DE102021003200A1 - Biocidal paper, biocidal document of value and method for its production - Google Patents

Abstract

The invention relates to a paper containing benzalkonium chloride, or benzalkonium chloride and didecyldimethylammonium chloride or benzalkonium chloride, didecyldimethylammonium chloride and γ-cyclodextrin, a method for producing the paper and a method for testing the foaming behavior of a composition which contains didecyldimethylammonium chloride or didecyldimethylammonium chloride and γ-cyclodextrin or benzalkonium chloride, didecyldimethylammonium chloride and γ-cyclodextrin. The paper according to the invention is particularly suitable as security paper for the production of documents of value such as banknotes. By using the combination of the compounds benzalkonium chloride, or benzalkonium chloride and didecyldimethylammonium chloride or benzalkonium chloride, didecyldimethylammonium chloride and γ-cyclodextrin, the paper has a virucidal, bactericidal and fungicidal finish.

Description

The invention relates to papers and objects made from or with the papers, such as documents of value with biocidal properties, methods for furnishing paper with biocidal properties, and a test method for assessing the foaming behavior of compositions for the biocidal furnishing of paper.

Many items made of paper or containing paper are handled multiple times by different people with little to no control over whether these people are potential carriers of harmful viruses, bacteria, fungi or other microorganisms. Many people are concerned that a carrier of such microorganisms could transfer them to the object it touches, making the object itself a potential vector of the microorganisms in question to another person who in turn touches the object. A prime example of such items are banknotes. Banknotes go from hand to hand many millions of times, whereby viruses, bacteria and fungi could in principle be transferred to the banknote paper. The concern is understandable but unjustified. It has been shown that microorganisms on banknotes, regardless of whether they are made of plant fibre, plastic or a combination thereof (hybrid banknotes) and on other objects made of or containing paper, only remain pathogenic for a few hours. In addition, most of the microorganisms found on banknotes and other frequently handled objects are not capable of harming the health of the average healthy user. Nevertheless, it cannot be ruled out that an unfortunate combination of circumstances could lead to the transmission of microorganisms that lead to a disease.

In order to eliminate any residual risks, it is therefore desirable to provide objects that are touched by several people with a biocidal finish. This applies in particular to documents of value or security documents such as passports and other identification documents of all kinds, credit cards, admission tickets, driving licenses and of course means of payment such as banknotes. However, it also affects a large number of other objects made of paper or containing paper, such as books, newspapers and magazines and packaging materials. Books and magazines can, for example, be lent out or laid out in medical practices where the risk of transmission of harmful microorganisms is above average. In principle, however, it can be sufficient for the transmission of a harmful microorganism if the same object is touched by two different people within the period of time that the microorganism in question is pathogenic (i.e. approximately up to 10 hours).

For the purposes of the present invention, viruses are also counted among the microorganisms, although many experts do not consider viruses to be microorganisms 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 direct their replication. Accordingly, virology is also regarded as a sub-area of microbiology.

Several attempts have been made to make paper biocidal, ie antibacterial and/or antifungal and/or antiviral, but the solutions found so far are not satisfactory.

In the patent application WO 03/084326 A2 it has been proposed to treat 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.

In the patent application WO 2010/128487 A2 it has been proposed to treat paper with virucides of natural origin such as monolaurin or lactoferrin. However, these substances are very expensive to obtain, and if they are produced in situ from less expensive starting compounds in the course of making the paper virucidal, a catalyst is required, which leads to processing difficulties such as deposits in the production plant.

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, 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 by very frequent touching of the paper, and give the paper a long-lasting biocidal, in particular virucidal, effect.

The substances used should also be compatible with the paper material and the manufacturing processes be compatible with the materials used in the paper, such as sizing and/or coating compositions, and can be applied to the paper or incorporated into the paper without any problems in terms of process technology. The process engineering suitability of a biocidal composition should preferably be able to be checked in advance.

A favorable cost/benefit ratio of the substance or substances imparting biocidal properties is also desirable.

The tasks are solved by the paper, the document of value, the method for furnishing paper with biocidal properties, the test method for assessing the foaming behavior and the use for the biocidal furnishing of paper, each with the features as specified in the independent claims. Advantageous embodiments of the invention are specified in the respective dependent claims.

