EP4359606A2 - Papier biocide, document de valeur biocide et procédé de fabrication correspondant - Google Patents

Papier biocide, document de valeur biocide et procédé de fabrication correspondant

Info

Publication number
EP4359606A2
EP4359606A2 EP22733853.0A EP22733853A EP4359606A2 EP 4359606 A2 EP4359606 A2 EP 4359606A2 EP 22733853 A EP22733853 A EP 22733853A EP 4359606 A2 EP4359606 A2 EP 4359606A2
Authority
EP
European Patent Office
Prior art keywords
paper
component
substrate material
coating
plastic film
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.)
Pending
Application number
EP22733853.0A
Other languages
German (de)
English (en)
Inventor
Michael Böhm
Andreas Gross
Rudolf Seidler
Bernhard Wiedner
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.)
Giesecke and Devrient Currency Technology GmbH
Original Assignee
Giesecke and Devrient Currency Technology GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Giesecke and Devrient Currency Technology GmbH filed Critical Giesecke and Devrient Currency Technology GmbH
Publication of EP4359606A2 publication Critical patent/EP4359606A2/fr
Pending legal-status Critical Current

Links

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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56—Rolls

Definitions

  • Biocidal paper biocidal document of value and method for its production paper.
  • viruses are also counted among the microorganisms, although viruses are not regarded as microorganisms by many experts due to the lack of an independent metabolism and the inability to reproduce independently. On the other hand, viruses have the ability to multiply within a suitable host cell and to control their replication. Accordingly, virology is also regarded as a subfield of microbiology.
  • Patent application WO 03/084326 A2 proposed treating paper with didecyldimethylammonium chloride and a fungicidal agent.
  • Didecyldimethylammonium chloride (DDAC) has bactericidal properties. The application of DDAC to paper or its incorporation into paper is difficult since compositions with DDAC tend to foam.
  • WO 2021/123118 A1 discloses the biocidal treatment of documents of value such as banknotes with 3-iodo-2-propynylbutyl carbamate (IPBC) and diiodomethyl-p-tolyl sulfone and silver phosphate glass.
  • IPBC 3-iodo-2-propynylbutyl carbamate
  • the object of the present invention is to avoid the disadvantages of the prior art and to show a way of providing paper with biocidal, ie bactericidal and/or fungicidal and/or virucidal, in particular virucidal, properties.
  • the substance or substances used for the biocidal finish should preferably be non-toxic, cannot be removed from the paper even if the paper is touched very frequently, and should give the paper a long-lasting biocidal, in particular virucidal, effect.
  • the biocidal effect should preferably be achieved with the smallest possible amounts of biocidally active substance.
  • the substances used should be compatible with the paper material and the materials used in the manufacture of the paper, such as sizing and/or coating compositions, and be capable of being applied to the paper or incorporated into the paper without any problems in terms of process technology.
  • the procedural suitability of a biocidal composition should preferably be able to be checked in advance.
  • security papers for the production of documents of value such as banknotes, for example, are often provided with coatings to protect against contamination or for the purpose of protection against forgery, or are made from polymer papers or hybrid papers.
  • the biocidally active substances are therefore advantageously suitable not only for the biocidal treatment of paper based on plant fibers, but also for the biocidal treatment of polymer papers and hybrid papers.
  • the biocidal effect should not be reduced, or at least not lost, if the paper is provided with one or more coatings, for example with a protective varnish.
  • a favorable cost/benefit ratio of the substance or substances imparting biocidal properties is also desirable.
  • Paper having a substrate material made of fibers or a film characterized in that it is equipped with a component (a) and optionally with a component (b), wherein component (a) contains a benzalkonium halide and component (b) contains at least one compound selected from the group consisting of didecyldimethylammonium halides, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone and thiabendazole.
  • component (b) contains at least one didecyldimethylammonium halide and ⁇ -cyclodextrin.
  • Paper according to embodiment 1 or 2 characterized in that, in addition to the substrate material, it has other components such as a dry strength agent or a wet strength agent and/or a surface size and/or one or more coatings.
  • - is a fiber paper which has a substrate material of vegetable fibers or of plastic fibers or of a mixture of vegetable fibers and plastic fibers, wherein component (a) is in the substrate material or in a coating on the substrate material, or
  • - is a hybrid paper comprising a substrate material of vegetable fibers or a mixture of vegetable fibers and plastic fibers bonded to a plastic film on one or both major surfaces, component (a) being present in the substrate material or in a coating the surface of the plastic film or substrate material, or covering the two major surfaces of a plastic film, where component (a) is in the substrate material or in a coating on the surface of the substrate material, or
  • Paper according to embodiment 4 characterized in that it also contains component (b), where component (b) is in the same part of the paper as component (a) or in a different part of the paper.
  • Paper according to embodiment 4 characterized in that it is a fiber paper which has a surface finish on at least one of its two main surfaces and at least one coating on the same or the other main surface, with component (a) in the surface sizing and optionally in the coating.
  • Paper according to embodiment 4 characterized in that it is a hybrid paper which is connected to a plastic film on at least one of its two main surfaces, the plastic film having a first coating and component (a) being located in the first coating .
