EP2148954B2 - Crease-resistant security sheet, manufacturing process thereof and security document comprising same - Google Patents

Crease-resistant security sheet, manufacturing process thereof and security document comprising same Download PDF

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Publication number
EP2148954B2
EP2148954B2 EP08805868.0A EP08805868A EP2148954B2 EP 2148954 B2 EP2148954 B2 EP 2148954B2 EP 08805868 A EP08805868 A EP 08805868A EP 2148954 B2 EP2148954 B2 EP 2148954B2
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EP
European Patent Office
Prior art keywords
fibers
sheet
fact
manufacturing
dry weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP08805868.0A
Other languages
German (de)
French (fr)
Other versions
EP2148954A2 (en
EP2148954B1 (en
Inventor
Henri Rosset
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ArjoWiggins Security SAS
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ArjoWiggins Security SAS
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Application filed by ArjoWiggins Security SAS filed Critical ArjoWiggins Security SAS
Priority to SI200831123A priority Critical patent/SI2148954T2/en
Priority to SI200831123T priority patent/SI2148954T1/en
Priority to PL08805868T priority patent/PL2148954T5/en
Publication of EP2148954A2 publication Critical patent/EP2148954A2/en
Application granted granted Critical
Publication of EP2148954B1 publication Critical patent/EP2148954B1/en
Publication of EP2148954B2 publication Critical patent/EP2148954B2/en
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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
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H21/42—Ribbons or strips
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/26—Special paper or cardboard manufactured by dry method; Apparatus or processes for forming webs by dry method from mainly short-fibre or particle material, e.g. paper pulp
    • D21H5/265—Treatment of the formed web
    • D21H5/2657—Consolidation
    • D21H5/2664—Addition of a binder, e.g. synthetic resins or water