Paper within the meaning of the present invention is both fiber paper and polymer paper and hybrid paper. As the name suggests, 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. However, fiber papers can also have a certain proportion of plastic fibers, preferably up to a maximum of 20% by weight of plastic fibers. Examples of suitable plastics are polyethylene terephthalate, polypropylene and polyethylene. Polymer papers are made of polymer materials, i. H. they are plastic films, for example made of polyethylene terephthalate, biaxially stretched polypropylene or polyethylene, and so-called hybrid papers are fiber papers which are provided with a plastic film on one or both surfaces, as is also used for polymer papers. The plastic film can be glued to the paper, for example, or a plastic can be extruded directly onto the paper. Polymer papers are provided with coatings to make them opaque and printable. The plastic foils of hybrid papers are also provided with suitable coatings to improve printability.

According to the invention, benzalkonium chloride (BAC) is used to make paper biocidal. Benzalkonium chloride is a mixture of alkyl benzyl dimethyl ammonium chlorides where the alkyl moiety consists of C ₈ to C ₁₈ groups. Benzalkonium chloride is known for its preservative and disinfecting effect and is used, among other things, in pharmaceutical compositions.

According to the invention, it was found that benzalkonium chloride (BAC) has a combination of properties that make it outstandingly suitable for providing paper with biocides. It has a virucidal, bactericidal and fungicidal effect and is extremely compatible with paper substrate materials as well as with compositions for finishing the paper such as sizing, 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 it 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 it has no negative effects on the security features present in such security papers. It is inexpensive, surprisingly does not tend to foam in contrast to the compound DDAC used hitherto in the prior art, which is also a quaternary ammonium compound, and is therefore significantly easier to process than these. The use of foaming substances can lead to a loss of quality in the treated paper. In the case of security papers which have security features due to their special use, the visibility or the correct detectability of the security features can also be impaired. Another advantage of BAC is that although it is sufficiently mobile in the treated paper to reach microorganisms located there and render them harmless, it is bound firmly enough that no transfer to the users of the treated paper can take place. Any negative effects are therefore excluded.

Benzalkonium chloride (BAC) can be used alone or advantageously combined with didecyldimethylammonium chloride (DDAC) to further enhance biocidal activity. However, as mentioned above, DDAC has the property of causing foaming in compositions to which it is added, which makes processing difficult and can lead to a deterioration in the quality of the treated papers. According to the invention it has now been found that foaming can be suppressed by the addition of γ-cyclodextrin, which means that sizings, lacquers, coating colors, adhesives and other compositions used in the production of paper that contain both DDAC and γ-cyclodextrin without process engineering difficulties can be processed. A spraying or printing of solutions or suspensions such as inks that contain both DDAC and γ-cyclodextrin is easily possible from the point of view of processing technology. In addition, it was found that γ-cyclodextrin can improve the virucidal effect of DDAC. According to the invention, it is therefore preferred, when BAC is used in combination with DDAC, to also use γ-cyclodextrin as well.

γ-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 γ-cyclodextrin was previously unknown.

However, the addition of γ-cyclodextrin to compositions containing DDAC, when used to biocide paper, tends to degrade printability, especially wet ink adhesion, and washfastness compared to papers treated with the same composition without γ-cyclodextrin. This can be counteracted by using a combination of BAC, DDAC and γ-cyclodextrin to biocide the paper.

According to a first variant of the present invention, all three compounds BAC, DDAC and γ-cyclodextrin can be applied to or incorporated into the paper together as components of a single composition.

According to a second variant, BAC on the one hand and DDAC plus γ-cyclodextrin on the other hand can be applied to or incorporated into the paper separately as components of two different compositions. In this second variant, it is advisable to carry out the application or introduction in such a way that the paper is first equipped with the DDAC and γ-cyclodextrin component of the biocidal combination according to the invention, for example impregnated with a sizing liquor, and in a second step with BAC is equipped, for example is equipped with a BAC-containing coating. With this ordering, wet paint adhesion and to some extent washfastness are determined by the properties of BAC rather than the properties of the DDAC plus γ-cyclodextrin compounds. Surprisingly, even when DDAC, γ-cyclodextrin and BAC are applied together in a single process step and as components of a single composition, the wash resistance and wet paint adhesion are determined by the BAC component.

According to a further variant of the invention, it is also possible to carry out the biocidal treatment of paper by means of BAC and DDAC, ie without using γ-cyclodextrin. This third variant is particularly suitable when good washing resistance and good wet paint adhesion play an important role, while a certain amount of foaming can be accepted. In this variant, too, BAC and DDAC can be applied to the paper or introduced into the paper as components of a single composition in the same process step, or alternatively as components of two different compositions in two separate process steps. The order of application or introduction is irrelevant for combinations without γ-cyclodextrin.