  • Paper according to embodiment 8 characterized in that it also contains component (b), wherein component (b) is either in the first coating and/or in a second coating applied to the first coating.
  • Paper according to embodiment 4 characterized in that it is a polymer paper which also contains component (b), where component (b) is either in the same coating as component (a) and/or in a further coating.
  • the benzalkonium halide is benzalkonium chloride and/or benzalkonium bromide.
  • Security paper with at least one security feature characterized in that it is made from or with a paper according to one of embodiments 1 to 15.
  • Document of value such as a bank note or security document such as an identification document, characterized in that it has a security paper according to embodiment 16.
  • Method for providing a paper with biocidal, in particular virucidal properties having the following steps:
  • component (a) contains a benzalkonium halide and component (b) contains at least one compound selected from the group , which consists of didecyldimethylammonium halides, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone and thiabendazole, and
  • component (b) contains at least one didecyldimethylammonium halide and g-cyclodextrin.
  • the paper is a fiber paper that has a substrate material made of vegetable fibers or plastic fibers or a mixture of vegetable fibers and plastic fibers, and component (a) is added to the pulp during the manufacture of the substrate material or as part of a Surface glue applied to the substrate material or is introduced into the substrate material or is applied to the substrate material as part of a coating composition, or
  • the paper is a polymeric paper having a substrate material of plastic film, and component (a) is applied to the plastic film as part of a coating composition.
  • the paper is a hybrid paper which has a substrate material made from vegetable fibers or from a mixture of vegetable fibers and plastic fibers which is connected to a plastic film on one or both main surfaces or covering the two main surfaces of a plastic film, component (a)
  • the substrate material is only bonded to a plastic film on one of its main surfaces, is mixed with the pulp during manufacture of the substrate material, or is incorporated into the substrate material as part of a surface size, or as part of a coating composition on the main surface not bonded to the plastic film surface of the substrate material and is also applied as part of a coating composition to the surface of the plastic film,
  • the substrate material is connected to each of its two main surfaces with a plastic film, as part of a coating composition reduction is applied to the surfaces of the plastic films, and
  • the substrate material covers the two main surfaces of a plastic film, is mixed into the pulp during manufacture of the substrate material, or is incorporated into the substrate material as part of a surface size, or is applied to the main surfaces of the substrate material as part of a coating composition.
  • the paper is a fiber paper which has a surface size and at least one coating on at least one of its main surfaces, with component (a) being applied to the substrate material as part of the surface size or in the substrate material is introduced.
  • component (a) is applied as part of a surface size or a first coating composition to a major surface of the substrate material and/or as part of a first coating composition to a surface of the plastic film, and that further component (b) is applied, wherein component (b) is applied either as a component of the first coating composition and/or as a component of a second coating composition applied over the first coating or surface size.
  • Test method for assessing the foaming behavior of a composition containing a didecyldimethylammonium halide or a didecyldimethylammonium halide and g-cyclodextrin characterized in that
  • composition is filled into a cylindrical container
  • the volume is measured again immediately after the cessation of air injection and at a time t after the cessation of air injection
  • the foam-related increase in volume is calculated immediately after blowing in air and at time t.
  • compositions tested may of course each additionally contain one or more compounds selected from the group consisting of benzalkonium halides, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone and thiabendazole.
  • the paper, the security paper, the document of value, the method for furnishing a paper with biocidal properties, the use for the biocidal furnishing of paper and the test method for assessing the foaming behavior represent aspects of the same invention. Therefore, disclosure applies in connection with an aspect of the present invention likewise for the remaining aspects of the present invention.
  • the terms "a, an, one, one" are to be understood as meaning "at least one, one, one, one".
  • Halides are fluorides, chlorides, bromides and iodides. Chlorides and bromides, especially chlorides, are preferred.
  • Fiber paper within the meaning of the present invention is both fiber paper and polymer paper and hybrid paper.
  • fiber paper consists of fibres, preferably exclusively plant fibres.
  • Security papers i.e. papers for the production of security documents or documents of value such as identity papers or banknotes, are preferably made from cotton fibers.
  • fiber papers can also contain a certain proportion of plastic fibers or even consist entirely of plastic fibers. Examples of suitable plastics are polyethylene terephthalate, polypropylene and polyethylene.
  • Polymer papers consist of polymer materials, i. H. they are plastic films, for example made of polyethylene terephthalate, biaxially stretched polypropylene or polyethylene.
  • Hybrid papers are fiber papers that have a plastic film on one or both surfaces, as is also used for polymer papers, but also plastic films that have fiber paper on both surfaces.
  • Hybrid papers are therefore film/fiber substrate composites, in particular with the structure film/fiber substrate/foil, but film/fiber substrate and fiber substrate/foil/fiber substrate structures are also possible.
  • the plastic film can be glued (laminated) to the paper, for example, or a plastic can be extruded directly onto the paper.
  • Polymer papers are coated to make them opaque and printable.
  • the plastic foils of hybrid papers are also used for better printing provided with suitable coatings.
