrication des billets de banque : l'offset, la taille douce et la typographie. La résistance de ces encres a été évaluée par une série de tests chimiques (trempage dans différents produits chimiques) et mécaniques.The adhesion of the inks to the paper support according to the invention was evaluated for three types of printing characteristic of the manufacture of banknotes: offset, intaglio and typography. The resistance of these inks has been evaluated by a series of chemical (soaking in different chemicals) and mechanical tests.
Parmi les tests mécaniques, on retrouve le « test de froissement ou crumpling » qui évalue la résistance au froissement du support papier et des encres imprimées sur ce dernier à l'état sec et humide.Among the mechanical tests, we find the “crumpling or crumpling test” which assesses the resistance to creasing of the paper support and the inks printed on it in the dry and wet state.
Pour le « crumpling humide », l'échantillon est placé dans l'eau pendant 15 minutes avant de réaliser le froissement. Le froissement est répété 4, 8 et 40 fois sur l'échantillon sec et sur l'échantillon humide, 4 et 8 fois, à l'aide d'un appareil de crumpling IGT décrit plus haut dans le texte.For "wet crumpling", the sample is placed in water for 15 minutes before performing the crumpling. Crumpling is repeated 4, 8 and 40 times on the dry sample and on the wet sample, 4 and 8 times, using an IGT crumpling device described above in the text.
Après les tests, le papier et les différentes impressions (offset, offset à effet fluorescent, numérotage et taille douce) sont évalués visuellement et les dommages sont notés de 0 à 4, avec les significations suivantes : 0 = disparition des éléments, 1 = plus 50% de changement, 2 = moins de 50% de changement, 3 = léger changement, 4 = aucun changement.After the tests, the paper and the different printings (offset, offset with fluorescent effect, numbering and intaglio) are evaluated visually and the damage is noted from 0 to 4, with the following meanings: 0 = disappearance of the elements, 1 = more 50% change, 2 = less than 50% change, 3 = slight change, 4 = no change.
Par l'expression « disparition des éléments », on entend la disparition totale de l'impression, de sorte qu'elle n'est plus visible sur le billet.By the expression "disappearance of the elements" is meant the total disappearance of the printing, so that it is no longer visible on the ticket.
Les résultats obtenus sont mentionnés dans le tableau 2 ci-dessous.
La tenue des encres est bonne avec des résultats équivalents à ceux obtenus sur des papiers sans traitement selon l'invention. Par exemple, pour l'offset fluo, il est courant d'avoir des notes de 0 ou 1 aux tests d'eau chaude et de lessive sur un papier standard non traité.The hold of the inks is good with results equivalent to those obtained on papers without treatment according to the invention. For example, for fluorescent offset, it is common to have scores of 0 or 1 in hot water and lye tests on standard untreated paper.
Les résistances au crumpling sont bonnes, notamment après le test très agressif de 40 froissements à l'état sec (dernière ligne).Resistance to crumpling is good, especially after the very aggressive test of 40 crumplings in the dry state (last line).
Globalement, les résultats obtenus dans cet exemple sont satisfaisants, le traitement n'a pas d'impact négatif sur la tenue des encres sur le support et ne nécessitera donc pas un post-vernissage obligatoire pour renforcer cette tenue.Overall, the results obtained in this example are satisfactory, the treatment has no negative impact on the hold of the inks on the support and will therefore not require compulsory post-varnishing to reinforce this hold.
Dans l'exemple 2, le traitement tel que décrit par l'invention est appliqué par une machine d'enduction bobine-bobine à lame d'air de laize 1300 mm (produit A puis produit B en ligne), sur du papier vélin 100% coton. La vitesse de défilement machine pendant l'enduction était de 60m/min.In Example 2, the treatment as described by the invention is applied by a roll-to-roll coating machine with an air knife of width 1300 mm (product A then product B in line), on 100 mm vellum paper. % cotton. The machine run speed during coating was 60 m/min.
Le produit A est séché avec des fours à air chaud avant d'appliquer le produit B lui-même séché par four à air chaud.Product A is dried with hot air ovens before applying product B itself dried by hot air oven.
Les résultats obtenus dans cette configuration sur papier vélin 100% coton sont détaillés dans le tableau 3. Les grammages secs déposés par face étaient les suivants : produit A = 1.4 g/m2, produit B = 1.5 g/m2. Les résultats obtenus avec la solution selon l'invention ont été comparés au papier seul, non traité.
La perméabilité à l'air après froissement (x8) de l'exemple 2 est plus de quatre fois plus faible que le papier non traité.The creased air permeability (x8) of Example 2 is more than four times lower than the untreated paper.
La résistance à l'eau après froissement (crumpling x1) est également améliorée : l'absorption d'eau est deux fois plus faible avec le support selon l'invention qu'avec le support non traité.The resistance to water after crumpling (crumpling x1) is also improved: water absorption is twice lower with the support according to the invention than with the untreated support.
