EP4010529A1 - Papier de sécurité - Google Patents
Papier de sécuritéInfo
- Publication number
- EP4010529A1 EP4010529A1 EP20751497.7A EP20751497A EP4010529A1 EP 4010529 A1 EP4010529 A1 EP 4010529A1 EP 20751497 A EP20751497 A EP 20751497A EP 4010529 A1 EP4010529 A1 EP 4010529A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibrous substrate
- substrate according
- dry weight
- fibers
- anionic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 31
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- 125000000129 anionic group Chemical group 0.000 claims description 11
- 229940099451 3-iodo-2-propynylbutylcarbamate Drugs 0.000 claims description 10
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 claims description 10
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- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 claims 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000905 isomalt Substances 0.000 description 1
- 235000010439 isomalt Nutrition 0.000 description 1
- HPIGCVXMBGOWTF-UHFFFAOYSA-N isomaltol Natural products CC(=O)C=1OC=CC=1O HPIGCVXMBGOWTF-UHFFFAOYSA-N 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
- CSSYQJWUGATIHM-IKGCZBKSSA-N l-phenylalanyl-l-lysyl-l-cysteinyl-l-arginyl-l-arginyl-l-tryptophyl-l-glutaminyl-l-tryptophyl-l-arginyl-l-methionyl-l-lysyl-l-lysyl-l-leucylglycyl-l-alanyl-l-prolyl-l-seryl-l-isoleucyl-l-threonyl-l-cysteinyl-l-valyl-l-arginyl-l-arginyl-l-alanyl-l-phenylal Chemical compound C([C@H](N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CS)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CS)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)C1=CC=CC=C1 CSSYQJWUGATIHM-IKGCZBKSSA-N 0.000 description 1
- 229940078795 lactoferrin Drugs 0.000 description 1
- 235000021242 lactoferrin Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229960001375 lactose Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- JQAACYUZYRBHGG-QHTZZOMLSA-L magnesium;(2s)-5-oxopyrrolidine-2-carboxylate Chemical compound [Mg+2].[O-]C(=O)[C@@H]1CCC(=O)N1.[O-]C(=O)[C@@H]1CCC(=O)N1 JQAACYUZYRBHGG-QHTZZOMLSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
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- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- CGIHFIDULQUVJG-VNTMZGSJSA-N phytantriol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCC[C@@](C)(O)[C@H](O)CO CGIHFIDULQUVJG-VNTMZGSJSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 239000001259 polydextrose Substances 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- CRPCXAMJWCDHFM-UHFFFAOYSA-M sodium;5-oxopyrrolidine-2-carboxylate Chemical compound [Na+].[O-]C(=O)C1CCC(=O)N1 CRPCXAMJWCDHFM-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 241001529453 unidentified herpesvirus Species 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
- 241001430294 unidentified retrovirus Species 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229940051021 yellow-fever virus Drugs 0.000 description 1
- OWVLYQRCCIEOPF-QHTZZOMLSA-L zinc;(2s)-5-oxopyrrolidine-2-carboxylate Chemical compound [Zn+2].[O-]C(=O)[C@@H]1CCC(=O)N1.[O-]C(=O)[C@@H]1CCC(=O)N1 OWVLYQRCCIEOPF-QHTZZOMLSA-L 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
- D21H21/18—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
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Definitions
- the present invention relates to the field of paper and more particularly that of banknotes. More specifically, it aims to provide a paper substrate endowed with sufficient mechanical strength to prevent banknotes, made from this substrate, from undergoing an excessive microbial load during their aging in circulation.
- banknotes are very deteriorated and very dirty.
- the analysis of various denominations of used banknotes, known as "at the end of their life” makes it possible to highlight a phenomenon of physicochemical modification of banknotes in high circulation and intense mechanical degradation.
- banknotes are soft because they lack their original characteristic stiffness. Numerous tears completely through in the thickness are present and we also observe numerous initiation of peripheral tears on the edges of the banknotes.
- the paper is completely unstructured. It has numerous perforation points on the fatigue areas of the substrate subjected to repeated crumpling and folding. The internal structure of the note is severely dislocated; the fibers are untied and the result is an increase in the porosity of the sheet such that the thickness of the most degraded banknotes is almost doubled compared to the thickness original. The surface treatments or coatings disappear or fragment increasing the apparent porosity of the ticket surface.