  • Fiber papers are usually sized. They are preferably equipped with a surface sizing agent, which serves, among other things, to improve printability.
  • biocide means bactericidal and/or fungicidal and/or virucidal.
  • fungicidal and/or virucidal In order to obtain a desired spectrum of activity, several substances can be combined with one another.
  • benzalkonium halides in particular benzalkonium chloride (BAC) and benzalkonium bromide, are used for the biocidal treatment of paper.
  • Benzalkonium halides are a mixture of alkyl benzyl dimethyl ammonium halides where the alkyl moiety consists of Cs to Cix groups.
  • Benzalkonium halides are known for their preservative and disinfecting effects. Benzalkonium chloride in particular is therefore used, inter alia, in pharmaceutical compositions.
  • benzalkonium halides have a combination of properties that make them outstandingly suitable for providing paper with biocides. Above all, they have a virucidal and bactericidal effect, but also fungicide, and are excellently compatible both with paper substrate materials and with compositions for finishing the paper, such as sizings, coating agents, coating colors, etc. Stability problems of the treated papers, such as discoloration or premature aging, do not occur. It is particularly advantageous that they can also be used without any problems for providing special papers with biocides, such as the security papers used to produce documents of value, since they have no negative effects on the security features present in such security papers.
  • Each benzalkonium halide may be used alone or in admixture with one or more other benzalkonium halides, or combined with one or more other compounds also having virucidal and/or bactericidal and/or fungicidal activity to further improve biocidal activity.
  • such compounds are didecyldimethylammonium halides (didecyldimethylammonium fluoride, didecyldimethylammonium chloride, didecyldimethylammonium bromide, didecyldimethylammonium iodide), in particular didecyldimethylammonium chloride and didecyldimethylammonium bromide, 3-iodo-2-propynylbutylcarbamate (IPBC), diiodomethyl-p-tolylsulfone and thiabendazole.
  • didecyldimethylammonium halides didecyldimethylammonium fluoride, didecyldimethylammonium chloride, didecyldimethylammonium bromide, didecyldimethylammonium bromide, 3-iodo-2-propynylbutylcarbamate (IPBC), di
  • Benzalkonium halides and didecyldimethylammonium halides are both bactericidal, virucidal and fungicidal, while 3-iodo-2-propynylbutylcarbamate, diiodo-methyl-p-tolyl sulfone and thiabendazole are bactericidal and fungicidal.
  • Benzalkonium halides are preferably used in encapsulated form to protect the sensitive compounds. Despite their encapsulation, they are biocidally effective.
  • the compounds customary for encapsulation purposes can be used as encapsulation materials. Polymethylurea, polysaccharides and polyacrylates are particularly suitable.
  • BAHal for benzalkonium halide
  • BAC for benzalkonium chloride
  • BABr for benzalkonium bromide
  • DDAHal didecyldimethylammonium halide
  • DDAC didecyldimethylammonium chloride
  • DDABr didecyldimethylammonium bromide
  • IPBC 3-iodo-
  • DDAHal didecyldimethylammonium halides
  • g-cyclodextrin sizings, varnishes, coating colors, adhesives and other compositions used in the manufacture of paper that contain both a DDAhal and g-cyclodextrin without procedural difficulties can be processed.
  • Spraying or printing on solutions or suspensions, such as inks that contain both a DDAHal and ⁇ -cyclodextrin is also easily possible from the processing point of view.
  • ⁇ -cyclodextrin can improve the virucidal effect of DDAHa1. According to the invention, it is therefore preferred to also use ⁇ -cyclodextrin in compositions in which a DDAHal is used.
  • g-Cyclodextrin and other lower cyclodextrins are known to form inclusion complexes with apolar organic compounds. Lower cyclodextrins are completely harmless to health, they are even used as a food additive. The foam-inhibiting effect of g-cyclodextrin was previously unknown.
  • a component (a) and preferably additionally a component (b) is used according to the invention for the biocidal finish of the paper.
  • Component (a) is a benzalkonium halide or a mixture of two or more benzalkonium halides
  • component (b) is a compound or a mixture of two or more compounds selected from the group consisting of didecyldimethylammonium halides (a didecyldimethylammonium halide or a mixture of two or more didecyldimethylammonium halides), 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone and thiabendazole.
  • Both component (a) and component (b) can thus consist of one or more compounds, whereby the compounds of components (a) and (b) can be used as a mixture in a single composition or used individually as components of several different compositions can become.
  • the individual compositions can contain the same or different mixtures of compounds of components (a) and (b), or component (a) can be mixed into one composition (or several compositions) while component (b) can be mixed into another composition (or several other compositions) to be mixed.
  • a paper can be provided with biocidal properties according to the invention, for example, by mixing component (a) or components (a) and (b) into the paper pulp during production of the paper substrate and thus becoming part of the fiber substrate material and/or one or more of the compositions used to finish the paper.
  • sizing liquors surface sizing
  • coating colors coatings
  • coatings coatings
  • any other composition that is used in the production of a specific paper even if the paper in question is not to be equipped with biocidal properties can be considered.