Definitions

  • the invention relates to a method of manufacturing a crush resistant security sheet and a security document comprising the sheet.
  • the object of the present invention is therefore to provide a method of manufacturing a security sheet which has a good resistance to wrinkling.
  • a wrinkle-resistant security sheet comprising fibers, an anionic polymer in a proportion of between 5 and 45% by dry weight relative to the total weight of the dry fibers and having a temperature. glass transition greater than - 40 ° C and a main cationic flocculating agent in an amount of between 1 and 5% by dry weight relative to the total weight of the fibers in dry.
  • the process of the invention makes it possible, by using an anionic polymer and flocculating agent (s), to precipitate said anionic polymer on the fibers and to obtain a security sheet having resistance properties. wrinkling particularly high.
  • total fiber weight should be understood as meaning “total dry fiber weight” unless otherwise indicated.
  • anionic polymer is meant here a polymer having anionic groups. This polymer was used in the form of a dispersion or an emulsion in a stabilized aqueous medium, also called latex. Polymers in aqueous dispersion are commonly used and known to those skilled in the paper industry.
  • said aqueous suspension further comprises a secondary cationic flocculating agent in an amount of between 0.001 and 0.006% by dry weight relative to the total weight of the fibers.
  • said formed sheet further comprises a secondary cationic flocculating agent in an amount of between 0.001 and 0.006% by dry weight relative to the total weight of the fibers.
  • a secondary cationic flocculating agent in an amount of between 0.001 and 0.006% by dry weight relative to the total weight of the fibers.
  • said aqueous suspension is obtained from a fiber mixture and from said main cationic flocculating agent, to which said anionic polymer and said cationic flocculating agent are added. secondary before proceeding to the formation of said sheet.
  • This embodiment has the advantage that it can be applied to aqueous suspensions of "standard" fibers used for the manufacture of safety sheets because they comprise wet strength agents which can also be used as flocculation agents. in the context of the present invention.
  • said anionic polymer is added before said secondary flocculation agent.
  • the Applicant has found that the presence of an anionic polymer and flocculating agent (s) in the composition of the sheet formed according to the method of the invention significantly improved the crease resistance of said sheet.
  • the sheet formed according to the method of the invention may have a porosity after crumpling close to that of an uncrumpled sheet, that is to say that the folds caused by crumpling substantially do not weaken the paper. This feature allows the security sheet formed according to the invention to have a very high circulation time.
  • the sheet formed according to the process of the invention also has a very high double-fold resistance.
  • the sheet formed according to the method of the invention has a tear strength equivalent to or greater than that of a similar sheet free of anionic polymer.
  • said anionic polymer present in the composition of the formed sheet has a glass transition temperature of between -30 ° C. and 10 ° C.
  • glass transition temperature means the temperature below which the polymer is rigid. As the temperature increases, the polymer passes through a transition state that allows the macromolecular chains to slip relative to one another and the polymer softens.
  • the proportion of said anionic polymer in the composition of the sheet is between 10 and 30% by dry weight relative to the total weight of the fibers.
  • the fibers used in the composition of the sheet comprise cellulosic fibers, in particular cotton fibers.
  • said cellulosic fibers are present in a proportion greater than 60% by dry weight relative to the total dry weight of the composition of the sheet.
  • said cellulosic fibers represent at least 70% by dry weight of the total amount of fibers.
  • said cellulosic fibers are cotton fibers and represent at least 70% by dry weight of the total amount of fibers.
  • the fibers used in the composition of the sheet may comprise synthetic fibers.
  • This embodiment is particularly advantageous because it makes it possible to further improve the tear-resistance properties of the sheet according to the invention.
  • the Applicant has found that, surprisingly, the use of synthetic fibers, generally used to strengthen the paper, had a synergistic effect with the use of the anionic polymer.
  • the Applicant has measured that the sheets containing synthetic fibers, while maintaining a high wrinkle resistance, also had a particularly high tear resistance.
  • the tear resistance of the sheets according to this particular embodiment of the invention is greater than the tear resistance of the sheets according to the invention without synthetic fibers and the tear resistance of sheets comprising synthetic fibers. but no anionic polymer.
  • the synthetic fibers are in a proportion of between 5 and 30% by dry weight relative to the total weight of the fibers.
  • the sheet comprises cotton fibers in a proportion of at least 70% by dry weight relative to the total weight of the fibers and synthetic fibers in a proportion of between 10 and 30% in dry weight relative to the total weight of the fibers, the sum total of cotton fibers and synthetic fibers being equal to 100.
  • the security sheets formed according to the process of the invention comprising synthetic fibers have a tear strength greater than 1300 mN.
  • said synthetic fibers are chosen from polyamide fibers and / or polyester fibers. They may be, for example, polyamide 6-6 fibers or polyester fibers marketed by Kuraray under the trade name EP133.
  • the anionic polymer present in the security sheet comprises a polymer having carboxyl functions.
  • said polymer is a carboxylated syrene-butadiene copolymer.
  • Such copolymers are available, for example, from Dow Chemical Company with different glass transition temperatures.
  • the main cationic flocculating agent is a cationic resin.
  • this resin is a polyamide-amine-epichloridin resin, called PAAE resin.
  • the main cationic flocculating agent is chosen from polyacrylamides, polyethyleneimines, polyvinylamines and their mixtures.
  • the secondary cationic flocculating agent is chosen from polyacrylamides, polyethylenimines, polyvinylamines and their mixtures.
  • the security sheet comprises at least one security element.
  • said security element is chosen from optically variable devices (OVD), in particular interferential elements, in particular iridescent elements, holograms, security threads, watermarks, boards, pigments or luminescent fibers. and / or magnetic and / or iridescent and / or metallic, and combinations thereof.
  • ODD optically variable devices
  • interferential elements in particular iridescent elements, holograms, security threads, watermarks, boards, pigments or luminescent fibers.
  • iridescent elements in particular iridescent elements, holograms, security threads, watermarks, boards, pigments or luminescent fibers. and / or magnetic and / or iridescent and / or metallic, and combinations thereof.
  • the sheet according to the invention may comprise an RFID device (radio frequency identification device).
  • the security sheet comprises at least one at least partially fiber-free zone, also known as a "window" zone.
  • the security sheet according to the invention comprises a thread or a security band incorporated into said sheet, and appearing in at least one window.
  • the security sheet comprises mineral fillers in an amount of 1 to 10% by dry weight relative to the total weight of the fibers.
  • said mineral fillers are present in a proportion of between 1 and 5% by dry weight relative to the total weight of the fibers.
  • These fillers are chosen, for example from calcium carbonate, kaolin and titanium dioxide, or mixtures thereof.
  • the method of manufacturing the security sheet comprises a step in which at least one face of said sheet, after dewatering of said suspension is coated with a surfacing layer.
  • This surfacing layer may make it possible, for example to improve the bending and / or tensile strength properties or even the durability properties of said sheet, as described below.
  • the formed security sheet may further comprise an outer surfacing layer.
  • These surfacing layers, coated on at least one side of a sheet, are well known to those skilled in the art and allow, for example for a layer based on a polyvinyl alcohol to improve the double-fold resistance properties. and pulling the sheet.
  • the security sheet formed according to the method of the invention may comprise a surfacing layer intended to reinforce its durability properties, such as that for example a layer whose composition is described in the application EP 1 319 104 and which comprises a transparent or translucent elastomeric binder, such as a polyurethane, and a colloidal silica.
  • the invention also relates to a security document comprising the security sheet as obtained by the method described above.
  • the invention relates to a banknote.
  • the Applicant has carried out three series of tests: the series 1 and 2 on non-surfaced sheets and the series 3 on sheets coated with a surfacing layer, as are generally the sheets included in the security documents such as than banknotes.
  • a security sheet is produced whose composition corresponds to the basic composition of a large number of banknotes currently in circulation.
  • said sheet is formed wet on a paper machine of round shape, from an aqueous suspension comprising only cotton fibers and a wet strength agent (here a PAAE resin) in a proportion of 2.1% by dry weight relative to the weight of the fibers.
  • a wet strength agent here a PAAE resin
  • the resulting sheet has a basis weight of 85.2 g / m 2 , and a thickness of 142 microns.
  • a sheet formed according to the process of the invention comprising cotton-only fibers, a carboxylated styrene-butadiene copolymer with a glass transition temperature of -25 ° C., is produced on a paper machine of round shape. a proportion of 11% by dry weight relative to the weight of the fibers and a main flocculation agent in the form of a PAAE resin in a proportion of 2.3% by dry weight relative to the total weight of the fibers.
  • the PAAE resin also has a role of wet strength agent, as in Comparative Example 1.
  • the resulting sheet has a basis weight of 87.6 g / m 2 and a thickness of 124 microns.
  • a sheet of paper formed according to the process of the invention is made by taking up the composition of Example 2 and adding a polyacrylamide as a secondary flocculating agent in a proportion of 0.001% relative to the total weight of the fibers.
  • the resulting sheet has a basis weight of 86.9 g / m 2 and a thickness of 125 microns.
  • the resulting sheet has a basis weight of 86.5 g / m 2 and a thickness of 121 microns.
  • a security sheet is produced whose composition corresponds to the basic composition of a large number of banknotes currently in circulation.
  • said sheet is formed wet on a laboratory form, from an aqueous suspension of cotton-only fibers comprising a wet strength agent (here a PAAE resin) in a proportion of 2.5% by dry weight relative to the total weight of the fibers.
  • a wet strength agent here a PAAE resin
  • the resulting sheet has a basis weight of 80.5 g / m 2 , and a thickness of 137 microns.
  • a sheet of paper formed according to the process of the invention comprising cotton-only fibers, a carboxylated styrene-butadiene copolymer having a glass transition temperature of 5 ° C in an amount of 25% by dry weight relative to the total weight of the fibers, a PAAE resin as main flocculating agent (also having a role of wet strength agent) in a proportion of 3.1% by dry weight relative to to the total weight of fibers and a polyacrylamide as a secondary flocculating agent in a proportion of 0.003% by dry weight, relative to the total weight of the fibers.
  • the resulting sheet has a basis weight of 82.7 g / m 2 , and a thickness of 132 microns.
  • a sheet of paper formed according to the process of the invention comprising cotton-only fibers, a carboxylated styrene-butadiene copolymer having a glass transition temperature of 5 ° C in an amount of 11% by dry weight relative to the total weight of the fibers, a PAAE resin as main flocculation agent (also having a role of wet strength agent) in a proportion of 2.8% by dry weight relative to to the total weight of fibers and a polyacrylamide as a secondary flocculating agent in a proportion of 0.002% by dry weight, based on the total weight of the fibers.
  • the resulting sheet has a basis weight of 83.4 g / m 2 and a thickness of 136 microns.
  • a wet sheet is formed on a round paper machine from an aqueous suspension of cotton-only fibers comprising a wet strength agent (PAAE resin) in a proportion of 2.1. % by dry weight relative to the total weight of the fibers.
  • PAAE resin wet strength agent
  • the sheet of paper obtained is coated with a surfacing layer, intended to improve the durability of the sheet, comprising a polyurethane binder and a colloidal silica, as described in the application EP 1 319 104 .
  • the resulting sheet has a basis weight of 85.8 g / m 2 , and a thickness of 97 microns.
  • a security sheet is made comprising the same constituents as in Comparative Example 8, but part of the cotton fibers have been replaced by polyamide fibers so that the proportion of cotton fibers is 85% by dry weight. and the proportion of polyamide fibers is 15% by dry weight relative to the total weight of the fibers in dry.
  • a sheet of paper according to the process of the invention comprising cotton-only fibers, is formed on a round paper machine, a carboxylated styrene-butadiene copolymer having a glass transition temperature of -26 ° C. a proportion of 11% by dry weight relative to the total weight of the fibers in dry state and a PAAE resin as main floculation agent (also having a role of wet strength agent) in a proportion of 2.3% in dry weight relative to the total weight of fibers in dry.
  • the resulting sheet has a basis weight of 92.8 g / m 2 and a thickness of 103 microns.
  • a sheet of paper according to the process of the invention comprising cotton-only fibers, is formed on a round paper machine, a carboxylated styrene-butadiene copolymer having a glass transition temperature of -26 ° C. an amount of 11% by dry weight relative to the total weight of the fibers, a PAAE resin as main flocculating agent in a proportion of 2.1% by dry weight relative to the total weight of fibers in dry and a polyacrylamide as agent of secondary flocculation in a proportion of 0.001% by dry weight relative to the total weight of the fibers in dry.
  • the resulting sheet has a basis weight of 86.9 g / m 2 and a thickness of 100 microns.
  • a paper sheet is formed according to the process of the invention, comprising only cotton fibers, a carboxylated styrene-butadiene copolymer having a glass transition temperature of -26 ° C. to 25% by dry weight relative to the total weight of the dry fibers, a PAAE resin as main flocculating agent (also having a role of wet strength agent) in an amount of 2.6% by weight. dry weight relative to the total weight of dry fibers and polyacrylamide as a secondary flocculating agent in a proportion of 0.004% by dry weight relative to the total weight of the fibers in dry.
  • the resulting sheet has a basis weight of 82.9 g / m 2 and a thickness of 95 microns.
  • a sheet of paper is formed according to the process of the invention by taking up the composition of Example 12, but replacing a portion of the cotton fibers with polyamide fibers so that the proportion of polyamide fibers is 15% by weight relative to the total weight of the fibers in dry.
  • the resulting sheet has a basis weight of 85.4 g / m 2 and a thickness of 108 microns.
  • the porosity measurements before and after creasing (8 wrinkles at each test) are performed according to standard NF Q03-076. Wrinkles are made by a device of the brand IGT "NBS Crumpling Device”.
  • the double-fold resistance measurements are carried out according to the ISO 5626 standard.
  • the double fold resistance is greatly increased compared to the sheet of Comparative Example 1 (increase between 16 and 53%).
  • the sheets according to Examples 6 and 7 formed according to the process of the invention have substantially improved after-creasing porosities compared with Comparative Example 5 taken as a reference (decrease between 17 and 48% of the porosity after creasing).
  • the double fold resistance is greatly increased compared to the sheet of Comparative Example 5 taken as a reference (increase between 87 and 122%).
  • the sheets formed according to the process of the invention of Examples 10 to 13 show an improvement, relative to the sheet free of anionic polymer of Comparative Example 8 taken as a reference, of between 27% and 186%.
  • the sheet of Comparative Example 9 does not include anionic polymer but comprises polyamide fibers in a proportion of 15%.
  • the tear strength of the sheet of Comparative Example 8 is 13% lower than that of the sheet of Comparative Example 2, which confirms the effect of the synthetic fibers.
  • Examples 10 to 12 show tearing values lower than or equal to those of Comparative Example 8 and lower than those of Comparative Example 9, ie the presence of an anionic polymer alone. has no beneficial influence on the tear strength.
  • Example 13 has a higher tear strength value than that of Comparative Example 8, but is also significantly higher (+ 59%) than that of Comparative Example 9. It follows that the combination of presence of synthetic fibers and anionic polymer in the composition of the security sheet has a synergistic effect on the tear strength of said sheet.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Cleaning In Electrography (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

L'invention concerne un procédé de fabrication d'une feuille de sécurité résistante au froissement et un document de sécurité comprenant cette feuille.The invention relates to a method of manufacturing a crush resistant security sheet and a security document comprising the sheet.