- banknotes which are generally about 110 ⁇ m thick, quickly gain more than 30 ⁇ m in thickness and their porosity can exceed 200 ml / min.
- these biocides allow effective protection of substrates against the development of germs, in particular the main families of bacteria and microscopic fungi, and also prevent the risk of cross-contamination by pathogenic germs (bacteria, molds and viruses), in particular during the exchange of tickets from hand to hand. This type of protection is effective on cuts throughout their circulation.
- the invention therefore aims to provide a substrate which addresses the problem of substrate destructuring during heavy traffic and the associated undesirable effects described above.
- the present invention also aims to provide a fibrous substrate whose low level of porosity is not significantly altered after crumpling. It also aims to provide a fibrous substrate whose internal cohesion is significantly improved to greatly prevent the opening of the sheet which derives therefrom during its circulation.
- the present invention further aims to provide a fibrous substrate provided with an anti-fouling surface protection but also more at heart, improved.
- the present invention also aims to ensure sustainability of the antimicrobial efficacy existing on banknotes. It aims in particular to significantly limit the level of uptake of microbial microscopic soiling.
- the present invention relates to a fibrous substrate obtained by the wet process, resistant to creasing and to soiling and comprising by mass at least 40% to 96% by dry weight of fibers, in particular cellulosic, relative to on the dry weight of said substrate, from 1% to 20% by dry weight relative to the dry weight of fibers, of at least one anionic polymer having a glass transition temperature greater than - 40 ° C, in particular carboxylated, of 0, 5% to 5% by dry weight of at least one cationic precipitating agent, relative to the dry weight of fibers, and from 0.001% to 1% by dry weight of at least one biocidal agent, and preferably 0.001% at 0.2% by dry weight of at least one biocidal agent, said anionic polymer being present in a precipitated form on the surface of said fibers.
- a fibrous substrate as defined above combines a strongly reinforced resistance to destructuring with an effective biocidal chemical protection made durable, including under
- the substrate according to the invention has a porosity after wrinkling which is at most equal to 50 ml / min, assessed according to the ISO 5636-3 standard.
- the substrate according to the invention has a Scott Bond internal cohesion, assessed according to the Tappi 569 om-09 standard or according to the ISO 16260 standard, greater than 1000 J / m 2 , in particular greater than 1300 J / m 2 , or even greater than 1500. J / m 2 .
- the anionic polymer is chosen from carboxylated styrene-butadiene copolymers.
- the fibrous substrate according to the invention is a cellulosic fibrous substrate, manufactured by the wet route, in particular by the papermaking route and, as stated above, it further comprises an anionic polymer in the precipitate state and at least one biocidal agent.
- the fibrous substrate according to the invention comprises from 1% to 20% by dry weight, preferably from 1% to 10% by dry weight, and more preferably from 3% to 8% by dry weight of anionic polymer (s) ), relative to the dry weight of fibers.
- This or these anionic polymer (s) is (are) present in the substrate according to the invention in a form precipitated at the surface of the fibers.
- precipitated form is meant that the anionic polymer is present in the form of a plurality of solid microdeposits, more exactly in the form of polymer particles distributed on the surface of the fibers constituting the fibrous substrate according to the invention.
- the distribution of the polymer particles on the fibers must be as homogeneous as possible.
- the anionic polymer suitable for the invention can be a homopolymer or a co-polymer.
- an anionic polymer is a polymer carrying negative charges. It can be derived from the anionic functionalization of so-called neutral polymers because they are uncharged.
- Anionic polymers suitable for the invention have a glass transition temperature above -40 ° C.
- glass transition temperature is understood to mean the temperature below which the polymer is rigid. As the temperature increases, the polymer goes through a transition state which allows the macromolecular chains to slide relative to each other and the polymer softens.
- the anionic polymer present in the security sheet is a polymer having carboxyl functions.
- a polymer is obtained by homo-polymerization of at least one monomer or co-polymerization of at least two monomers chosen from acrylic acid, methacrylic acid, acrylonitrile, acrylate. alkyl, alkyl methacrylate, acrylamide, methacrylamide, N-methylol acrylamide, styrene and butadiene.
- the anionic polymer is chosen from acrylic homo- and co-polymers, acrylate homo- and co-polymers, carboxylated styrene-butadiene copolymers and mixtures thereof.