  • Corresponding compositions are one known to those skilled in the art of papermaking. As a rule, they do not require any modification in order to be able to serve as a carrier medium for components (a) and/or (b).
  • the impregnation with size(s) and the application of paints or other coating materials, for example based on acrylate or polyurethane-containing binders, can be carried out in a completely conventional manner. Significant changes in process parameters such as drying times and drying temperatures are not necessary.
  • components (a) and (b) can also be applied to the paper to be treated and/or incorporated into the paper to be treated as constituents of additional impregnating agents and/or coating agents, i.e. as constituents of one or more compositions, which are used exclusively for the biocidal treatment of the paper.
  • Aqueous solutions in particular are suitable for this purpose, but also solutions in any other solvents in which components (a) and (b) are soluble and which are compatible with the paper in question.
  • dispersions can also be used.
  • components (a) and (b) into the paper are in no way restricted and in principle all known application or incorporation methods can be used, such as impregnation, printing, spraying, spreading, etc. of the compositions containing components (a) and/or (b).
  • components (a) and (b) can be applied to or incorporated into paper as parts of the same or as parts of different compositions. Application or incorporation as constituents of different compositions is preferred. In the case of separate application or incorporation, the components (a) and (b) can be found in the same or in different areas of the paper in the finished paper, for example in a surface size and in a coating. It makes sense, but not mandatory to provide the biocidal active substances at least in the area close to the surface, ie in the area with which microorganisms first come into contact and which is touched by a user.
  • biocidal active ingredient in particular an active ingredient of component (b), in the last composition used in the course of the paper manufacturing process or finishing process, in order to ensure that the replication or growth of viruses, bacteria and fungi that come into contact with the paper is efficiently inhibited.
  • biocidal active ingredient in particular an active ingredient of component (b)
  • component (b) in the last composition used in the course of the paper manufacturing process or finishing process, in order to ensure that the replication or growth of viruses, bacteria and fungi that come into contact with the paper is efficiently inhibited.
  • component (a) and, if appropriate, component (b) as constituents of a surface sizing liquor and to also carry out the biocidal treatment of the paper at the same time as it is surface sized.
  • Surface sizing liquors as carrier media for the biocide combination according to the invention have the advantage that on the one hand they penetrate the paper substrate to a certain extent and thus transport the biocide components into the paper substrate, and on the other hand they form a layer on the paper substrate so that the biocidal components are also located on the surface of the paper substrate and thus relatively close to the viruses, bacteria and fungi contacting the paper.
  • surface sizes are used in relatively large amounts compared to other paper treatment and finishing agents, so that relatively large amounts of biocidal components can also be introduced into the paper substrate and applied to the paper substrate.
  • This protective top layer ten are mostly UV-crosslinking paints with binders based on acrylate and/or polyurethane (100% systems).
  • the printable coatings are mostly produced from aqueous dispersions based on acrylate and/or polyurethane, where the dispersing agent is preferably removed by air drying. The same applies to hybrid papers, which only have a plastic film on one main surface, for the "free" main surface.
  • component (a) preferably is provided as part of the surface sizing.
  • component (b) preferably being provided as part of the surface sizing.
  • didecyldimethylammonium halides primarily have bactericidal, but also virucidal and fungicidal properties, and 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolyl sulfone and thiabendazole have bactericidal and especially fungicidal properties.
  • each of these compounds is most suitable for supplementing the biocidal activity of component (a).
  • At least one coating is therefore preferably provided with at least one biocidal compound of component (b).
  • sufficient biocidal protection can also be achieved with the aid of component (a) alone, even if component (a) is in a surface sizing of the substrate material and the substrate material has one or more coatings.
  • the biocide combination according to the invention is not only suitable for the biocidal finishing of fiber papers (of papers with a substrate based on plant fibers with or without the addition of plastic fibers or with a substrate made of plastic fibers), but also for the biocidal finishing of so-called “hybrid Papers”, as they are often used in the field of security papers in particular.
  • Hybrid papers have a fiber paper substrate, preferably a paper substrate based on plant fibers.
  • the fiber paper substrate is covered with a plastic film on one or both surfaces.
  • components (a) and (b) can also be present exclusively or additionally in one or more coatings of the plastic film(s), for example in an ink acceptance layer.
  • the biocidal active ingredients are also preferably applied as components of coating compositions, in particular of an ink-receptive layer.
  • Papers according to the invention preferably contain 0.01 to 1.5 g BAHal/m 2 paper surface, particularly preferably 0.10 to 1.0 g BAHal/m 2 paper surface, and very particularly preferably 0.20 to 0.50 g BAHal /m 2 paper surface, where "m 2 paper surface” denotes the surface area of one side of the paper.
  • euro banknotes have an area of around 0.01 m 2 .
  • Papers according to the invention also contain preferably 0.01 to 0.30 g component (b)/m 2 paper surface, particularly preferably 0.02 to 0.20 g component
  • component (b)/m 2 paper surface and most preferably 0.03 to 0.10 g component (b)/m 2 paper surface.