Tout comme dans l'exemple 1, le traitement appliqué conserve son effet barrière même après froissement du support.Just as in Example 1, the treatment applied retains its barrier effect even after the support has been crumpled.
La résistance à l'huile est améliorée de cinq points au recto et au verso par rapport au papier non traité. Ce résultat est inférieur à celui obtenu dans l'exemple 1, résultat qui peut être attribué d'une part à la différence de technique d'application ("bar coating" dans un cas et couchage à lame d'air dans l'autre) et, d'autre part, aux valeurs de rugosité du support traité qui sont plus élevées que celles obtenues dans l'exemple 1.Oil resistance is improved by five points on the front and back compared to untreated paper. This result is lower than that obtained in Example 1, a result which can be attributed on the one hand to the difference in application technique ("bar coating" in one case and air knife coating in the other) and, on the other hand, to the roughness values of the treated support which are higher than those obtained in example 1.
En effet, comme précédemment décrit dans l'explication du kit test, la rugosité de surface du support peut avoir un impact sur la résistance à l'huile. A noter qu'il est possible de faire baisser la rugosité en calandrant le support après enduction et séchage de ce dernier.Indeed, as previously described in the explanation of the test kit, the surface roughness of the support can have an impact on the oil resistance. Note that it is possible to reduce the roughness by calendering the support after coating and drying of the latter.
Les résultats de double pli de la solution selon l'invention sont trois fois supérieurs au papier standard non traité.The double fold results of the solution according to the invention are three times better than standard untreated paper.
La résistance à l'état humide est également améliorée : de 7% au recto et 6% au verso.Wet strength is also improved: 7% on the front and 6% on the back.
Dans cet exemple, on montre que l'on peut accentuer une propriété (ici le double pli) pour obtenir des résistances très élevées (moyenne SM/ST >10 000) en ayant une résistance à l'huile correcte.In this example, we show that we can accentuate a property (here the double ply) to obtain very high resistances (average SM/ST >10,000) by having the correct oil resistance.
En dosant les proportions d'agent A et B, il est possible de modifier les propriétés finales du papier selon ce qui est souhaité.By dosing the proportions of agent A and B, it is possible to modify the final properties of the paper according to what is desired.
Tout comme pour l'exemple 1, l'adhésion des encres a été évaluée sur le papier ainsi produit pour trois types d'impression caractéristiques de la fabrication des billets de banque : l'offset, la taille douce et la typographie.As for example 1, the adhesion of the inks was evaluated on the paper thus produced for three types of printing characteristic of the manufacture of banknotes: offset, intaglio and typography.
Les résultats obtenus sont détaillés dans le tableau 4 ci-dessous :
Les conclusions de l'exemple 1 se confirment avec notamment de bonnes tenues au crumpling même après 40 froissements à sec. Le traitement appliqué ne perturbe pas l'adhésion des encres sur le papier.The conclusions of example 1 are confirmed with in particular good resistance to crumpling even after 40 dry crumplings. The treatment applied does not disturb the adhesion of the inks to the paper.
Le traitement selon l'invention a été appliqué sur plusieurs papiers vélin provenant de différents fournisseurs pour vérifier la compatibilité et l'efficacité du traitement sur différents papiers.
Comme le montre le tableau :
Le traitement est compatible avec différents papiers Vélin.As the table shows:
The treatment is compatible with various Vellum papers.
Après traitement des papiers, les résultats exhibent tous une tendance nette et franche à l'augmentation de cette propriété de double plis qui, sauf une exception, montre des valeurs 3 à 5 fois plus élevés en sens marche et près de 2 fois plus élevés en moyenne en sens travers.After treatment of the papers, the results all show a clear and distinct tendency to increase this double-folding property which, with one exception, shows values 3 to 5 times higher in the machine direction and almost 2 times higher in the machine direction. average in the transverse direction.
Concernant la perméabilité à l'air, certaines valeurs sont basses après traitement car le papier non traité avait déjà une perméabilité à l'air peu élevée.
Légende : SM = sens marche et ST = sens traversRegarding the air permeability, some values are low after treatment because the untreated paper already had a low air permeability.
Legend: SM = forward direction and ST = transverse direction
Claims (14)
- Highly durable paper medium for printing a security document, especially a banknote, comprising cellulose fibers, according to a proportion of at least 50% by mass relative to the total mass of the paper medium in the dry state, additives and adjuvants, at least one binder, and which further comprises at least one oleophobic and hydrophobic agent based on an organic compound containing perfluoropolyether (PFPE) groups, according to a concentration greater than 0% and less than or equal to 5% by mass in the dry state relative to the total mass of the paper medium in the dry state,
characterized in that it also comprises at least one non-fibrous structural reinforcement agent of the family of softening agents, i.e., agents increasing the flexibility of cellulose fibres, according to a quantity comprised between 0.5% and 15% by mass relative to the total mass of the paper medium in the dry state. - Paper medium according to claim 1, further characterized by the fact that the Young modulus of said medium, measured according to standard ISO 1924 is less by at least 30%, preferably by 50 to 60%, than that of a paper medium without said structural reinforcement agent.