- acrylic copolymers the following may be mentioned in particular:
- said polymer is a carboxylated styrene -butadiene copolymer.
- Such copolymers are available, for example, from The Dow Chemical Company with various glass transition temperatures.
- the anionic polymer is a carboxylated styrene-butadiene copolymer, and preferably has a glass transition temperature ranging from -30 ° C to -20 ° C, in particular from -27 ° C to -23 ° C, and more preferably of the order of -25 ° C.
- this anionic polymer can also be non-carboxylated.
- anionic polymers Mention may be made, as representative of these other forms of anionic polymers, of the anionic forms of polyacrylamides and of polystyrene co-polymers, such as in particular styrene-butadiene copolymers.
- the anionic polymer has a Tg greater than 23 ° C.
- the polymer (s) having a glass transition temperature greater than 23 ° C are chosen from polyacrylics, polyacrylates, polyacrylamides, anionic forms of polystyrenes, polyvinyls, polyethylenes, polyurethanes, and their mixtures.
- the polymer (s) exhibiting a glass transition temperature greater than 23 ° C. are chosen from acrylic polymers (or polyacrylics), that is to say homopolymers or copolymers comprising at least one acrylic monomer, namely acrylic homopolymers or acrylic copolymers.
- acrylic copolymers there may be mentioned in particular:
- the polymer (s) exhibiting a glass transition temperature of greater than 23 ° C. are chosen from acrylic homopolymers.
- Such polymers are available in anionic dispersion, for example:
- the anionic polymer (s) can be non-crosslinkable, crosslinkable using an external crosslinker or even self-crosslinkable.
- the anionic polymer (s) are self-crosslinkable.
- the drying step can lead to crosslinking of the polymers, in a step subsequent to the implementation of the method according to the invention.
- anionic polyurethane mention may in particular be made of the anionic forms of polyurethane-polyesters, polyurethane -polyethers and polyurethane -polycarbonates, and their mixtures.
- said anionic polyurethane is a polyurethane-polyester.
- Impranil DLC Edrelity at break
- Tg - 34 ° C
- said anionic polyurethane is not crosslinkable.
- Cationic precipitation agent A fibrous substrate according to the invention further comprises an effective amount of at least one cationic precipitating agent.
- This cationic precipitating agent by modifying the electrostatic charge of the anionic cellulose fibers, allows, among other things, the attachment of the anionic polymer particles to the fibers.
- the term “effective amount” is understood to mean the amount of cationic precipitating agent required to allow almost all, preferably all, of the anionic polymer to be precipitated from the surface of the fibers.
- This amount of cationic precipitating agent is to be considered with regard to the chemical nature of the associated polymer, in particular its ionicity, and can therefore vary.
- the cationic precipitating agent is selected from polyaluminum chlorides, water-soluble cationic polymers, in particular from cationic starches, polyamides, polyacrylamides, polyethyleneimines, polyvinylamines and mixtures thereof.
- the cationic precipitating agent comprises at least one cationic resin.
- the cationic precipitating agent is chosen from polyamide resins, in particular from polyamide -polyamine-epichlorohydrin resins, known as PAAE resins.
- the fibrous substrate comprises two cationic precipitating agents.
- the fibrous substrate comprises as cationic precipitating agent at least one polyamide -polyamine-epichlorohydrin resin and optionally at least one cationic polyacrylamide.
- the fibrous substrate according to the invention advantageously comprises from 0.5% to 5% by dry weight, in particular from 0.8% to 3.5% by dry weight of cationic precipitation agent (s), for example relative to the dry weight of fibers.
- the fibrous substrate according to the invention comprises fibers. These fibers can be natural, artificial and / or synthetic. According to one embodiment of the invention, the fibers forming part of the composition of the sheet comprise natural fibers.
- cellulosic fibers such as wood fibers, for example hardwood fibers, softwood fibers or their mixture, cotton fibers, bamboo, straw, abaca, 'asperto, hemp, jute, flax, sisal and their mixtures.
- the fibers can be bleached, semi-bleached or unbleached.
- the fibers entering into the composition of the substrate comprise cellulosic fibers, in particular cotton fibers.
- Cotton fibers notably improve the mechanical strength of the substrate, in particular the burst strength and tear resistance.