In the following, benzalkonium chloride (BAC) is referred to as component (a) and didecyldimethylammonium chloride (DDAC), optionally in combination with γ-cyclodextrin, as component (b). Component (a) can be used alone for the biocidal treatment of paper, but components (a) and (b) are preferably used in combination, component (b) particularly preferably also containing γ-cyclodextrin.

The equipment according to the invention of a paper with biocidal properties is such that component (a) or components (a) and (b) are already mixed into the paper pulp during production of the paper substrate and thus become part of the fiber substrate material and/or a or mixed with several of the compositions used to finish the paper. For example, sizing liquors (internal sizing, surface sizing), coating colors and, in principle, any other composition that is used in the production of a specific paper even if the paper in question is not to be provided with biocidal properties are suitable for this purpose. Corresponding compositions are known to a person 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.

According to an alternative procedure, the components (a) and (b) can also be applied to the paper to be treated and/or incorporated into the paper to be treated as components of additional impregnating agents and/or coating agents, i.e. as components 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.

The type of application or incorporation of components (a) and (b) into the paper is in no way restricted and in principle all known application or incorporation methods are possible, such as impregnation, printing, spraying, spreading, etc. of the compositions containing components (a) and/or (b).

As mentioned, components (a) and (b) can be applied to or incorporated into paper as parts of the same or as parts of different compositions. In the case of separate application or incorporation, the finished paper can have components (a) and (b) in the same or in different areas of the paper, e.g. in the fiber substrate and in a coating. It makes sense to provide the biocidal active ingredients at least in the area close to the surface, i.e. in the area with which microorganisms first come into contact and which is touched by a user. Therefore, there is preferably at least one biocidal active substance (BAC or BAC and DDAC) in the last composition used during the paper manufacturing process or finishing process, in order to ensure that the replication or growth of viruses, bacteria and fungi coming into contact with the paper is efficiently inhibited.

It is particularly preferred to provide the components (a) and (b) as constituents of a surface sizing liquor and to 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 biocidal 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 viruses, bacteria and fungi contacting the paper. In addition, 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.

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), but also for the biocidal finishing of so-called "hybrid papers", as they are found in particular on the Field of security papers are commonly used. Hybrid papers have a fiber paper substrate, preferably a plant fiber based paper substrate, which is provided with a plastic film on one or both surfaces. In hybrid papers of this type, 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. In the case of polymer papers, the biocidal active ingredients are also preferably applied as components of coating compositions.

Papers according to the invention preferably contain 0.01 to 1.00 g BAC/m ² paper surface, particularly preferably 0.10 to 0.80 g BAC/m ² paper surface, and very particularly preferably 0.30 to 0.60 g BAC/m ² Paper surface area, where "m ² paper surface area" means the surface area of one side of the paper.

Papers according to the invention also preferably contain 0.01 to 0.30 g DDAC/m ² paper surface, particularly preferably 0.03 to 0.20 g DDAC/m ² paper surface, and very particularly preferably 0.06 to 0.10 g DDAC/m 2 ² paper surface.

Since papers have two surfaces to be protected (main surfaces), they typically contain twice the amounts of BAC or DDAC specified above.

When BAC and DDAC are used together, BAC and DDAC are preferably used in a molar ratio of BAC:DDAC in the range of 0.3 to 3.0 (0.3:1 to 3.0:1), more preferably in the range of 0 .5 to 2.0, and very particularly preferably in the range from 0.8 to 1.2. BAC is a mixture of alkyl benzyl dimethyl ammonium chlorides, where the alkyl group can consist of C ₈ to C ₁₈ chains. Accordingly, the molar mass can vary depending on which mixture is used. In a combination of BAC and DDAC, lower amounts than specified above are sufficient for BAC and DDAC, whereby in Sum (BAC plus DDAC) the amounts specified for BAC should be aimed for.

The amount of γ-cyclodextrin used to avoid unwanted foaming when using DDAC depends on the amount of DDAC used. The molar ratio of γ-cyclodextrin:DDAC 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.