  • the amounts given relate in each case to the total amount of all compounds of the respective component. If component (b) contains, for example, a didecyldimethylammonium halide and 3-iodo-2- propynylbutyl carbamate, the total amount of the two compounds together is preferably 0.01 to 0.30 g/m 2 paper surface.
  • Suitable amounts for compounds of component (b) are about 0.01 to 0.30 g DDAHal/m 2 paper surface, preferably 0.05 to 0.20 g DDAHal/m 2 paper surface, and for the compounds IPBC, diiodomethyl p-tolylsulfone and thiabendazole in each case 0.01 to 0.05 g/m 2 paper surface, preferably 0.02 to 0.03 g/m 2 paper surface.
  • the benzalkonium halide and the didecyldimethylammonium halide are preferably used in a molar ratio of BAHal:DDAHal in the range from 0.3:1 to 3.0:1, more preferably in the range from 0.7:1 to 1.3:1, and the benzalkonium halide and the compounds IPBC, diiodomethyl-p-tolylsulfone and thiabendazole are preferably used in a molar ratio of BAHal/IPBC or diiodomethyl-p-tolylsulfone or thiabendazole in the range from 30:1 to 5:1, particularly preferably in the range from 15: 1 to 8:1 used.
  • the molar ratio of BAHak component (b) is preferably in the range from 0.3:1 to 15:1, more preferably in the range from 1:1 to 10:1.
  • benzalkonium halides can vary considerably depending on the alkyl groups present and the halides present, and the molar mass of DDAHal can also vary considerably depending on the halide present.
  • component (a) and component (b) allow the amount of biocide required to achieve a specific effect to be significantly reduced compared to using component (a) or component (b) alone.
  • Components (a) and (b) work synergistically together.
  • DDAHal when using DDAHal as component (b) or as part of component (b), it may be necessary, from the embodiment described as preferred, to provide component (b) as part of a coating, while component (a) is contained in a surface sizing is to deviate.
  • Didecyldimethylammonium halides tend to foam and are therefore preferably used in accordance with the invention together with an addition of ⁇ -cyclodextrin.
  • compositions containing DDAHal when used to biocide paper, tends to degrade printability, especially wet ink adhesion, and washfastness compared to papers treated with the same composition without g-cyclodextrin.
  • This can be counteracted by using a combination of BAHal, DDAHal and g-cyclodextrin to make the paper biocidal.
  • all three compounds BAHal, DDAHal and ⁇ -cyclodextrin can be applied to the paper or incorporated into the paper together as components of a single composition.
  • the composition can optionally contain one or more further compounds of component (b).
  • BAHal on the one hand and DDAHa1 plus g-cyclodextrin on the other hand can be applied to the paper or introduced into the paper separately as components of two different compositions.
  • wet paint adhesion and to some extent washfastness are determined by the properties of BAHal rather than the properties of the DDAHa1 plus g-cyclodextrin compounds.
  • BAHal the washing resistance and wet paint adhesion are determined by the BAHal component.
  • Further compounds of component (b) can be applied in a separate composition or together with DDAHa1 or together with BAHa1.
  • the amount of g-cyclodextrin used to avoid unwanted foam formation when using DDAHa1 depends on the amount of DDAHa1 used.
  • the molar ratio g-cyclodextrin:DDAHal is preferably in the range from 2.0 to 10.0 (2:1 to 10:1), particularly preferably in the range from 1.0 to 7.0, and very particularly preferably in the range of 4.0 to 5.0.
  • concentration of the active ingredients in the respective carrier media such as sizing liquors or coatings must be adjusted appropriately so that the desired biocide concentrations are obtained in the finished paper.
  • Factors to be considered here include the thickness of the coating to be applied, the amount of sizing liquor absorbed by the paper, whether the biocides are to be applied or incorporated using a single carrier medium, or whether several carrier media are to be used for this purpose.
  • the biocides can be applied to the paper, for example, as an additive to a surface size, but they can also be added to other paper coating agents such as paints or varnishes.
  • Security papers for the production of documents of value are equipped with numerous layers which serve different purposes, as is known to a person skilled in the field of security papers and documents of value. In principle, each of these layers can be used as a carrier layer for biocides, with surface sizes and certain coatings being used preferably as carrier layers for biocides, as described above.
  • the concentrations in the individual carrier media can be lower than when the paper is treated with a biocide using a single carrier medium.
  • concentrations for a specific application can easily be determined by a person skilled in the art in a few experiments. Suitable concentrations may range from 0.01 to 10% by weight of biocide in the carrier medium.
  • the optimum amount of g-cyclodextrin for regulating the foaming behavior for a specific carrier medium, for example a glue, and a desired concentration of DDAHa1 in the carrier medium can be determined very well by a test method developed by the inventors of the present invention.
  • the principle of the test procedure for assessing the foaming behavior is to fill a 500mL cylinder (VWRI612-3838) with an amount of 50 g of the biocide-containing composition, immediately after filling, measure the volume occupied by the composition, stir at 300 rpm for 5 minutes, then inflate for 3 minutes (Sterican® 0.8x120mm standard disposable cannula with 0 .57mm, 0.1L/min) and measure the volume again immediately after stopping air blowing and 1 minute after stopping air blowing.