- the fibrous substrate according to the invention comprises from 40% to 96% by dry weight, preferably from 60% to 96% by dry weight, more preferably from 70% to 96% by dry weight of fibers, in particular cellulosic, relative to the total dry weight of the fibrous substrate.
- the fibrous substrate according to the invention comprises at least 70% by dry weight of cellulosic fibers, relative to the dry weight of fibers.
- said cellulosic fibers are wood fibers.
- said cellulosic fibers are cotton fibers.
- said cellulosic fibers are a mixture of cotton fibers and wood fibers.
- the cotton fibers represent at least 50% by dry weight, relative to the dry weight of fibers, the rest of the fibers being so-called short wood fibers, based on hardwoods.
- the fibers forming part of the composition of the substrate can comprise synthetic fibers.
- the presence of synthetic fibers, mixed with cellulosic fibers, in the substrate according to the invention improves the tear resistance properties of said substrate.
- the fibers, in particular cotton fibers, considered as starting material may be in a previously anionized form, or their negative charge is previously increased in absolute value, by polymers capable of increasing.
- the negative surface charge of fibers such as anionic polymers soluble in water and having an affinity with wood fibers.
- anionic polymers can be chosen from cellulose derivatives such as carboxymethylcellulose (CMC).
- the fibrous substrate according to the invention is free from glass fibers.
- the substrate is a banknote substrate.
- biocide covers any agent effective for regulating and / or inhibiting the growth of microorganisms such as viruses, fungi and bacteria.
- biocide according to the invention can be chosen from bacteriostatic, bactericidal, fungistatic, fungicidal, virucidal agents and mixtures thereof.
- a fibrous substrate according to the invention is impregnated on the surface and / or in depth with at least one biocide.
- the biocide according to the invention is a mixture of at least two biocidal agents, one being a bacteriostatic and / or bactericidal agent and the other a fungistatic and / or fungicidal agent.
- the fibrous substrate according to the invention contains at least one bacteriostatic and / or bactericidal agent chosen from compounds based on chitosan or derivatives of chitin, based on quaternary ammonium, on zinc zeolite, on ions. silver and triclosan and mixtures thereof.
- the fibrous substrate according to the invention contains at least one bacteriostatic and / or bactericidal agent based on didecyl dimethyl ammonium chloride.
- the fibrous substrate comprises at least didecyl dimethyl ammonium chloride or silver chloride, preferably at least silver chloride, as a biocidal agent.
- silver chloride exhibits, together with its bacteriostatic and / or bactericidal activity, a virucidal activity and therefore particularly advantageous given the objective pursued by the present invention. invention.
- the fibrous substrate according to the invention contains at least one fungistatic and / or fungicidal agent chosen from compounds based on isothiazoline or derivatives. isothiazolone, chitosan or derivatives of chitin, quaternary ammonium, zinc zeolite, silver ions and triclosan.
- the fibrous substrate according to the invention contains at least one fungistatic agent and / or fungicide based on p - [(Diiodomethyl) sulfonyl] toluol in the form of an aqueous dispersion.
- the fibrous substrate according to the invention contains at least one fungistatic agent and / or fungicide based on iodopropynyl butylcarbamate in the form of an aqueous dispersion.
- the fibrous substrate according to the invention contains at least one fungistatic agent and / or fungicide based on methyl-1H-benzimidazol-2-ylcarbamate in the form of an aqueous dispersion.
- the fibrous substrate according to the invention contains at least one virucide, in particular of natural origin.
- viral denotes any compound having the capacity to kill or inhibit viruses.
- the virucide according to the present invention is more particularly dedicated to killing and / or inhibiting a pathogenic virus with regard to mammals and more particularly to humans.
- Such viruses can be naked viruses or enveloped viruses.
- retroviruses By way of representative of the pathogenic viruses for humans which may be considered according to the invention, mention may more particularly be made of retroviruses, cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackie viruses, the virus of encephalomyocarditis, picomaviruses including rhinoviruses, DNA or RNA viruses in particular flaviviridae, AIDS virus, influenza viruses, smallpox virus, yellow fever virus, hepatitis C, herpes viruses, Epstein-Barr virus, varicella-zoster virus, rubella virus, simian virus 40 or SV40, or even coronaviruses.