When applying or incorporating the biocidal active ingredients, the concentration of the active ingredients in the respective carrier media such as sizing liquors or coating agents must be adjusted appropriately so that the desired biocide concentrations are obtained in the finished paper. Factors to be taken into account 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 introduced using a single carrier medium, or whether several carrier media are to be used for this purpose. For example, the biocides could on the one hand be applied to the paper as an additive to a surface size and on the other hand also be added to other paper coating agents such as paints or varnishes. Security papers for the production of documents of value, for example, are provided with numerous layers that 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. If the biocides are distributed over several carrier media, ie applied in several steps, the concentrations in the individual carrier media can be lower than when the paper is treated with a biocide using a single carrier medium. The most suitable 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 γ-cyclodextrin to regulate the foaming behavior for a specific carrier medium, for example a glue, and a desired concentration of DDAC 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 method for assessing the foaming behavior is to fill a 500mL graduated cylinder (VWRI612-3838) with an amount of 50 g of the biocide-containing composition, immediately after filling, measure the volume occupied by the composition, for 5 minutes at 300 RPM, then insufflation for 3 minutes (Sterican® 0.8x120mm standard disposable cannula, 0.57mm inner diameter, 0.1 L/min) and the volume immediately after the air insufflation is stopped and 1 minute after it is stopped of blowing air again. 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%.

$$\left[\left({\text{V}}_{\text{T}4}-{\text{V}}_{\text{T}0}\right):{\text{V}}_{\text{T}0}\right]\cdot 100\le 10$$

A composition is suitable for finishing paper with the biocide combination according to the invention if the foam-related increase in volume is at most 100% immediately after the end of air blowing (at time T3, ie three minutes after the start of air blowing) and after 1 minute 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 cylinder (at time T0, ie before blowing in air), ie the following conditions ( 1) and (2) must both be met. $$\left[\left({\text{V}}_{\text{T}3}-{\text{V}}_{\text{T}0}\right):{\text{V}}_{\text{T}0}\right]\cdot 100\le 100$$

$$\left[\left({\text{V}}_{\text{T}4}-{\text{V}}_{\text{T}0}\right):{\text{V}}_{\text{T}0}\right]\cdot 100\le 10$$

• V_T0 = Volumen unmittelbar nach dem Befüllen des Zylinders,
• V_T3 = Volumen unmittelbar nach Beendigung des Einblasens von Luft,
• V_T4 = Volumen nach T3 plus 1 Minute Ruhen.

The following applies:

• V _T0 = volume immediately after filling the cylinder,
• V _T3 = volume immediately after cessation of air injection,
• V _T4 = volume after T3 plus 1 minute rest.

$$\left[\left({\text{V}}_{\text{T}4}-{\text{V}}_{\text{T}0}\right)\cdot 100\right]\cdot {\text{V}}_{\text{T}4}\le 9,1$$

In other words: The "air fraction" in the total volume at time T3 may not exceed 50%, and at time T4 may still be a maximum of 9.1%, expressed by conditions (3) and (4): $$\left[\left({\text{V}}_{\text{T}3}-{\text{V}}_{\text{T}0}\right)\cdot 100\right]\cdot {\text{V}}_{\text{T}3}\le 50$$

$$\left[\left({\text{V}}_{\text{T}4}-{\text{V}}_{\text{T}0}\right)\cdot 100\right]\cdot {\text{V}}_{\text{T}4}\le 9,1$$

For example, if a composition in the above-mentioned standing cylinder has a volume of 50 ml at time T0, the volume at time T3 must not exceed 100 ml and at time T4 a maximum of 55 ml, corresponding to an air content of 50 ml at time T3 or 5 ml at time T4.

The test procedure can be omitted for compositions that contain only BAC as the biocidal active substance, since BAC shows no tendency to form foam. For compositions that Containing DDAC and showing unsatisfactory foaming behavior in the above test, add γ-cyclodextrin and repeat the test procedure. By adding a sufficient amount of γ-cyclodextrin, the foaming behavior can be brought into an acceptable range. Guide values for the molar ratios of γ-cyclodextrin and DDAC are given above.

The antifoaming effect of γ-cyclodextrin was verified using a sizing composition containing DDAC.

24.00 g of polyvinyl alcohol (Poval 28/99 from Kuraray, JP) were dissolved in 763.60 g of deionized water with a hardness of 20 at 80°C. After cooling to below 50°C, 12.00 g glycerol (86.5% in water) and 0.40 g Agitan 299 (from Münzing Chemie GmbH) and different amounts of DDAC (Bt-H Q IV from Bt-H Biozidtechnik and Handels UG) added. Furthermore, γ-cyclodextrin (Cavamax from Wacker Chemie) was added in different amounts and stirred for 30 minutes with the temperature gradually decreasing to room temperature. Compositions with different amounts of BAC were also tested. An identically prepared sizing composition which contained neither DDAC, BAC nor γ-cyclodextrin was tested as a reference composition.