Actuellement, de nombreux documents de sécurité, tels que des billets de banque ou des documents d'identité, comprennent des supports en papier. Un inconvénient des supports en papiers utilisés est qu'ils résistent mal au froissement. Ainsi, les zones froissées présentent des plis profonds, irréversibles, qui résistent mal à la salissure, de sorte que ces zones froissées sont affaiblies et donnent souvent lieu à des déchirures. Ceci est particulièrement désavantageux dans le cas de documents qui, lors de leur manipulation, sont fréquemment pliés ou froissés, comme par exemple des billets de banque, la présence de plis les fragilisant et réduisant leur durée de vie, et rendant leur traitement automatisé malaisé, par exemple lors des vérifications d'authenticité ou d'usure sur machine de tri.Currently, many security documents, such as banknotes or identity documents, include paper supports. A disadvantage of the used paper supports is that they resist bad wrinkling. Thus, the wrinkled areas have deep folds, irreversible, poor resistance to soiling, so that these wrinkled areas are weakened and often give rise to tears. This is particularly disadvantageous in the case of documents which, during their handling, are frequently folded or wrinkled, such as for example banknotes, the presence of folds weakening and reducing their life, and making their automated processing difficult, for example during verifications of authenticity or wear on a sorting machine.

Le but de la présente invention est donc de fournir un procédé de fabrication d'une feuille de sécurité qui présente une bonne résistance au froissement.The object of the present invention is therefore to provide a method of manufacturing a security sheet which has a good resistance to wrinkling.

La Demanderesse a trouvé que ce but était atteint en préparant une feuille de sécurité résistante au froissement comprenant des fibres, un polymère anionique en une proportion comprise entre 5 et 45 % en poids sec par rapport au poids total des fibres en sec et présentant une température de transition vitreuse supérieure à - 40°C et un agent de floculation cationique principal en une quantité comprise entre 1 et 5 % en poids sec par rapport au poids total des fibres en sec.The Applicant has found that this object was achieved by preparing a wrinkle-resistant security sheet comprising fibers, an anionic polymer in a proportion of between 5 and 45% by dry weight relative to the total weight of the dry fibers and having a temperature. glass transition greater than - 40 ° C and a main cationic flocculating agent in an amount of between 1 and 5% by dry weight relative to the total weight of the fibers in dry.

Ainsi, la présente invention concerne un procédé de fabrication d'une feuille de sécurité résistante au froissement, comprenant les étapes consistant à former ladite feuille par voie humide à partir d'une suspension aqueuse comprenant :

  • des fibres comprenant des fibres cellulosiques et/ou synthétiques.
  • une dispersion aqueuse stabilisée d'un polymère anionique en une proportion comprise entre et 45 % en poids sec par rapport au poids des fibres en sec et présentant une température de transition vitreuse supérieure à - 40 °C.
  • un agent floculant cationique en une quantité comprise entre 1 et 5% en poids sec par rapport au poids total des fibres en sec.
puis à essorer et sécher ladite feuille.Thus, the present invention relates to a method of making a wrinkle-resistant security sheet, comprising the steps of forming said sheet wet from an aqueous suspension comprising:
  • fibers comprising cellulosic and / or synthetic fibers.
  • a stabilized aqueous dispersion of anionic polymer in a proportion of between 45% and 45% by dry weight relative to the dry weight of the fibers and having a glass transition temperature greater than -40.degree.
  • a cationic flocculating agent in an amount of between 1 and 5% by dry weight relative to the total weight of the fibers in dry form.
then to wring and dry said sheet.

Le procédé de l'invention permet, grâce à l'utilisation d'un polymère anionique et d'agent(s) de floculation, de faire précipiter ledit polymère anionique sur les fibres et d'obtenir une feuille de sécurité présentant des propriétés de résistance au froissement particulièrement élevées.The process of the invention makes it possible, by using an anionic polymer and flocculating agent (s), to precipitate said anionic polymer on the fibers and to obtain a security sheet having resistance properties. wrinkling particularly high.

Dans la présente demande l'expression « poids total des fibres » doit être comprise comme signifiant « poids total des fibres en sec », sauf indication contraire.In the present application the term "total fiber weight" should be understood as meaning "total dry fiber weight" unless otherwise indicated.

Par « polymère anionique » on entend ici un polymère présentant des groupements anioniques. Ce polymère a été utilisé sous forme d'une dispersion ou d'une émulsion en milieu aqueux stabilisée, appelée aussi latex. Les polymères en dispersion aqueuse sont couramment utilisés et connus de l'homme du métier de l'industrie papetière.By "anionic polymer" is meant here a polymer having anionic groups. This polymer was used in the form of a dispersion or an emulsion in a stabilized aqueous medium, also called latex. Polymers in aqueous dispersion are commonly used and known to those skilled in the paper industry.

Afin d'évaluer la résistance au froissement de la feuille de sécurité, on a effectué des mesures de la porosité Bendtsen avant et après froissement. En effet, l'opération de froissement provoque, du fait des plis formés, une altération plus ou moins prononcée de la surface du papier, conduisant à une augmentation de sa porosité et donc de sa fragilité. En comparant la valeur de la porosité du papier avant et après froissement on peut donc évaluer la résistance au froissement de ce dernier. Moins l'augmentation de la porosité entre la feuille initiale et la feuille froissée est marquée, moins le papier est résistant au froissement. Le but est donc d'obtenir des valeurs de porosité après froissement les plus basses possibles.In order to evaluate the wrinkle resistance of the security sheet, Bendtsen porosity measurements were made before and after wrinkling. Indeed, the wrinkling operation causes, because of the folds formed, more or less pronounced alteration of the surface of the paper, leading to an increase in its porosity and therefore its fragility. Comparing the value of the porosity of the paper before and after creasing can therefore be evaluated the crease resistance of the latter. The less the increase in porosity between the initial sheet and the crumpled sheet, the less the paper is wrinkle resistant. The goal is therefore to obtain values of porosity after crumpling the lowest possible.

Selon un mode de réalisation de l'invention, ladite suspension aqueuse comprend en outre un agent de floculation cationique secondaire en une quantité comprise entre 0,001 et 0,006 % en poids sec par rapport au poids total des fibres.According to one embodiment of the invention, said aqueous suspension further comprises a secondary cationic flocculating agent in an amount of between 0.001 and 0.006% by dry weight relative to the total weight of the fibers.

Ainsi, selon un mode de réalisation de l'invention, ladite feuille formée comprend en outre un agent de floculation cationique secondaire en une quantité comprise entre 0,001 et 0,006 % en poids sec par rapport au poids total des fibres. Ce mode de réalisation est particulièrement avantageux lorsque la proportion du polymère anionique est élevée, en particulier lorsqu'elle dépasse 20 % en poids sec par rapport au poids total des fibres, car la présence de l'agent de floculation cationique secondaire permet de parfaire la floculation du polymère anionique.Thus, according to one embodiment of the invention, said formed sheet further comprises a secondary cationic flocculating agent in an amount of between 0.001 and 0.006% by dry weight relative to the total weight of the fibers. This embodiment is particularly advantageous when the proportion of the anionic polymer is high, in particular when it exceeds 20% by dry weight relative to the total weight of the fibers, because the presence of the secondary cationic flocculating agent makes it possible to perfect the flocculation of the anionic polymer.

Selon un mode de réalisation particulier de l'invention, ladite suspension aqueuse est obtenue à partir d'un mélange de fibres et dudit agent floculant cationique principal, auquel on ajoute ledit polymère anionique et ledit agent de floculation cationique secondaire avant de procéder à la formation de ladite feuille. Ce mode de réalisation présente l'avantage de pouvoir être appliqué à des suspensions aqueuses de fibres « standard » utilisées pour la fabrication des feuilles de sécurité car elles comprennent des agents de résistance à l'état humide qui peuvent également être utilisés comme agents de floculation principaux dans le cadre de la présente invention.According to a particular embodiment of the invention, said aqueous suspension is obtained from a fiber mixture and from said main cationic flocculating agent, to which said anionic polymer and said cationic flocculating agent are added. secondary before proceeding to the formation of said sheet. This embodiment has the advantage that it can be applied to aqueous suspensions of "standard" fibers used for the manufacture of safety sheets because they comprise wet strength agents which can also be used as flocculation agents. in the context of the present invention.

Selon un cas particulier du procédé, on ajoute ledit polymère anionique avant ledit agent de floculation secondaire.According to a particular case of the process, said anionic polymer is added before said secondary flocculation agent.

La Demanderesse a trouvé que la présence d'un polymère anionique et d'agent(s) de floculation dans la composition de la feuille formée selon le procédé de l'invention permettait d'améliorer de façon significative la résistance au froissement de ladite feuille. Ainsi, la feuille formée selon le procédé de l'invention peut présenter une porosité après froissement proche de celle d'une feuille non froissée, c'est à dire que les plis occasionnés par le froissement n'affaiblissent pratiquement pas le papier. Cette caractéristique permet à la feuille de sécurité formée selon l'invention d'avoir une durée de circulation très élevée.The Applicant has found that the presence of an anionic polymer and flocculating agent (s) in the composition of the sheet formed according to the method of the invention significantly improved the crease resistance of said sheet. Thus, the sheet formed according to the method of the invention may have a porosity after crumpling close to that of an uncrumpled sheet, that is to say that the folds caused by crumpling substantially do not weaken the paper. This feature allows the security sheet formed according to the invention to have a very high circulation time.