  • the process is carried out in a standard climate.
  • Standard climate means a temperature of 23 ⁇ 1°C and a relative humidity of 5 ⁇ 2%.
  • a composition is suitable for finishing paper with the biocide combination according to the invention if the foam-related increase in volume immediately after the end of air blowing (at time T3, ie three minutes after the start of air blowing) is at most 100% and after 1 minute of rest (at time T4, ie four minutes after the start of blowing in air) is still a maximum of 10%, in each case based on the volume immediately after filling the
  • V TO volume just after filling the cylinder
  • V T3 volume just after stopping air injection
  • V T4 volume after T3 plus 1 minute rest.
  • the "air fraction" in the total volume at time T3 may not exceed 50%, and at time T4 it may still be a maximum of 9.1%, expressed by conditions (3) and (4): [(V T3 -V TO ) 100]:V T3 ⁇ 50 (3)
  • compositions that do not contain DDAHal can also produce some foaming, but at a low enough level that it is not objectionable.
  • DDAHal that show unsatisfactory foaming behavior in the above test
  • Guide values for the molar ratios of g-cyclodextrin and DDAHal are given above.
  • the antifoaming effect of g-cyclodextrin was verified using a sizing composition containing DDAC.
  • FIG. 3 shows a cross section through a polymer paper according to the invention.
  • the embodiment of a paper 1 according to the invention shown in FIG. 1 is seated on a fiber substrate 2, for example made of cotton fibers.
  • a fiber substrate 2 for example made of cotton fibers.
  • the paper On one surface, hereinafter referred to as the first major surface, the paper is provided with a surface size 4, and on the opposite surface, hereinafter referred to as the second major surface, it is provided with a surface sizing 5.
  • the surface sizes 4, 5 are usually identical, but they can also be different.
  • Both the surface sizing 4 and the surface sizing 5 have an area 6 which is located on the respective glued surface of the fiber substrate 2 and an area 6' in which the sizing compositions have penetrated the fiber substrate 2.
  • the paper also has a first coating 7 on the first major surface and a first coating 8 on the second major surface, and in addition a second coating 9 on the first major surface applied to the first coating 7 .
  • first coating means a coating that has undergone some form of further treatment. For example, it can be printed or equipped with security elements. In the field of security papers, such coatings are preferably produced from aqueous dispersions based on acrylate and/or polyurethane.
  • a “second coating” is a coating that is applied to one surface of the paper during manufacture, i.e. it forms an outer layer. The second coating covers, for example, imprints and/or security elements that are on the first coating.
  • the second coating is a protective layer and is often made from paints with binders based on acrylate and/or polyurethane, which are crosslinked using suitable monomers. UV-crosslinking lacquers, in particular 100% systems, are preferred.
  • the coatings are preferably applied over the entire surface, but can also be applied over part of the surface. For example, the first coating can only be provided in those surface areas that are to be printed, while the second coating Device can only be provided in those surface areas in which an imprint or a security feature is to be protected against damage, dirt, wear or counterfeiting.
  • the imprint 12 and the security element 13 on the first main surface are protected by the protective lacquer layer 9.
  • the surface sizes 4, 5 and the coatings 7, 8 are used to provide the paper with biocides.
  • the surface sizings 4, 5 contain BAC or another BAHal such as BABr, and the coatings 7, 8 each contain IPBC or one or more other biocidal compounds from the group of component (b).
  • the second coating 9 there is no biocidally active compound.
  • the second coating 9 could also contain one or more biocidal compounds.
  • the benzalkonium halides are preferably used in encapsulated form, for example encapsulated in polymethylurea or a polysaccharide or a polyacrylate.
  • biocidal compounds it is also possible to add different biocidal compounds to the surface sizes 4, 5 and/or to add different biocidal compounds to the first coatings 7, 8. For reasons of simplified manufacturability, however, the same compositions are used as far as possible.
  • the embodiment of a paper 1 according to the invention shown in FIG. 2 also has a fiber substrate 2, for example fibers made of plant fibers such as cotton.
  • this substrate only has surface sizing 5 on its second main surface, while it is bonded to a plastic film 11, for example made of polypropylene, on its first main surface. It is therefore a hybrid paper.
  • the plastic film 11 is coated with a first coating 7 on which a print 12 and a security element 13 are located.
  • a second coating 9 covers and protects the imprint 12, the security element 13 and the exposed surface areas of the first coating 7.
  • Hybrid papers often have a plastic film on both main surfaces.
  • a plastic film is provided on only one of the surfaces while the opposite surface is glued.
  • the surface sizing 5 has an area 6 on the second main surface of the fibrous substrate and an area 6' which has penetrated into the fibrous substrate 2.
  • Imprints 12 are printed directly onto the surface sizing 5 .
  • a second coating 10 is applied to the imprints 12 and the free surface areas of the surface sizing 5 .
  • the second coating 9 on the first main surface and the second coating 10 on the second main surface are protective layers formed over the entire surface.
  • the coating composition for producing the second coatings 9, 10 is a mixture of DDAC, DDABr and g-cyclodextrin too mixed.