The volume immediately after filling into the cylinder, immediately after the air blowing was stopped and one minute after the air blowing was stopped, and the percentage increase in volume due to foaming immediately after the air blowing was stopped and one minute after the stopping of the air blowing were measured, respectively of blowing in air is calculated. It was found that none of the DDAC-free compositions foamed appreciably, while compositions containing DDAC but no γ-cyclodextrin foamed heavily and formed a stable foam. The addition of increasing amounts of γ-cyclodextrin inhibits foam formation and the foam that forms breaks down quickly.

Papers and documents of value such as banknotes, which are equipped with BAC or with BAC and DDAC according to the invention, are biocidal, i.e. they inhibit or prevent the growth of bacteria and fungi on the paper, and they cause inactivation of viruses, especially enveloped ones viruses on paper.

• Zwei identische Papiersubstrate aus Baumwollfasern, wie sie typischerweise zur Herstellung von Banknoten verwendet werden, wurden in einer Leimpresse (Einlehner-Laborleimpresse) jeweils mit einer Oberflächen-Leimflotte geleimt und 10 Minuten lang im Vakuumtrockner und danach 5 Minuten lang bei 120°C im Trockenschrank ausgehärtet. Eine der Leimflotten enthielt BAC, die andere enthielt BAC und DDAC. Ansonsten waren die Leimflotten identisch.

The antibacterial and antifungal effectiveness of BAC and of BAC in combination with DDAC can be seen from the following test results:

• Two identical paper substrates made of cotton fibers, as typically used for the production of banknotes, were each glued in a size press (Einlehner laboratory size press) with a surface size liquor and cured for 10 minutes in a vacuum dryer and then for 5 minutes at 120°C in a drying cabinet . One of the glue liquors contained BAC, the other contained BAC and DDAC. Otherwise the glue liquors were identical.

Test for antibacterial effectiveness

Samples of the papers were tested for antibacterial activity in accordance with the AATCC 100:2012 test method and for antifungal activity in accordance with the AATCC 30:2017 test method, Procedure III, which includes visual and microscopic evaluation.

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.

Samples of the paper measuring 2 cm×2 cm were tested. After applying 0.15 ml of germ suspension (diluted in 0.9% NaCl solution) to each specimen, the specimens were stored individually in a sterile Petri dish at 36°C. A sample was prepared for each contact time. At the end of the contact time, the germs were dissolved in 10 ml of BD D/E neutralizing broth and the number of germs was determined using a germ count method.

An additional sterilization of the sample material was not carried out. The test was carried out in triplicate.

T₀ = Anzahl an Keimen/Probe, unmittelbar nach der Inokulierung
T_x = Anzahl an Keimen/Probe, nach 6h bzw. 24h Inkubationszeit.The reduction in the number of germs was determined using the following equation: $$\%-\text{reduction}=\left[\left({\text{T}}_0-{\text{T}}_{\text{x}}\right):{\text{T}}_0\right]\times 100$$

T ₀ = number of germs/sample immediately after inoculation
T _x = number of germs/sample after 6 h or 24 h incubation time.

The results show that both test germs were deactivated very quickly on the papers according to the invention, both in the samples with BAC and in the samples with BAC and DDAC.

Test for antifungal effectiveness

Aspergillus niger (ATCC 6275) was used as the test fungus.

Circular specimens of the papers, each with a diameter of 4 cm, were tested.

Mineral salts agar according to AATCC 30 with 3% glucose was used as the nutrient medium and the incubation time was 7 days at 28°C. Each test was performed in duplicate.

The surface of the nutrient medium was inoculated with 1 ml of the prepared spore suspension and a moistened paper sample piece was placed on it. Then an additional 0.2 ml of the spore suspension was added to the specimens.

After the end of the incubation period, fungal growth on the surface of the sample pieces and on the surrounding agar nutrient medium was assessed visually and microscopically. It was found that even with a microscopic examination on the surface of the sample pieces according to the invention, no fungal growth could be observed, neither in the samples with BAC nor in the samples with BAC and DDAC.