La feuille formée selon le procédé de l'invention présente également une résistance au double-pli très élevée.The sheet formed according to the process of the invention also has a very high double-fold resistance.

De plus, la feuille formée selon le procédé de l'invention présente une résistance à la déchirure équivalente ou supérieure à celle d'une feuille similaire dépourvue de polymère anionique.In addition, the sheet formed according to the method of the invention has a tear strength equivalent to or greater than that of a similar sheet free of anionic polymer.

Au cours des expériences qu'elle a menées, la Demanderesse a trouvé que seules les feuilles comportant des polymères anioniques d'une température de transition vitreuse supérieure à - 40 °C présentaient d'excellentes caractéristiques de résistance au froissement. En effet, la Demanderesse a trouvé que les polymères anioniques d'une température de transition vitreuse inférieure à - 40 °C sont trop « mous » pour une application à une feuille de sécurité, et conduisent à des feuilles présentant des propriétés mécaniques, telles que la résistance à la traction, la résistance à la déchirure ou la résistance à l'éclatement à l'état sec et à l'état humide, détériorées.In our experiments, we found that only sheets with anionic polymers having a glass transition temperature above -40 ° C exhibited excellent wrinkle resistance characteristics. Indeed, the Applicant has found that anionic polymers with a glass transition temperature below -40 ° C are too "soft" for application to a security sheet, and lead to sheets with mechanical properties, such as Tensile strength, tear strength or resistance to bursting in the dry state and in the wet state, deteriorated.

Selon un mode de réalisation particulier de l'invention, ledit polymère anionique présent dans la composition de la feuille formée présente une température de transition vitreuse comprise entre - 30 °C et 10 °C.According to a particular embodiment of the invention, said anionic polymer present in the composition of the formed sheet has a glass transition temperature of between -30 ° C. and 10 ° C.

On entend par « température de transition vitreuse », la température au-dessous de laquelle le polymère est rigide. Lorsque la température augmente, le polymère passe par un état de transition qui permet aux chaînes macromoléculaires de glisser les unes par rapport aux autres et le polymère se ramollit.The term "glass transition temperature" means the temperature below which the polymer is rigid. As the temperature increases, the polymer passes through a transition state that allows the macromolecular chains to slip relative to one another and the polymer softens.

Selon un mode de réalisation préféré de l'invention, la proportion dudit polymère anionique dans la composition de la feuille est comprise entre 10 et 30 % en poids sec par rapport au poids total des fibres.According to a preferred embodiment of the invention, the proportion of said anionic polymer in the composition of the sheet is between 10 and 30% by dry weight relative to the total weight of the fibers.

Selon un mode de réalisation de l'invention, les fibres entrant dans la composition de la feuille comprennent des fibres cellulosiques, en particulier des fibres de coton.According to one embodiment of the invention, the fibers used in the composition of the sheet comprise cellulosic fibers, in particular cotton fibers.

En particulier, lesdites fibres cellulosiques sont présentes en une proportion supérieure à 60 % en poids sec par rapport au poids sec total de la composition de la feuille.In particular, said cellulosic fibers are present in a proportion greater than 60% by dry weight relative to the total dry weight of the composition of the sheet.

Selon un mode de réalisation particulier de l'invention, lesdites fibres cellulosiques représentent au moins 70 % en poids sec de la quantité totale de fibres.According to a particular embodiment of the invention, said cellulosic fibers represent at least 70% by dry weight of the total amount of fibers.

En particulier, lesdites fibres cellulosiques sont des fibres de coton et représentent au moins 70 % en poids sec de la quantité totale de fibres.In particular, said cellulosic fibers are cotton fibers and represent at least 70% by dry weight of the total amount of fibers.

De préférence, selon un autre mode de réalisation de l'invention, les fibres entrant dans la composition de la feuille peuvent comprendre des fibres synthétiques. Ce mode de réalisation est particulièrement avantageux, car il permet d'améliorer encore les propriétés de résistance à la déchirure de la feuille selon l'invention. En effet, au cours de ses recherches, la Demanderesse a trouvé que, de façon surprenante, l'utilisation de fibres synthétiques, généralement utilisées afin de renforcer le papier, présentait un effet synergique avec l'utilisation du polymère anionique. En effet, la Demanderesse a mesuré que les feuilles contenant des fibres synthétiques, tout en conservant une résistance au froissement élevée, présentaient de plus une résistance à la déchirure particulièrement élevée. La résistance à la déchirure des feuilles selon ce mode de réalisation particulier de l'invention est supérieure à la résistance à la déchirure des feuilles selon l'invention dépourvues de fibres synthétiques ainsi qu'à la résistance à la déchirure de feuilles comprenant des fibres synthétiques mais pas de polymère anionique.Preferably, according to another embodiment of the invention, the fibers used in the composition of the sheet may comprise synthetic fibers. This embodiment is particularly advantageous because it makes it possible to further improve the tear-resistance properties of the sheet according to the invention. Indeed, during his research, the Applicant has found that, surprisingly, the use of synthetic fibers, generally used to strengthen the paper, had a synergistic effect with the use of the anionic polymer. Indeed, the Applicant has measured that the sheets containing synthetic fibers, while maintaining a high wrinkle resistance, also had a particularly high tear resistance. The tear resistance of the sheets according to this particular embodiment of the invention is greater than the tear resistance of the sheets according to the invention without synthetic fibers and the tear resistance of sheets comprising synthetic fibers. but no anionic polymer.

Selon un mode de réalisation préféré de l'invention, les fibres synthétiques sont en une proportion comprise entre 5 et 30 % en poids sec par rapport au poids total des fibres.According to a preferred embodiment of the invention, the synthetic fibers are in a proportion of between 5 and 30% by dry weight relative to the total weight of the fibers.

Selon un mode de réalisation particulier de l'invention, la feuille comprend des fibres de coton en une proportion d'au moins 70 % en poids sec par rapport au poids total des fibres et des fibres synthétiques en une proportion comprise entre 10 et 30 % en poids sec par rapport au poids total des fibres, la somme totale des fibres de coton et des fibres synthétiques étant égale à 100.According to a particular embodiment of the invention, the sheet comprises cotton fibers in a proportion of at least 70% by dry weight relative to the total weight of the fibers and synthetic fibers in a proportion of between 10 and 30% in dry weight relative to the total weight of the fibers, the sum total of cotton fibers and synthetic fibers being equal to 100.

En particulier, les feuilles de sécurité formées selon le procédé de l'invention comprenant des fibres synthétiques présentent une résistance à la déchirure supérieure à 1300 mN.In particular, the security sheets formed according to the process of the invention comprising synthetic fibers have a tear strength greater than 1300 mN.

Selon un mode de réalisation préféré de l'invention, lesdites fibres synthétiques sont choisies parmi des fibres de polyamide et/ou les fibres de polyester. Il peut s'agir, par exemple de fibres de polyamide 6-6 ou de fibres de polyester commercialisées par la société Kuraray sous le nom commercial EP133.According to a preferred embodiment of the invention, said synthetic fibers are chosen from polyamide fibers and / or polyester fibers. They may be, for example, polyamide 6-6 fibers or polyester fibers marketed by Kuraray under the trade name EP133.

Selon un mode de réalisation de l'invention, le polymère anionique présent dans la feuille de sécurité comprend un polymère présentant des fonctions carboxyles. En particulier ledit polymère est un copolymère de syrène-butadiène carboxylé. De tels copolymères sont disponibles, par exemple, auprès de la société Dow Chemical Company avec différentes températures de transition vitreuse.According to one embodiment of the invention, the anionic polymer present in the security sheet comprises a polymer having carboxyl functions. In particular, said polymer is a carboxylated syrene-butadiene copolymer. Such copolymers are available, for example, from Dow Chemical Company with different glass transition temperatures.

Selon un mode de réalisation de l'invention, l'agent de floculation cationique principal est une résine cationique. En particulier, cette résine est une résine polyamide-amine-épichloridrine, dite résine PAAE.According to one embodiment of the invention, the main cationic flocculating agent is a cationic resin. In particular, this resin is a polyamide-amine-epichloridin resin, called PAAE resin.

Selon un autre mode de réalisation de l'invention, l'agent de floculation cationique principal est choisi parmi les polyacrylamides, les polyéthylèneimines, les polyvinylamines et leurs mélanges.According to another embodiment of the invention, the main cationic flocculating agent is chosen from polyacrylamides, polyethyleneimines, polyvinylamines and their mixtures.