  • the addition of g-cyclodextrin prevents the coating composition from foaming.
  • the coatings 9, 10 are identical, but of course they can also be different.
  • the embodiment of a paper 1 according to the invention shown in FIG. 3 is a polymer paper, which means it has a substrate made of a plastic film such as for example from polyethylene terephthalate.
  • the polymeric substrate is denoted by reference numeral 3 in the illustrated embodiment.
  • first coating In contrast to fiber substrates, polymer substrates are of course not glued. However, they are provided with various coatings, for example at least one coating that makes them opaque and printable. Coatings such as those referred to above as “first coating” are ideally suited for this purpose.
  • first coating 7 In the embodiment of a security paper according to the invention shown in FIG. 3, the first main surface is coated with a first coating 7 over its entire surface and the second main surface is coated with a first coating 8 over its entire surface.
  • the first coating 7 is an ink-receptive layer and has an imprint 12 and an adhesive security element 13
  • the first coating 8 on the opposite main surface of the paper is also an ink-receptive layer and has imprints 12 .
  • the imprint 12 and the security element 13 on the first coating 7 are protected by a second coating 9 applied over the entire surface.
  • Two coatings are available on the first main surface and only one coating on the second main surface for the biocidal finish of the paper. If the same composition is used to produce the first coating 7 and the first coating 8, it makes sense to mix all the substances that are to be used for the biocidal finish of the paper with this composition.
  • the coatings 7, 8 could both contain a mixture of BAC, IPBC and thiabendazole. No biocidal compound would then have to be added to the composition for producing the second coating 9 .
  • the biocidal effect on the second major surface would be provided exclusively by a compound of component (a). the through
  • biocidal protection provided by BAC or one or more other benzalkonium halides may be quite adequate.
  • biocidal compounds could be added to the composition used to make the first coating 7 and to the composition used to make the first coating 8, e.g. only BAC in the case of the first coating 7, and a mixture of BAC and IPBC in the case of the first coating 8.
  • the composition for making the second coating 9 would then have IPBC and thiabendazole added to it, for example, or only IPBC, or another component (b) compound.
  • Papers and documents of value such as banknotes which are equipped according to the invention with component (a) or with component (a) and component (b), are biocidally effective, i.e. they inhibit or prevent the growth of bacteria and fungi on the paper, and they cause inactivation of viruses, especially enveloped viruses on the paper.
  • component (a) as well as component (a) in combination with component (b) can be seen from the following test results: Two identical paper substrates made of cotton fibers, as typically used to produce banknotes, were each glued in a size press (Einlehner laboratory size press) with a surface size liquor and placed in a vacuum dryer for 10 minutes and then in a drying cabinet at 120°C for 5 minutes hardened. One of the glue liquors contained BAC, the other contained BAC and DDAC. Otherwise the glue liquors were identical.
  • the papers obtained contained 0.5 g BAC/m 2 paper surface or 0.3 g BAC and 0.2 g DDAC/m 2 paper surface. Samples of the papers were tested for antibacterial efficacy based on test method AATCC 100:2019 and for antifungal efficacy based on test method AATCC 30:2017, method IP, which includes visual and microscopic assessment. Test for antibacterial effectiveness
  • Staphylococcus aureus (DSM 799) and Escherichia coli (DSM 1576) were used as test germs. Contact times were 0h, 6h and 24h respectively. The contact temperature was 36°C, the nutrient medium was CASO agar and the incubation time was 2 days.
  • T x number of germs/sample after 6 h or 24 h incubation time.
  • Test for antifungal activity Aspergillus niger was used as the test fungus.
  • the surface of the nutrient medium was inoculated with 1 ml of the prepared spore suspension and a moistened paper sample was placed on it. Then an additional 0.2 ml of the spore suspension was added to the specimens.
  • Sized paper substrates with BAC in the sizing were tested for antiviral effectiveness based on the test method ISO 18184: 2014.
  • the paper substrates contained 0.5 g BAC/m 2 paper surface.
  • a defined amount of the bacteriophage phi6 is applied to an internal reference and to the test material and incubated for 2 hours.
  • the phages are then detached (“shaken out”) and diluted in a decade series.
  • the plaque forming units (PFU) per test material are determined by means of a plaque assay and the antiviral effectiveness M v is calculated from them.
  • M v value of the antiviral efficacy
  • IgV b mean value of the logarithm of the phage titers after 2 h contact with the reference sample
  • IgV c mean value of the logarithm of the phage titers after 2 h contact with the antiviral sample
  • Full antiviral efficacy is present when M v > 3, 0
  • a low antiviral effectiveness is present at 3.0 > M v > 2.0.
  • the samples tested showed full antiviral efficacy.
  • the first coating was made by applying an aqueous dispersion of acrylates, followed by air drying, and the second coating was made by applying a UV-curing varnish based on acrylates and curing the varnish.
  • each paper sample contained benzalkonium chloride (BAC), the first coating (if any) for sample #5 contained diiodomethyl-p-tolylsulfone, and the second coating (if any) for sample #3 and sample # 7 IPBC.