- retroviruses cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackie viruses
- virucide of natural origin is intended to denote any virucide pre-existing in nature or which can be synthesized from natural compounds existing in nature.
- the virucides of natural origin which can be used in the context of the present invention can thus be obtained either by extraction and purification from a natural medium containing them, or by synthesis from natural compounds.
- virucides mention may in particular be made of monolaurin which can be obtained by synthesis from glycerol and lauric acid.
- monolaurin is intended to denote both the naturally preexisting monolaurin and that obtained by synthesis from glycerol and lauric acid.
- the virucide of natural origin can in particular be chosen from monolaurin, lactoferrin and essential oils exhibiting antiviral activity, such as, for example, essential oil of laurel.
- the fibrous substrate in accordance with the invention may contain an effective amount of at least one virucide of natural origin, that is to say a sufficient amount thereof to provide the information medium incorporating it with properties. antivirals.
- the fibrous substrate in accordance with the invention may contain from 0.1 to 2.0% by dry weight, for example from 0.5 to 1.5% by dry weight, of virucide of natural origin relative to to its total weight.
- the biocide is at least monolaurin.
- the fibrous substrate comprises at least one pair of biocidal agents containing at least one 3-iodo-2-propynylbutyl carbamate, preferably in combination with at least didecyl dimethyl ammonium chloride or silver chloride, and more preferably in combination with at least silver chloride.
- the fibrous substrate comprises at least one 3-iodo-2-propynylbutyl carbamate and silver chloride.
- Such a couple is particularly advantageous because of its activity which is both bacteriostatic, bactericidal, fungistatic, fungicidal, yeasticidal and virucidal.
- the substrate according to the invention can be loaded in different ways with biocidal agent (s).
- these agents can be directly conveyed within the fibrous substrate, in particular by being incorporated in bulk or by impregnation.
- They can also be present at a surfacing and / or coating layer deposited on at least one of the faces of the substrate.
- they can be present at least at an ink printed on one side of the substrate.
- they may be present at least at the level of a varnish, for example an overprint varnish, deposited on at least one of the faces of the substrate.
- a varnish for example an overprint varnish
- a fibrous substrate may contain, as biocides, at least one virucide of natural origin and at least one bacteriostatic and / or bactericidal agent and / or at least one fungistatic and / or fungicidal agent.
- the biocide When the biocide is monolaurin, it can be synthesized in situ in the medium dedicated to promoting the immobilization of the biocide at the level of the substrate, during its preparation process.
- Monolaurin is generated by reacting lauric acid and glycerol in the presence of a catalyst, the catalyst preferably being a zeolite catalyst or a lipase.
- the fibrous substrate according to the invention can further comprise at least one humectant.
- a humectant is a compound capable of providing a hydration or even a hygro scopic effect.
- polyol type compounds such as, for example, glycerin, also called glycerol, propylene glycol, polyethylene glycol, butylene glycol, glyceryl triacetate, or sorbitol.
- the humectant considered is glycerol.
- the humectant considered is chosen from the following compounds:
- PCA - pidolic acid
- arginine PCA copper PCA, ethylhexyl PCA, lauryl PCA, magnesium PCA, sodium PCA, zinc PCA .
- fructose glucose, isomalt, lactose, maltitol, mannitol, polydextrose, sorbitol, sucrose or xylitol
- a fibrous substrate in accordance with the invention may contain from 0.5 to 4% by dry weight, for example from 1 to 3% by dry weight of humectant (s), and in particular of glycerol, relative to its total weight.
- humectant s
- glycerol glycerol
- the fibrous substrate according to the invention can also comprise at least one filler, in particular mineral.
- these fillers are intended in particular to increase the opacity, the whiteness and / or the printability of said fibrous substrate.
- the filler can be chosen from mineral fillers, in particular calcium carbonate, kaolin, titanium dioxide, talc, silicas, hydrated aluminas, aluminum silicates and their mixtures, and / or from organic fillers. , in particular plastic fillers or pigments.
- a fibrous substrate according to the invention may comprise from 2% to 25% by dry weight, preferably from 5% to 15% by dry weight of filler (s), relative to the dry weight of fibers.