- Paper medium according to claim 1 or 2, characterized by the fact that it has a mean value of machine direction / cross-machine direction double folding resistance greater by 100%, and preferably by 200%, than that of a paper medium without said structural reinforcement agent.
- Paper medium according to one of claims 1 or 3, characterized in that the concentration of cellulose fibres is greater than or equal to 85% and less than 100% by mass in the dry state relative to the total mass of said paper medium in the dry state.
- Paper medium according to one of claims 1 to 4, characterized in that the additives and adjuvants and binders are present according to a concentration greater than 0% and less than or equal to 15% by mass in the dry state relative to the total mass of said paper medium in the dry state.
- Paper medium according to one of the preceding claims, characterized in that the structural reinforcement agent is chosen from among surfactants.
- Paper medium according to one of claims 1 to 6, characterized in that said structural reinforcement agent is chosen from among cationic surfactants, especially among quaternary ammonium compounds and cationic polymers.
- Paper medium according to one of claims 1 to 5, characterized in that said structural reinforcement agent is chosen from among nonionic surfactants, especially in the group consisting of polybutylene, long-chain fatty acids, i.e., having a chain length of at least 10 carbon atoms, and ethoxylated amino acids.
- Paper medium according to one of claims 1 to 5, characterized in that said structural reinforcement agent is chosen from among anionic surfactants.
- Paper medium according to one of the preceding claims, characterized in that the perfluoropolyether groups have in their chemical formulas the basic fragments -(CF2CF2O)m-(CF2O)n- where m and n are integers.
- Security document, characterized in that it comprises a paper medium according to one of the preceding claims.
- Security document according to the preceding claim, characterized in that it is a banknote.
- Manufacturing method for a paper medium according to one of claims 1 to 10, characterized in that it comprises the following steps:a) suspending the cellulose fibres in water,b) refining the mixturec) adding additives, adjuvants and binderd) purifying and filtering the fibrous suspension,e) shaping the paper medium,f) pressing,g) pre-drying,h) coating the paper medium,i) post-drying,and in that it comprises steps of adding structural reinforcement agent(s) and adding oleophobic and hydrophobic agent(s), alone or in mixture, so that:- when they are added alone, i.e., individually:- the structural reinforcement agent is added at step c) and the oleophobic and hydrophobic agent is added at step h) or vice versa; or- both agents are applied in line on the paper machine one after the other in step h), the first of them being dried by hot air or infrared radiation, before applying the second, itself dried by hot air or infrared radiation;- when they are added into the mixture, this addition is done during step c) or during step h).
- Manufacturing method according to claim 13, characterized by the fact that the structural reinforcement agents and the oleophobic and hydrophobic agents are applied offline, separately or in mixture, by coating, dipping, impregnation, surfacing, spraying, air knife coating, curtain coating, pencil coating, coating by engraved rollers, pre-positioned or by transfer of the "size press" or "film press" type.
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FR1758867A FR3071518B1 (en) | 2017-09-26 | 2017-09-26 | PAPER HOLDER, SECURITY DOCUMENT INCLUDING IT, AND METHOD OF MANUFACTURE |
PCT/EP2018/075988 WO2019063560A1 (en) | 2017-09-26 | 2018-09-25 | Paper support, security document which comprises same and manufacturing process |
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US5200037A (en) * | 1988-05-23 | 1993-04-06 | The Procter & Gamble Company | Absorbent structures from mixed furnishes |
DE10148122A1 (en) | 2001-09-28 | 2003-04-24 | Giesecke & Devrient Gmbh | security paper |
MX2007015411A (en) | 2005-06-29 | 2008-02-19 | Henkel Kgaa | Process for softening hygienic paper. |
ES2607006T3 (en) * | 2008-07-01 | 2017-03-28 | Solvay Specialty Polymers Italy S.P.A. | Process to confer repellent to grease, oil and water to substrates |
FR2975408B1 (en) | 2011-05-18 | 2020-10-23 | Arjowiggins Security | HIGH DURABILITY SHEET FOR BANK NOTE MANUFACTURING |
FR3025532A1 (en) * | 2014-09-05 | 2016-03-11 | Oberthur Fiduciaire Sas | PAPER HOLDER, MANUFACTURING METHOD THEREFOR, AND SECURITY DOCUMENT MANUFACTURED THEREWITH |
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