Selon un mode de réalisation de l'invention, l'agent de floculation cationique secondaire est choisi parmi les polyacrylamides, les polyéthylènimines, les polyvinylamines et leurs mélanges.According to one embodiment of the invention, the secondary cationic flocculating agent is chosen from polyacrylamides, polyethylenimines, polyvinylamines and their mixtures.

Selon un mode de réalisation de l'invention, la feuille de sécurité comprend au moins un élément de sécurité.According to one embodiment of the invention, the security sheet comprises at least one security element.

En particulier, ledit élément de sécurité est choisi parmi les dispositifs optiquement variables (OVD), notamment les éléments à effet interférentiel, en particulier les éléments iridescents, les hologrammes, les fils de sécurité, les filigranes, les planchettes, les pigments ou fibres luminescents et/ou magnétiques et/ou iridescents et/ou métalliques, et leurs combinaisons.In particular, said security element is chosen from optically variable devices (OVD), in particular interferential elements, in particular iridescent elements, holograms, security threads, watermarks, boards, pigments or luminescent fibers. and / or magnetic and / or iridescent and / or metallic, and combinations thereof.

De plus, la feuille selon l'invention peut comporter un dispositif RFID (dispositif d'identification radio fréquence).In addition, the sheet according to the invention may comprise an RFID device (radio frequency identification device).

Selon un autre mode de réalisation de l'invention, la feuille de sécurité comprend au moins une zone dépourvue de fibres au moins partiellement, zone également appelée « fenêtre ».According to another embodiment of the invention, the security sheet comprises at least one at least partially fiber-free zone, also known as a "window" zone.

Selon un autre mode de réalisation, la feuille de sécurité selon l'invention comprend un fil ou une bande de sécurité incorporé(e) dans ladite feuille, et apparaissant dans au moins une fenêtre.According to another embodiment, the security sheet according to the invention comprises a thread or a security band incorporated into said sheet, and appearing in at least one window.

Selon un mode de réalisation de l'invention, la feuille de sécurité comprend des charges minérales en une quantité de 1 à 10 % en poids sec par rapport au poids total des fibres. En particulier, lesdites charges minérales sont présentes dans une proportion comprise entre 1 et 5 % en poids sec par rapport au poids total des fibres. Ces charges sont choisies, par exemple parmi le carbonate de calcium, le kaolin le dioxyde de titane ou leurs mélanges.According to one embodiment of the invention, the security sheet comprises mineral fillers in an amount of 1 to 10% by dry weight relative to the total weight of the fibers. In particular, said mineral fillers are present in a proportion of between 1 and 5% by dry weight relative to the total weight of the fibers. These fillers are chosen, for example from calcium carbonate, kaolin and titanium dioxide, or mixtures thereof.

Selon un mode de réalisation de l'invention, le procédé de fabrication de la feuille de sécurité comprend une étape dans laquelle au moins une face de ladite feuille, après égouttage de ladite suspension est revêtue d'une couche de surfaçage. Cette couche de surfaçage peut permettre, par exemple d'améliorer les propriétés de résistance au pliage et/ou à la traction ou bien encore les propriétés de durabilité de ladite feuille, comme décrit ci-après.According to one embodiment of the invention, the method of manufacturing the security sheet comprises a step in which at least one face of said sheet, after dewatering of said suspension is coated with a surfacing layer. This surfacing layer may make it possible, for example to improve the bending and / or tensile strength properties or even the durability properties of said sheet, as described below.

Ainsi, la feuille de sécurité formée peut comprendre en outre une couche de surfaçage externe. Ces couches de surfaçage, revêtues sur au moins une face d'une feuille, sont bien connues de l'homme du métier et permettent, par exemple pour une couche à base d'un alcool polyvinylique d'améliorer les propriétés de résistance au double pli et à la traction de la feuille. Selon un autre exemple, la feuille de sécurité formée selon le procédé de l'invention peut comprendre une couche de surfaçage destinée à renforcer ses propriétés de durabilité, telle que par exemple une couche dont la composition est décrite dans la demande EP 1 319 104 et qui comprend un liant élastomère transparent ou translucide, tel qu'un polyuréthane, et une silice colloïdale.Thus, the formed security sheet may further comprise an outer surfacing layer. These surfacing layers, coated on at least one side of a sheet, are well known to those skilled in the art and allow, for example for a layer based on a polyvinyl alcohol to improve the double-fold resistance properties. and pulling the sheet. According to another example, the security sheet formed according to the method of the invention may comprise a surfacing layer intended to reinforce its durability properties, such as that for example a layer whose composition is described in the application EP 1 319 104 and which comprises a transparent or translucent elastomeric binder, such as a polyurethane, and a colloidal silica.

L'invention concerne également un document de sécurité comprenant la feuille de sécurité telle qu'obtenue par le procédé décrit ci-dessus.The invention also relates to a security document comprising the security sheet as obtained by the method described above.

En particulier, l'invention concerne un billet de banque.In particular, the invention relates to a banknote.

L'invention va maintenant être décrite plus en détails à l'aide des exemples non limitatifs et exemples comparatifs suivants.The invention will now be described in more detail with the aid of the following non-limiting examples and comparative examples.

La Demanderesse a réalisé trois séries d'essais : les séries 1 et 2 portant sur des feuilles non surfacées et la série 3 portant sur des feuilles revêtues d'une couche de surfaçage, comme le sont généralement les feuilles comprises dans les documents de sécurité tels que les billets de banque.The Applicant has carried out three series of tests: the series 1 and 2 on non-surfaced sheets and the series 3 on sheets coated with a surfacing layer, as are generally the sheets included in the security documents such as than banknotes.

Des mesures de porosité avant puis après froissement, de résistance au double-pli et de résistance à la déchirure ont été réalisées sur les feuilles ainsi obtenues.Before and after wrinkle porosity measurements, double-fold resistance and tear resistance were performed on the sheets thus obtained.

Série 1Series 1 Exemple comparatif 1Comparative Example 1

On réalise une feuille de sécurité, dont la composition correspond à la composition de base d'un grand nombre de billets de banque actuellement en circulation.A security sheet is produced whose composition corresponds to the basic composition of a large number of banknotes currently in circulation.

Pour ce faire, on forme ladite feuille par voie humide, sur une machine à papier de forme ronde, à partir d'une suspension aqueuse comprenant des fibres uniquement de coton et un agent de résistance à l'état humide (ici une résine PAAE) en une proportion de 2,1 % en poids sec par rapport au poids des fibres.To do this, said sheet is formed wet on a paper machine of round shape, from an aqueous suspension comprising only cotton fibers and a wet strength agent (here a PAAE resin) in a proportion of 2.1% by dry weight relative to the weight of the fibers.

La feuille obtenue présente un grammage de 85,2 g/m2, et une épaisseur de 142 µm.The resulting sheet has a basis weight of 85.2 g / m 2 , and a thickness of 142 microns.

Exemple 2Example 2

On réalise, sur une machine à papier de forme ronde, une feuille formée selon le procédé de l'invention, comprenant des fibres uniquement de coton, un copolymère de styrène-butadiène carboxylé d'une température de transition vitreuse de - 25 °C en une proportion de 11 % en poids sec par rapport au poids des fibres et un agent de floculation principal sous la forme d'une résine PAAE en une proportion de 2,3 % en poids sec par rapport au poids total des fibres. La résine PAAE a également un rôle d'agent de résistance à l'état humide, comme dans l'exemple comparatif 1.A sheet formed according to the process of the invention, comprising cotton-only fibers, a carboxylated styrene-butadiene copolymer with a glass transition temperature of -25 ° C., is produced on a paper machine of round shape. a proportion of 11% by dry weight relative to the weight of the fibers and a main flocculation agent in the form of a PAAE resin in a proportion of 2.3% by dry weight relative to the total weight of the fibers. The PAAE resin also has a role of wet strength agent, as in Comparative Example 1.

La feuille obtenue présente un grammage de 87,6 g/m2 et une épaisseur de 124 µm.The resulting sheet has a basis weight of 87.6 g / m 2 and a thickness of 124 microns.

Exemple 3Example 3

On réalise une feuille de papier formée selon le procédé de l'invention en reprenant la composition de l'exemple 2 et en y ajoutant un polyacrylamide comme agent de floculation secondaire en une proportion de 0,001 % par rapport au poids total des fibres.A sheet of paper formed according to the process of the invention is made by taking up the composition of Example 2 and adding a polyacrylamide as a secondary flocculating agent in a proportion of 0.001% relative to the total weight of the fibers.

La feuille obtenue présente un grammage de 86,9 g/m2 et une épaisseur de 125 µm.The resulting sheet has a basis weight of 86.9 g / m 2 and a thickness of 125 microns.