- the fibrous substrate comprises at least by mass: from 40% to 96% by dry weight of fibers, in particular cellulosic, relative to the dry weight of said substrate, from 1% to 20% by dry weight relative to on the dry weight of fibers, of at least one carboxylated styrene butadiene copolymer, preferably having a glass transition temperature ranging from -30 ° C to -20 ° C, and more preferably of the order of -25 ° C, from 0.5% to 5% by dry weight of at least one cationic precipitating agent, based on the dry weight of fibers, preferably a polyamide-polyamine-epichloridrine resin, and from 0.001% to 1% by dry weight d 'at least one biocidal agent comprising at least silver chloride, and preferably in combination with at least 3-iodo-2-propynylbutyl carbamate.
- the fibrous substrate comprises at least by mass: from 60% to 96%, or even from 70% to 96% by dry weight of fibers, in particular cellulosic, relative to the dry weight of said substrate, of 1 % to 10%, or even from 3% to 8% by dry weight relative to the dry weight of fibers, of at least one carboxylated styrene butadiene copolymer, preferably having a glass transition temperature ranging from -30 ° C to - 20 ° C, and more preferably of the order of -25 ° C, from 0.8% to 3.5% by dry weight of at least one cationic precipitating agent, relative to the dry weight of fibers, preferably a polyamide-polyamine-epichloridrine resin, and from 0.002% to 0.5% by dry weight of silver chloride, preferably in combination with from 0.01% to 0.6% by dry weight of 3-iodo carbamate -2-propynylbutyl.
- the invention also relates to a method of manufacturing a fibrous substrate according to the invention.
- this manufacturing process comprises at least the steps consisting in: a) having an aqueous suspension comprising fibers, in particular cellulosic fibers, as defined above and at least one filler, in particular mineral, as defined above. above, b) contacting said suspension with at least one colloidal dispersion of at least one anionic polymer as defined above and of at least one cationic precipitating agent as defined above under conditions effective to precipitate said polymer on the surface of said fibers, c) producing a fibrous substrate from said suspension, and d) draining, pressing and drying said substrate, obtained at the end of step c), said method further comprising at least one step consisting in contacting said substrate used in step d) obtained at the end of step d) or formed according to said method with at least one biocidal agent under conditions effective to immobilize an amount ef effectiveness of said biocide at said substrate.
- said fibrous substrate is immersed during step d) or at the end of step d) in a solution containing at least one
- a surface spraying of said fibrous substrate obtained at the end of step d) is carried out with a solution containing at least one biocide
- the said fibrous substrate obtained at the end of step d) is coated with a coating solution containing at least one biocide.
- At least one face of said substrate, obtained at the end of step d), is surfaced with a surfacing bath containing at least one biocide.
- said fibrous substrate obtained at the end of step d), and preferably having been consecutively coated and / or surfaced is printed using an ink containing at least one biocide.
- the process is applied to at least one face of said fibrous substrate obtained at the end of step d), and preferably having been consecutively coated and / or surfaced and printed, of an overprint varnish containing at least one biocide.
- these different modes of immobilization of the biocidal agent at the level of the substrate can, if necessary, be combined. However, these combinations must be compatible with the manifestation, at the substrate level, of the desired biocidal activity.
- said substrate is brought into contact with at least one pair of biocidal agents, in particular a pair of 3-iodo-2-propynylbutyl carbamate in combination with at least didecyl dimethyl ammonium chloride. or silver chloride, preferably silver chloride.
- This contacting is more particularly carried out in a single step.
- the substrate is impregnated simultaneously with the two biocides.
- the suspension used in step c) further comprises at least one charge retention agent and one bulk bonding agent.
- Said manufacturing process according to the invention is a wet process, in particular a papermaking process. It is for example implemented on a single-jet paper machine with a flat table or a round shape.
- said paper machine is a multi-jet paper machine comprising at least two sheet forming members, for example chosen from flat tables, round shapes and / or “shortformer” cylinders.
- Carrying out each of the steps of the method is not limited to a particular embodiment.
- the fibrous substrate can be produced in step c) by projection or suction of the suspension on a moving canvas.
- any other method of preparation known to those skilled in the art can be considered.
- the aqueous suspension of fibers and fillers, the colloidal dispersion of at least one anionic polymer and the cationic precipitating agent are advantageously introduced in bulk.
- the anionic polymer is precipitated from the surface of the fibers, in the presence of at least one cationic precipitating agent.