QUOTES INCLUDED IN DESCRIPTION

This list of the documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 03084326 A2 [0006]
• WO 2010128487 A2 [0007]

Claims (15)

Paper comprising a fiber or film substrate material, characterized in that it is provided with a component (a) and optionally with a component (b), wherein component (a) contains benzalkonium chloride (BAC) and component (b) Didecyldimethylammonium chloride (DDAC) and optionally γ-cyclodextrin. paper after claim 1 , 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. paper after claim 1 or 2 , characterized in that it is - a fiber paper which has a substrate material made from vegetable fibers or from a mixture of vegetable fibers and plastic fibers, with component (a) being in the substrate material or in a coating on the substrate material, or - a hybrid paper which has a substrate material of vegetable fibers or of a mixture of vegetable fibers and plastic fibers bonded to a plastic film on one or both major surfaces, component (a) being in the substrate material or in a coating on the surface of the plastic film or of the substrate material, or - is a polymer paper which has a substrate material of a plastic film, with component (a) being in a coating of the plastic film. paper after claim 3 , 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 after one of Claims 1 until 4 , characterized in that on each of its two main surfaces there is 0.01 to 1.00 g BAC/m ² paper surface, preferably 0.10 to 0.80 g BAC/m ² paper surface, particularly preferably 0.30 to 0.60 g BAC/m ² paper surface, and optionally also 0.01 to 0.30 g DDAC/m ² paper surface, preferably 0.03 to 0.20 g DDAC/m ² paper surface, particularly preferably 0.06 to 0.10 g DDAC /m ² paper surface contains. paper after one of Claims 1 until 5 , characterized in that it contains BAC and DDAC in a molar ratio of BAC:DDAC in the range from 0.3 to 3.0, preferably from 0.5 to 2.0, particularly preferably from 0.8 to 1.2. paper after one of Claims 1 until 6 , characterized in that it contains γ-cyclodextrin and DDAC in a molar ratio of γ-cyclodextrin: DDAC in the range from 2.0 to 10.0, preferably from 1.0 to 7.0, particularly preferably from 4.0 to 5, 0 contains. Security paper with at least one security feature, characterized in that it consists of or with a paper according to one of Claims 1 until 7 is made. Document of value such as a banknote or security document such as an identity document, characterized in that it is a security paper claim 8 having. Process for providing a paper with biocidal, in particular virucidal, properties, having the following steps: - providing a paper substrate material made of fibers or a film, - providing component (a) and optionally component (b) in a biocidally effective amount, component (a) containing benzalkonium chloride (BAC) and component (b) containing didecyldimethylammonium chloride (DDAC) and optionally γ-cyclodextrin, and - Applying and/or incorporating component (a) and optionally component (b) onto or into the paper substrate material. procedure after claim 10 , characterized in that: - the paper is a fiber paper which has a substrate material of vegetable fibers or a mixture of vegetable fibers and plastic fibers, and component (a) is mixed into the pulp during the manufacture of the substrate material or as a component of a surface size incorporated into the substrate material or applied to the substrate material as part of a coating composition, or - the paper is a polymer paper which has a plastic film substrate material and component (a) is applied to the plastic film as part of a coating composition. procedure after claim 10 , characterized in that the paper is a hybrid paper having a substrate material made of vegetable fibers or from a mixture of vegetable fibers and plastic fibers ver on one or both major surfaces with a plastic film is bonded, wherein component (a) - if the substrate material is only bonded to a plastic film on one of its main surfaces, is mixed into the pulp during manufacture of the substrate material or is introduced into the substrate material as a component of a surface size and also as a component of a coating composition the surface of the plastic film is applied, and if the substrate material is bonded to a plastic film on each of its two main surfaces, it is applied to the surfaces of the plastic films as part of a coating composition. Procedure according to one of Claims 10 until 12 , characterized in that the paper is also provided with component (b), wherein component (b) is incorporated into or onto the paper in the same manner as component (a) or as part of a different composition than component (a). is applied. Use of benzalkonium chloride (BAC), or a combination of BAC and didecyldimethylammonium chloride (DDAC), or a combination of BAC, DDAC and γ-cyclodextrin for the virucidal, bactericidal and fungicidal finish of paper. Test method for assessing the foaming behavior of a composition containing DDAC or DDAC and γ-cyclodextrin or BAC and DDAC and γ-cyclodextrin, characterized in that - the composition is filled into a cylindrical container, - its volume is measured, - air is introduced into the composition is blown, - the volume is measured again immediately after the end of the air injection and at a time t after the end of the air injection, and - from the measured volumes the increase in volume due to the foam is calculated immediately after the air injection and at the time t will.