Exemple 4Example 4

On réalise une feuille de papier formée selon le procédé de l'invention, comprenant les mêmes constituants que dans l'exemple 3, le polymère anionique étant présent en une proportion de 25 % en poids sec par rapport au poids des fibres, l'agent de floculation principal en une proportion de 2,6 % en poids sec par rapport au poids total des fibres et l'agent de floculation cationique secondaire dans une proportion de 0,004 % en poids sec par rapport au poids total des fibres.A sheet of paper formed according to the process of the invention, comprising the same constituents as in Example 3, is produced, the anionic polymer being present in a proportion of 25% by dry weight relative to the weight of the fibers, the agent main flocculation in a proportion of 2.6% by dry weight relative to the total weight of the fibers and the secondary cationic flocculation agent in a proportion of 0.004% by dry weight relative to the total weight of the fibers.

La feuille obtenue présente un grammage de 86,5 g/m2 et une épaisseur de 121 µm.The resulting sheet has a basis weight of 86.5 g / m 2 and a thickness of 121 microns.

Série 2Series 2 Exemple comparatif 5Comparative Example 5

On réalise une feuille de sécurité, dont la composition correspond à la composition de base d'un grand nombre de billets de banque actuellement en circulation.A security sheet is produced whose composition corresponds to the basic composition of a large number of banknotes currently in circulation.

Pour ce faire, on forme ladite feuille par voie humide, sur une formette de laboratoire, à partir d'une suspension aqueuse de fibres uniquement de coton comprenant un agent de résistance à l'état humide (ici une résine PAAE) en une proportion de 2,5 % en poids sec par rapport au poids total des fibres.To do this, said sheet is formed wet on a laboratory form, from an aqueous suspension of cotton-only fibers comprising a wet strength agent (here a PAAE resin) in a proportion of 2.5% by dry weight relative to the total weight of the fibers.

La feuille obtenue présente un grammage de 80,5 g/m2, et une épaisseur de 137 µm.The resulting sheet has a basis weight of 80.5 g / m 2 , and a thickness of 137 microns.

Exemple 6Example 6

On réalise, sur une formette de laboratoire, une feuille de papier formée selon le procédé de l'invention, comprenant des fibres uniquement de coton, un copolymère de styrène-butadiène carboxylé présentant une température de transition vitreuse de 5 °C en une quantité de 25 % en poids sec par rapport au poids total des fibres, une résine PAAE comme agent de floculation principal (ayant également un rôle d'agent de résistance à l'état humide) en une proportion de 3,1 % en poids sec par rapport au poids total de fibres et un polyacrylamide comme agent de floculation secondaire en une proportion de 0,003 % en poids sec, par rapport au poids total des fibres.A sheet of paper formed according to the process of the invention comprising cotton-only fibers, a carboxylated styrene-butadiene copolymer having a glass transition temperature of 5 ° C in an amount of 25% by dry weight relative to the total weight of the fibers, a PAAE resin as main flocculating agent (also having a role of wet strength agent) in a proportion of 3.1% by dry weight relative to to the total weight of fibers and a polyacrylamide as a secondary flocculating agent in a proportion of 0.003% by dry weight, relative to the total weight of the fibers.

La feuille obtenue présente un grammage de 82,7 g/m2, et une épaisseur de 132 µm.The resulting sheet has a basis weight of 82.7 g / m 2 , and a thickness of 132 microns.

Exemple 7Example 7

On réalise, sur une formette de laboratoire, une feuille de papier formée selon le procédé de l'invention, comprenant des fibres uniquement de coton, un copolymère de styrène-butadiène carboxylé présentant une température de transition vitreuse de 5 °C en une quantité de 11 % en poids sec par rapport au poids total des fibres, une résine PAAE comme agent de floculation principal (ayant également un rôle d'agent de résistance à l'état humide) en une proportion de 2,8 % en poids sec par rapport au poids total de fibres et un polyacrylamide comme agent de floculation secondaire en une proportion de 0,002 % en poids sec, par rapport au poids total des fibres.A sheet of paper formed according to the process of the invention comprising cotton-only fibers, a carboxylated styrene-butadiene copolymer having a glass transition temperature of 5 ° C in an amount of 11% by dry weight relative to the total weight of the fibers, a PAAE resin as main flocculation agent (also having a role of wet strength agent) in a proportion of 2.8% by dry weight relative to to the total weight of fibers and a polyacrylamide as a secondary flocculating agent in a proportion of 0.002% by dry weight, based on the total weight of the fibers.

La feuille obtenue présente un grammage de 83,4 g/m2 et une épaisseur de 136 µm.The resulting sheet has a basis weight of 83.4 g / m 2 and a thickness of 136 microns.

Série 3Series 3 Exemple comparatif 8Comparative Example 8

On forme une feuille par voie humide, sur une machine à papier de forme ronde, à partir d'une suspension aqueuse de fibres uniquement de coton comprenant un agent de résistance à l'état humide (résine PAAE) en une proportion de 2,1 % en poids sec par rapport au poids total des fibres. Après formation, la feuille de papier obtenue est enduite d'une couche de surfaçage, destinée à améliorer la durabilité de la feuille, comprenant un liant polyuréthane et une silice colloïdale, comme décrit dans la demande EP 1 319 104 .A wet sheet is formed on a round paper machine from an aqueous suspension of cotton-only fibers comprising a wet strength agent (PAAE resin) in a proportion of 2.1. % by dry weight relative to the total weight of the fibers. After forming, the sheet of paper obtained is coated with a surfacing layer, intended to improve the durability of the sheet, comprising a polyurethane binder and a colloidal silica, as described in the application EP 1 319 104 .

La feuille obtenue présente un grammage de 85,8 g/m2, et une épaisseur de 97 µm.The resulting sheet has a basis weight of 85.8 g / m 2 , and a thickness of 97 microns.

Exemple comparatif 9Comparative Example 9

On réalise une feuille de sécurité comprenant les mêmes constituants que dans l'exemple comparatif 8, mais dont une partie des fibres de coton ont été remplacées par des fibres en polyamide de sorte que la proportion de fibres de coton est de 85 % en poids sec et la proportion de fibres polyamide est de 15 % en poids sec par rapport au poids total des fibres en sec.A security sheet is made comprising the same constituents as in Comparative Example 8, but part of the cotton fibers have been replaced by polyamide fibers so that the proportion of cotton fibers is 85% by dry weight. and the proportion of polyamide fibers is 15% by dry weight relative to the total weight of the fibers in dry.

Exemple 10Example 10

On forme, sur une machine à papier de forme ronde, une feuille de papier selon le procédé de l'invention, comprenant des fibres uniquement de coton, un copolymère de styrène-butadiène carboxylé présentant une température de transition vitreuse de -26 °C en une proportion de 11% en poids sec par rapport au poids total des fibres en sec et une résine PAAE comme agent de floculation principal (ayant également un rôle d'agent de résistance à l'état humide) en une proportion de 2,3 % en poids sec par rapport au poids total de fibres en sec.A sheet of paper according to the process of the invention, comprising cotton-only fibers, is formed on a round paper machine, a carboxylated styrene-butadiene copolymer having a glass transition temperature of -26 ° C. a proportion of 11% by dry weight relative to the total weight of the fibers in dry state and a PAAE resin as main floculation agent (also having a role of wet strength agent) in a proportion of 2.3% in dry weight relative to the total weight of fibers in dry.

La feuille obtenue présente un grammage de 92,8 g/m2 et une épaisseur de 103 µm.The resulting sheet has a basis weight of 92.8 g / m 2 and a thickness of 103 microns.

Exemple 11Example 11

On forme, sur une machine à papier de forme ronde, une feuille de papier selon le procédé de l'invention, comprenant des fibres uniquement de coton, un copolymère de styrène-butadiène carboxylé présentant une température de transition vitreuse de -26 °C en une quantité de 11 % en poids sec par rapport au poids total des fibres, une résine PAAE comme agent de floculation principal en une proportion de 2,1 % en poids sec par rapport au poids total de fibres en sec et un polyacrylamide comme agent de floculation secondaire en une proportion de 0,001 % en poids sec par rapport au poids total des fibres en sec.A sheet of paper according to the process of the invention, comprising cotton-only fibers, is formed on a round paper machine, a carboxylated styrene-butadiene copolymer having a glass transition temperature of -26 ° C. an amount of 11% by dry weight relative to the total weight of the fibers, a PAAE resin as main flocculating agent in a proportion of 2.1% by dry weight relative to the total weight of fibers in dry and a polyacrylamide as agent of secondary flocculation in a proportion of 0.001% by dry weight relative to the total weight of the fibers in dry.

La feuille obtenue présente un grammage de 86,9 g/m2 et une épaisseur de 100 µm.The resulting sheet has a basis weight of 86.9 g / m 2 and a thickness of 100 microns.