  • BAC benzalkonium chloride
  • the structure of the samples and the amount of biocide present in each case can be seen from Table 2 below.
  • Table 2 means no coating was present means the coating contained no biocide All tested samples showed a satisfactory biocidal effect, ie they were antiviral, antibacterial and antifungal. The effect was also obtained in those samples containing only component (a) (BAC) as the biocidal compound, and was also obtained even when only the surface sizing contained the biocidal compound and the paper was additionally coated with one or two coatings that were free of biocidal compounds.
  • BAC component
  • the biocidal effect in particular the fungicidal effect, was significantly improved if diiodomethyl-p-tolylsulfone (sample no. 5) was also present in the first coating or IPBC was also present in the second coating (sample nos. 3 and 7).
  • component (a) and component (b) made it possible to significantly reduce the total amount of biocide required (sample nos. 3, 5, 7).
  • Components (a) and (b) act synergistically together.

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  • Life Sciences & Earth Sciences (AREA)
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  • Paper (AREA)

Abstract

L'invention concerne un papier qui contient un composant (a) et éventuellement un composant (b), le composant (a) contenant un halogénure de benzalkonium et le composant (b) au moins un composé choisi dans le groupe constitué d'halogénures de didécyldiméthylammonium, de 3-iodo-2-propinylbutylcarbamate, de diiodométhyl-p-tolylsulfone et de thiabendazole. Si le composant (b) contient un halogénure de didécyldiméthylammonium, il contient de préférence également de la γ-cyclodextrine. L'invention concerne également un procédé de fabrication de ce papier et un procédé pour tester le comportement moussant de compositions qui contiennent des halogénures de didécyldiméthylammonium. Le papier selon l'invention convient en particulier comme papier de sécurité pour la fabrication de documents de valeur tels que des billets de banque. L'utilisation d'un halogénure de benzalkonium, de préférence en combinaison avec au moins un composé du composant (b), confère au papier des propriétés virucides, bactéricides et fongicides.
EP22733853.0A 2021-06-22 2022-06-17 Papier biocide, document de valeur biocide et procédé de fabrication correspondant Pending EP4359606A2 (fr)

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DE102021003200.4A DE102021003200A1 (de) 2021-06-22 2021-06-22 Biozides Papier, biozides Wertdokument und Verfahren zu seiner Herstellung
PCT/EP2022/025279 WO2022189043A2 (fr) 2021-06-22 2022-06-17 Papier biocide, document de valeur biocide et procédé de fabrication correspondant

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DE202024103620U1 (de) * 2024-07-02 2025-10-14 Tannpapier Gmbh Substrat mit antimikrobiellen Eigenschaften

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WO1998005206A1 (fr) * 1996-08-02 1998-02-12 Hickson International Plc Compositions de sel d'ammonium quaternaire et procedes de traitement de substrats
FR2838025B1 (fr) 2002-04-08 2005-08-05 Arjo Wiggins Support d'information presentant des proprietes biocides et son procede de fabrication
DE102005045129A1 (de) * 2005-09-21 2007-03-22 Schülke & Mayr GmbH Zubereitung zur fungiziden und algiziden Ausrüstung alkalischer Beschichtungszusammensetzungen
CA2629247C (fr) * 2005-11-28 2012-03-20 Sanjiv Agarwal Feuille hygienique composee de papier recycle et processus de fabrication de feuille hygienique a partir de papier recycle
FR2945180B1 (fr) 2009-05-07 2013-02-22 Arjowiggins Security Support d'information presentant des proprietes antivirales et son procede de fabrication
CA2784922C (fr) 2010-01-18 2018-05-01 Cascades Canada Ulc Papiers minces antimicrobiens et leur procede de fabrication
EP2538781B1 (fr) * 2010-02-23 2016-08-03 Clariant S.A. Procédé de co-encapsulation de composés actifs sur le plan biocide dans des minéraux argileux fonctionnalisés par des composés azote
RU2571899C2 (ru) * 2010-10-25 2015-12-27 ЛЕНКСЕСС Дойчланд ГмбХ Содержащая пенфлуфен фунгицидная композиция, ее применение, древесина, древесные материалы или комбинированные материалы из древесины и пластика, содержащие эту композицию, и способ защиты древесины, древесных материалов из древесины и пластика
DE102012004127A1 (de) * 2012-03-01 2013-09-05 Giesecke & Devrient Gmbh Sicherheitspapier
GB2515473A (en) 2013-06-18 2014-12-31 Robert Timothy Gros Anti microbial inks and sealants
CN105324530B (zh) * 2013-06-20 2018-01-19 巴斯夫欧洲公司 微纤维化的纤维素组合物的制备方法
HK1218145A1 (zh) * 2013-07-22 2017-02-03 爱适瑞运营法国公司 包含活性剂的纤维素纤维料幅和用於制造包含活性剂的纤维素纤维料幅的方法
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FR3105250B1 (fr) 2019-12-19 2021-12-31 Oberthur Fiduciaire Sas Vernis protecteur en particulier pour les documents de sécurité

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