- This bringing together can be achieved by the simultaneous or sequential addition of the colloidal dispersion of at least one anionic polymer and at least one cationic precipitating agent.
- the cationic precipitating agent is added to the aqueous suspension first, then the dispersion of at least one anionic polymer is incorporated into the mixture in a second step.
- This embodiment which is particularly advantageous in combination with the use of cotton fibers, makes it possible to modify the electrostatic charge of the fibers in order to make them cationic and thus allow the fixing and precipitation of the anionic polymer particles on the fibers made cationic.
- the surfacing bath is applied by a size press to at least one of the faces of the fibrous substrate according to the invention.
- the manufacturing process according to the invention can comprise an additional step of coating or coating on one side, preferably on both sides, of the substrate.
- the coating or the coating can be done by a air knife system, curtain coating, by a pencil, blade or doctor blade, roller system, in particular pre-dosed, engraved or transfer.
- the present invention also relates to the use of a fibrous substrate according to the invention for preparing a banknote or a security sheet.
- the banknote according to the invention has the same properties as the fibrous substrate according to the invention and measured according to the characterization methods defined above for the fibrous substrate.
- the banknote according to the invention has a Scott Bond internal cohesion, assessed according to the Tappi 569 om-09 standard, greater than 1000 J / m 2 , in particular greater than 1300 J / m 2 , or even greater than 1500 J / m 2 .
- the substrate has a porosity after crumpling which is at most equal to 80 mL / min, preferably at most equal to 50 mL / min, appreciated according to standard ISO 5636-3. As shown by the exemplary embodiments detailed below, such porosity advantageously allows less contamination of the substrate after crumpling of the latter.
- the substrate according to the invention is a security sheet which incorporates at least one security element allowing the authentication of said sheet.
- said security element is chosen from visual devices, in particular optically variable devices, called OVDs, holograms, lenticular devices, elements with an interference effect, in particular iridescent elements, liquid crystals, pigments with an interference effect. magnetically orientable and multilayer interference structures.
- optically variable devices can be present on security threads integrated into the fibrous substrate or, on bands or patches affixed or printed on the fibrous substrate.
- said security element is chosen from so-called luminescent elements, revealable under UV or IR, these luminescent elements possibly in the form particles, fibrettes, planchettes, security thread integrated at least in part in the fibrous substrate, bands or patches affixed or printed on the fibrous substrate.
- said security element is chosen from automatically detectable elements, in particular optically or magnetically, these detectable elements commonly called markers or taggants being integrated in the fibrous substrate or in visual or luminescent security elements.
- a security sheet according to the invention can also include a radio frequency identification device, called RFID, also providing an identification and traceability function to the security sheet.
- RFID radio frequency identification device
- the present invention also relates to a security document comprising a security sheet according to the invention.
- the security document according to the invention is an official document, in particular an identity document, a passport, a residence permit or a visa.
- compositions are as follows:
- Base 1 100 dry parts of refined cellulosic fibers, 5 dry parts of titanium dioxide, 2.5 dry parts of PAAE polyamide -polyamine-epichlorohydrin resin.
- Base 2 95 dry parts of refined cellulosic fibers, 5 dry parts of titanium dioxide, 2.5 dry parts of PAAE resin and 5 dry parts of carboxylated styrene butadiene copolymer with a Tg of -25 ° C (Dow XZ 94755.04 latex now called LIGOS U 4056 and marketed by the company Trinseo).
- Each of the bases undergoes a size press treatment from among the following treatments:
- Treatment A without biocide:
- Treatment B (integrating a bacteriostatic agent and a fungicidal agent):
- the assimilable microbial load is defined as the number of Staphylococcus aureus bacteria present on the paper after inoculation by immersion of the inoculum for one minute, draining and then extraction.
- the inoculum used is a inoculum of Staphylococcus aureus ATCC 6538 at a concentration of 2.11.106 CFU / ml (Colony Forming Unit / ml).
- Bendtsen air permeability in cm 3 / min
- Bendtsen porosity are carried out according to the ISO 5636-3 standard.
- the measurements are carried out before and after 8 crumpling, carried out by a device of the IGT brand “NB S Crumbling Device”.
- a paper is produced from the base 2 to which a treatment B 'is applied.
- Treatment B ' corresponding to treatment B in which didecyl chloride dimethyl ammonium is replaced by silver chloride.