Exemple 12Example 12

On forme, sur une machine à papier de forme ronde, une feuille de papier selon le procédé de l'invention, comprenant des fibres uniquement de coton, un copolymère de styrène butadiène carboxylé présentant une température de transition vitreuse de -26 °C en une quantité de 25 % en poids sec par rapport au poids total des fibres en sec, une résine PAAE comme agent de floculation principal (ayant également un rôle d'agent de résistance à l'état humide) en une quantité de 2,6 % en poids sec par rapport au poids total de fibres en sec et un polyacrylamide comme agent de floculation secondaire en une proportion de 0,004 % en poids sec par rapport au poids total des fibres en sec.On a paper machine of round shape, a paper sheet is formed according to the process of the invention, comprising only cotton fibers, a carboxylated styrene-butadiene copolymer having a glass transition temperature of -26 ° C. to 25% by dry weight relative to the total weight of the dry fibers, a PAAE resin as main flocculating agent (also having a role of wet strength agent) in an amount of 2.6% by weight. dry weight relative to the total weight of dry fibers and polyacrylamide as a secondary flocculating agent in a proportion of 0.004% by dry weight relative to the total weight of the fibers in dry.

La feuille obtenue présente un grammage de 82,9 g/m2 et une épaisseur de 95 µm.The resulting sheet has a basis weight of 82.9 g / m 2 and a thickness of 95 microns.

Exemple 13Example 13

On forme, sur une machine à papier de forme ronde, une feuille de papier selon le procédé de l'invention en reprenant la composition de l'exemple 12, mais en remplaçant une partie des fibres de coton par des fibres polyamides de sorte que la proportion en fibres polyamide est de 15 % en poids par rapport au poids total des fibres en sec.On a paper machine of round shape, a sheet of paper is formed according to the process of the invention by taking up the composition of Example 12, but replacing a portion of the cotton fibers with polyamide fibers so that the proportion of polyamide fibers is 15% by weight relative to the total weight of the fibers in dry.

La feuille obtenue présente un grammage de 85,4 g/m2 et une épaisseur de 108 µm.The resulting sheet has a basis weight of 85.4 g / m 2 and a thickness of 108 microns.

Tests et RésultatsTests and Results

Les mesures de porosité avant et après froissement (8 froissements à chaque essai) sont effectuées selon la norme NF Q03-076. Les froissements sont effectués par un appareil de la marque IGT « NBS Crumpling Device ».The porosity measurements before and after creasing (8 wrinkles at each test) are performed according to standard NF Q03-076. Wrinkles are made by a device of the brand IGT "NBS Crumpling Device".

Les mesures de résistance au double-pli sont effectuées selon la norme ISO 5626.The double-fold resistance measurements are carried out according to the ISO 5626 standard.

Les mesures de résistance à la déchirure sont effectuées selon la norme EN 21974.Tear resistance measurements are made according to EN 21974.

Afin d'évaluer la résistance à l'état humide, on a mesuré la résistance à l'éclatement selon la norme ISO NF Q03-053, sur les feuilles humides et sèches. On a ensuite obtenu la valeur de la résistance à l'état humide (REH) selon la formule suivante : REH = Résistance à l ′ éclatement à l ′ état humide Résistance à l ′ éclatement à l ′ état sec × 100

Figure imgb0001
Tableau 1 Essai Exemple comparatif Exemple 2 Exemple 3 Exemple 4 Porosité avant froissement (cm3/min) 22 26 24 27 Porosité après froissement (cm3/min) 206 147 145 89 Amélioration % référence - 28,7 % - 29,7 % - 56,84 % Résistance à l'état humide (%) 48,6 50,3 52 52,5 Résistance au double pli (nombre de plis) 2620 3061 3304 4012 Amélioration % référence +16,8 % +26,1 % + 53,1 % Tableau 2 Essai Exemple comparatif 5 Exemple 6 Exemple 7 Porosité avant froissement (cm3/min) 131 101 117 Porosité après froissement (cm3/min) 1043 545 855 Amélioration référence - 47,8 % -18,1 % Résistance au double pli (nombre de plis) 666 1479 1248 Amélioration référence +122,1 % +87,4 % Tableau 3 Essai Exemple comparatif 8 Exemple comparatif 9 Exemple 10 Exemple 11 Exemple 12 Exemple 13 Porosité avant froissement (cm3/min) 0 0 0 0 0 0 Porosité après froissement (cm3/min) 103 - 41 24 15 12 Amélioration référence - 61,2 % - 77 % - 85 % - 88 % Résistance à l'état humide (%) 54,5 - 57,7 60,0 61,2 63,9 Résistance au double pli (nombre de plis) 3074 4655 4331 3908 5579 8807 Amélioration % référence - + 41 % + 27 % + 81 % +186 % Résistance à la déchirure (mN) 760 870 820 760 660 1380 Amélioration % - 13 % référence - 6 % - 13 % - 24 % + 59 % In order to evaluate wet strength, the burst strength according to ISO NF Q03-053 was measured on wet and dry leaves. The value of wet strength (WER) was then obtained according to the following formula: REH = Resistance to ' bursting ' wet state Resistance to ' bursting ' dry state × 100
Figure imgb0001
 <u> Table 1 </ u> Trial Comparative example Example 2 Example 3 Example 4 Porosity before creasing (cm 3 / min) 22 26 24 27 Porosity after creasing (cm 3 / min) 206 147 145 89 Improvement % reference - 28.7% - 29.7% - 56.84% Resistance in the wet state (%) 48.6 50.3 52 52.5 Double fold resistance (number of plies) 2620 3061 3304 4012 Improvement % reference + 16.8% + 26.1% + 53.1% Trial Comparative Example 5 Example 6 Example 7 Porosity before creasing (cm 3 / min) 131 101 117 Porosity after creasing (cm 3 / min) 1043 545 855 Improvement reference - 47.8% -18.1% Double fold resistance (number of plies) 666 1479 1248 Improvement reference +122.1% +87.4% Trial Comparative Example 8 Comparative Example 9 Example 10 Example 11 Example 12 Example 13 Porosity before creasing (cm 3 / min) 0 0 0 0 0 0 Porosity after creasing (cm 3 / min) 103 - 41 24 15 12 Improvement reference - 61.2% - 77% - 85% - 88% Resistance in the wet state (%) 54.5 - 57.7 60.0 61.2 63.9 Double fold resistance (number of plies) 3074 4655 4331 3908 5579 8807 Improvement % reference - + 41% + 27% + 81% +186% Tear resistance (mN) 760 870 820 760 660 1380 Improvement % - 13% reference - 6% - 13% - 24% + 59%

Série 1Series 1

Comme le montre le tableau 1 des résultats de la série 1, les feuilles de sécurité des exemples 2 à 4 présentent des porosités après froissement nettement améliorées par rapport à l'exemple comparatif 1 pris comme référence (diminution de la porosité après froissement comprise entre 28 et 56 %).As shown in Table 1 of the results of series 1, the safety sheets of Examples 2 to 4 have substantially improved after-creasing porosities compared to Comparative Example 1 taken as a reference (decrease in post-crease porosity between 28.degree. and 56%).

De la même façon, pour les feuilles formées selon le procédé de l'invention, la résistance au double pli est fortement augmentée par rapport à la feuille de l'exemple comparatif 1 (augmentation comprise entre 16 et 53 %).In the same way, for the sheets formed according to the process of the invention, the double fold resistance is greatly increased compared to the sheet of Comparative Example 1 (increase between 16 and 53%).

Enfin, on note que les feuilles des exemples 2 à 4 formées selon le procédé de l'invention présentent des valeurs de résistance à l'état humide très proches et même légèrement supérieures à celle de l'exemple comparatif 1, ce qui montre que l'agent de floculation utilisé (la résine PAAE) conserve son rôle d'agent de résistance à l'état humide.Finally, it is noted that the sheets of Examples 2 to 4 formed according to the process of the invention have very similar wet strength values and even slightly higher than that of Comparative Example 1, which shows that the flocculating agent used (the PAAE resin) retains its role of wet strength agent.

Série 2Series 2

Comme le montre le tableau 2 des résultats de la série 2, les feuilles selon les exemples 6 et 7 formées selon le procédé de l'invention présentent des porosités après froissement nettement améliorées par rapport à l'exemple comparatif 5 pris comme référence (diminution entre 17 et 48 % de la porosité après froissement).As shown in Table 2 of the results of series 2, the sheets according to Examples 6 and 7 formed according to the process of the invention have substantially improved after-creasing porosities compared with Comparative Example 5 taken as a reference (decrease between 17 and 48% of the porosity after creasing).

De la même façon, pour les feuilles formées selon le procédé de l'invention, la résistance au double pli est fortement augmentée par rapport à la feuille de l'exemple comparatif 5 pris comme référence (augmentation comprise entre 87 et 122 %).Similarly, for the sheets formed according to the process of the invention, the double fold resistance is greatly increased compared to the sheet of Comparative Example 5 taken as a reference (increase between 87 and 122%).