- the amounts of silver chloride and of 3-iodo-2-propynylbutyl carbamate in treatment B ' are determined so as to obtain, by dry weight relative to the fibrous substrate, 0.0036% of silver chloride and 0 , 15% of 3-iodo-2-propynylbutyl carbamate, ie a total of 0.1536% of biocide by dry weight relative to the fibrous substrate.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1909003A FR3099768B1 (fr) | 2019-08-06 | 2019-08-06 | Papier de sécurité |
PCT/EP2020/071444 WO2021023601A1 (fr) | 2019-08-06 | 2020-07-29 | Papier de sécurité |
Publications (3)
Publication Number | Publication Date |
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EP4010529A1 true EP4010529A1 (fr) | 2022-06-15 |
EP4010529C0 EP4010529C0 (fr) | 2024-03-27 |
EP4010529B1 EP4010529B1 (fr) | 2024-03-27 |
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Application Number | Title | Priority Date | Filing Date |
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EP20751497.7A Active EP4010529B1 (fr) | 2019-08-06 | 2020-07-29 | Papier de sécurité |
Country Status (4)
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EP (1) | EP4010529B1 (fr) |
BR (1) | BR112022002208A2 (fr) |
FR (1) | FR3099768B1 (fr) |
WO (1) | WO2021023601A1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102020006601A1 (de) | 2020-10-27 | 2022-04-28 | Giesecke+Devrient Currency Technology Gmbh | Banknote mit antiviralem Schutzlack, Verfahren zur Herstellung einer Banknote mit antiviralem Schutzlack und Verwendung einer Banknote mit antiviralem Schutzlack als antiviralen Gegenstand |
CN113278107B (zh) * | 2021-05-11 | 2022-05-17 | 济宁南天农科化工有限公司 | 一种互穿网络型水性聚氨酯-聚丙烯酰胺箱板纸增强剂 |
FR3122806B1 (fr) * | 2021-05-17 | 2024-03-29 | Oberthur Fiduciaire Sas | Composition antivirale pour le traitement de surface d’un article |
WO2023213977A1 (fr) | 2022-05-06 | 2023-11-09 | Oberthur Fiduciaire Sas | Composition aqueuse antimicrobienne |
FR3135271A1 (fr) | 2022-05-06 | 2023-11-10 | Oberthur Fiduciaire Sas | Papier-peint à propriétés biocides |
DE102022133075A1 (de) | 2022-12-13 | 2024-06-13 | Giesecke+Devrient Currency Technology Gmbh | Sicherheitssubstrat, Sicherheitspapier und Herstellungsverfahren |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2838025B1 (fr) | 2002-04-08 | 2005-08-05 | Arjo Wiggins | Support d'information presentant des proprietes biocides et son procede de fabrication |
FR2916768B1 (fr) * | 2007-05-31 | 2009-07-24 | Arjowiggins Licensing Soc Par | Feuille de securite resistante au froissement, son procede de fabrication et un document de securite la comprenant |
FR2945180B1 (fr) | 2009-05-07 | 2013-02-22 | Arjowiggins Security | Support d'information presentant des proprietes antivirales et son procede de fabrication |
FR2967074B1 (fr) | 2010-11-08 | 2013-06-28 | Arjowiggins Security | Compositions fluides aptes a former un revetement presentant des proprietes antivirales |
FR3061212A1 (fr) * | 2016-12-27 | 2018-06-29 | Arjowiggins Security | Substrat fibreux cellulosique resistant a la falsification par clivage. |
-
2019
- 2019-08-06 FR FR1909003A patent/FR3099768B1/fr active Active
-
2020
- 2020-07-29 EP EP20751497.7A patent/EP4010529B1/fr active Active
- 2020-07-29 WO PCT/EP2020/071444 patent/WO2021023601A1/fr active Application Filing
- 2020-07-29 BR BR112022002208A patent/BR112022002208A2/pt unknown
Also Published As
Publication number | Publication date |
---|---|
EP4010529C0 (fr) | 2024-03-27 |
EP4010529B1 (fr) | 2024-03-27 |
FR3099768A1 (fr) | 2021-02-12 |
BR112022002208A2 (pt) | 2022-06-07 |
WO2021023601A1 (fr) | 2021-02-11 |
FR3099768B1 (fr) | 2021-08-06 |
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