Série 3Series 3

Comme le montre le tableau 3 récapitulatif des résultats de la série 3, les feuilles de sécurité des exemples comparatifs 8 et 9 et des différents exemples 10 à 13 présentent des porosités avant froissement nulles, contrairement aux feuilles des séries 1 et 2. Ceci s'explique par la présence d'une couche de surfaçage qui « bouche » les pores à la surface des feuilles.As shown in Table 3 summarizing the results of series 3, the safety sheets of Comparative Examples 8 and 9 and the various Examples 10 to 13 have zero crease before porosity, unlike the sheets of series 1 and 2. This is explains by the presence of a surfacing layer that "clogs" the pores on the surface of the leaves.

Après froissement, toutes les feuilles des exemples présentent une porosité inférieure à celle de l'exemple comparatif 8. Le taux d'amélioration par rapport à l'exemple comparatif 8 pris comme référence varie entre 77 % et 88 %. La porosité après froissement des feuilles formées selon le procédé de l'invention est très proche de la porosité avant froissement de l'exemple comparatif 8.After crumpling, all the sheets of the examples have a porosity lower than that of Comparative Example 8. The improvement rate compared with Comparative Example 8 taken as a reference varies between 77% and 88%. The porosity after creasing of the sheets formed according to the process of the invention is very close to the porosity before creasing of Comparative Example 8.

Concernant la résistance au double pli, les feuilles formées selon le procédé de l'invention des exemples 10 à 13 présentent une amélioration, par rapport à la feuille dépourvue de polymère anionique de l'exemple comparatif 8 pris comme référence, comprise entre 27 % et 186 %.With regard to the double-fold resistance, the sheets formed according to the process of the invention of Examples 10 to 13 show an improvement, relative to the sheet free of anionic polymer of Comparative Example 8 taken as a reference, of between 27% and 186%.

Concernant la résistance à la déchirure, on a effectué une comparaison entre les exemples 10 à 13 et l'exemple comparatif 9 pour pouvoir apprécier la synergie entre la présence de fibres synthétiques et d'un polymère anionique.Concerning the tear resistance, a comparison was made between Examples 10 to 13 and Comparative Example 9 in order to be able to appreciate the synergy between the presence of synthetic fibers and an anionic polymer.

En effet, la feuille de l'exemple comparatif 9 ne comprend pas de polymère anionique mais comprend des fibres polyamide en une proportion de 15 %. La résistance à la déchirure de la feuille de l'exemple comparatif 8 est de 13 % inférieure à celle de la feuille de l'exemple comparatif 2, ce qui confirme l'effet des fibres synthétiques.Indeed, the sheet of Comparative Example 9 does not include anionic polymer but comprises polyamide fibers in a proportion of 15%. The tear strength of the sheet of Comparative Example 8 is 13% lower than that of the sheet of Comparative Example 2, which confirms the effect of the synthetic fibers.

Les exemples 10 à 12 présentent des valeurs de résistance à la déchirure inférieures ou égales à celles de l'exemple comparatif 8 et inférieures à celles de l'exemple comparatif 9, c'est à dire que la présence d'un polymère anionique seul n'a pas d'influence bénéfique sur la résistance à la déchirure.Examples 10 to 12 show tearing values lower than or equal to those of Comparative Example 8 and lower than those of Comparative Example 9, ie the presence of an anionic polymer alone. has no beneficial influence on the tear strength.

L'exemple 13 présente, lui, une valeur de résistance à la déchirure supérieure à celle de l'exemple comparatif 8 mais également nettement supérieure (+ 59 %) à celle de l'exemple comparatif 9. Il en ressort que la combinaison de la présence de fibres synthétiques et d'un polymère anionique dans la composition de la feuille de sécurité présente un effet synergique sur la résistance à la déchirure de ladite feuille.Example 13 has a higher tear strength value than that of Comparative Example 8, but is also significantly higher (+ 59%) than that of Comparative Example 9. It follows that the combination of presence of synthetic fibers and anionic polymer in the composition of the security sheet has a synergistic effect on the tear strength of said sheet.

Enfin, on note que les feuilles des exemples 10 à 13 formées selon le procédé de l'invention présentent des valeurs de résistance à l'état humide très proches et même légèrement supérieures à celle de l'exemple comparatif 8, ce qui montre que l'agent de floculation utilisé (la résine PAAE) conserve son rôle d'agent de résistance à l'état humide.Finally, it is noted that the sheets of Examples 10 to 13 formed according to the process of the invention have wet strength values very close to and even slightly higher than that of Comparative Example 8, which shows that The flocculating agent used (the PAAE resin) retains its role as a wet strength agent.

Claims (16)

  1. A method of manufacturing a crumple-resistant security sheet, comprising the steps consisting in forming said sheet by a wet-process technique from an aqueous suspension comprising
    • fibers comprising cellulose fibers and/or synthetic fibers,
    • a stabilized aqueous dispersion of an anionic polymer in a proportion lying in the range 5 to 45% by dry weight relative to the total dry weight of the fibers, and presenting a glass transition temperature greater than -40°C,
    • a cationic flocculation agent in a quantity lying in the range 1 to 5% by dry weight relative to the total dry weight of the fibers;
    and then wringing and drying said sheet.
  2. A manufacturing method according to claim 1, characterized by the fact that said sheet further comprises a secondary cationic flocculation agent in a quantity lying in the range 0.001 to 0.006% by dry weight relative to the total dry weight of the fibers.
  3. A manufacturing method according to any preceding claims, characterized by the fact that said anionic polymer presents a glass transition temperature lying in the range -30°C to 10°C.
  4. A manufacturing method according to any preceding claims, characterized by the fact that said cellulose fibers are cotton fibers.
  5. A manufacturing method according to any preceding claims, characterized by the fact that said synthetic fibers are chosen from polyamide fibers and/or polyester fibers.
  6. A manufacturing method according to any preceding claims, characterized by the fact that said anionic polymer comprises a polymer presenting carboxyl functions.
  7. A manufacturing method according to any one of claims 5 to 6, characterized by the fact that said sheet presents tear strength greater than 1300 mN.
  8. A manufacturing method according to the preceding claim, characterized by the fact that said anionic polymer comprises a carboxylated styrene butadiene copolymer.
  9. A manufacturing method according to any preceding claims, characterized by the fact that said main cationic flocculation agent is a cationic resin.
  10. A manufacturing method according to the preceding claim, characterized by the fact that said cationic resin is a polyamide-amine-epichlorohydrin resin.
  11. A manufacturing method according to any one of claims 1 to 10, characterized by the fact that said main cationic flocculation agent is chosen from polyacrylamides, polyethyleneimines, polyvinylamines, and mixtures thereof.
  12. A manufacturing method according to any one of claims 2 to 11, characterized by the fact that said secondary cationic flocculation agent is chosen from polyacrylamides, polyethyleneimines, polyvinylamines, and mixtures thereof.
  13. A manufacturing method according to any preceding claims, characterized by the fact that said sheet includes at least one security element.
  14. A manufacturing method according to any preceding claims, characterized by the fact that said sheet further comprises an outer coating layer.
  15. A manufacturing method according to any preceding claims, characterized by the fact that a coating layer is applied to at least one face of said security sheet.
  16. A security document, in particular a banknote, characterized by the fact that it includes a security sheet obtained using the method as defined according to any preceding claims.
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KR101496371B1 (en) 2015-02-26
SI2148954T2 (en) 2017-06-30
CN101711297B (en) 2012-07-04
ES2339419T3 (en) 2014-01-28
ES2339419T1 (en) 2010-05-20
TW200916633A (en) 2009-04-16
US20100078930A1 (en) 2010-04-01
BRPI0812055A2 (en) 2014-11-18
SI2148954T1 (en) 2014-01-31
PL2148954T5 (en) 2017-10-31
FR2916768B1 (en) 2009-07-24
WO2008152299A2 (en) 2008-12-18
RU2485237C2 (en) 2013-06-20
FR2916768A1 (en) 2008-12-05
CN101711297A (en) 2010-05-19
BRPI0812055B1 (en) 2019-06-25
WO2008152299A3 (en) 2009-03-12
CA2688172A1 (en) 2008-12-18
ES2339419T5 (en) 2017-07-17
EP2148954A2 (en) 2010-02-03
EP2148954B1 (en) 2013-10-23
AR066775A1 (en) 2009-09-09
US10023998B2 (en) 2018-07-17
RU2009143616A (en) 2011-07-10
KR20100019463A (en) 2010-02-18
DE08805868T1 (en) 2010-09-09
PL2148954T3 (en) 2014-04-30
UA96190C2 (en) 2011-10-10

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