EP4340611A1 - Supports poreux à propriétés biocides - Google Patents

Supports poreux à propriétés biocides

Info

Publication number
EP4340611A1
EP4340611A1 EP22728626.7A EP22728626A EP4340611A1 EP 4340611 A1 EP4340611 A1 EP 4340611A1 EP 22728626 A EP22728626 A EP 22728626A EP 4340611 A1 EP4340611 A1 EP 4340611A1
Authority
EP
European Patent Office
Prior art keywords
composition according
biocidal
weight
porous support
composition
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
EP22728626.7A
Other languages
German (de)
English (en)
French (fr)
Inventor
Henri Rosset
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oberthur Fiduciaire SAS
Original Assignee
Oberthur Fiduciaire SAS
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 Oberthur Fiduciaire SAS filed Critical Oberthur Fiduciaire SAS
Publication of EP4340611A1 publication Critical patent/EP4340611A1/fr
Pending legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • 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 invention relates to the field of porous supports with biocidal properties, in particular that of sheet materials and more particularly that of fibrous materials such as papers, non-woven materials and textiles, in particular printing and writing papers, coated papers, copy paper, packaging cardboard produced from virgin and/or recycled fibres, leather, wood, security paper, security documents, banknote holders.
  • the invention aims in particular to propose a composition and a method useful for conferring a surface biocidal activity and guaranteeing hydrophobicity to the porous substrates from which these supports are derived.
  • a cellulosic fibrous material such as a banknote or cardboard, generally has a tendency to absorb moisture, which clearly favors the development of microorganisms within them. and/or contributes to their subsistence.
  • the most frequent solution consists in treating the support concerned, and more generally its base substrate formed of a cellulosic material, with at least one biocidal agent.
  • the incorporation of this or these biocidal agents at the level of the basic substrate can be done by immersing said substrate in a solution of said biocidal agent, by spraying, surfacing, or even coating this substrate with a solution containing said biocidal agent.
  • biocidal agents By way of representative of the biocidal agents, thus conventionally implemented, mention may in particular be made of p-[(Diiodomethyl)sulfonyl]toluol, 3-iodo-2-propynylbutyl carbamate, methyl-1H-benzimidazol-2-ylcarbamate, monolaurin, compounds based on isothiazoline or derivatives of isothiazolone, chitosan, quaternary ammonium salts in particular didecyl dimethyl ammonium chloride, zinc zeolites and silver ions...
  • biocidal agents often only have a majority specific biocidal activity, that is to say bactericidal, fungicidal or virucidal and it is then mandatory to combine them to obtain broad-spectrum biocidal efficacy. This is obviously an additional constraint because the conditions for implementing these biocidal agents are not always identical.
  • compounds based on quaternary ammonium, in particular didecyl dimethyl ammonium chloride (DD AC) are known as particularly advantageous biocidal agents because they have multiple biocidal properties, in particular antibacterial, antifungal and antiviral ( EP2 457 440B).
  • quaternary ammonium compounds also have the specificity of being strongly cationic compounds and tend to strongly hydrophilize the substrates in which they are incorporated.
  • hydrophilic binders such as polyvinyl alcohols or starches and applied to a cellulosic substrate
  • the level of hydrophobicity of this substrate quantifiable by the control of water absorption Cobb, decreases and for example, the required standard of 20 to 40 g/m 2 for writing printing papers or wrapping papers can no longer be achieved.
  • cellulosic supports resulting from recycling have the particularity of being more difficult to hydrophobize than noble cellulosic supports.
  • the aim of the invention is precisely to propose a biocidal protection, which is economically acceptable for substrates dedicated to mass packaging.
  • biocidal agent present on the lists of biocidal products authorized for food contact.
  • the present invention thus proposes a new biocidal composition for the surface treatment of a substrate.
  • the present invention relates to a biocidal composition for the surface treatment of a porous substrate, comprising:
  • biocidal compound based on quaternary ammonium in particular a quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC)
  • a biocidal compound based on quaternary ammonium in particular a quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC)
  • the biocidal composition comprises at least one biocidal compound based on quaternary ammonium chosen from polymeric or non-polymeric quaternary ammonium salts, in particular from non-polymeric quaternary ammonium salts, and more particularly comprises at least didecyl dimethyl ammonium chloride (DDAC).
  • DDAC didecyl dimethyl ammonium chloride
  • the present invention relates to a biocidal composition for the surface treatment of a porous substrate, comprising: - at least one hydrophilic binder,
  • biocidal compound based on quaternary ammonium chosen from non-polymeric quaternary ammonium salts of the following formula ( ⁇ 3 ⁇ 4) 2 A 2 N + C in which:
  • A identical or different, represent linear C 6 to C 20 alkyl groups, and X is an anion chosen from halide anions and sulphonate anions, and
  • At least one cationic fining agent chosen in particular from alkenyl ketene dimers (AnKD), alkyl ketene dimers (AKD), styrene-acrylates (SAE), rosins, alkenyl succinic anhydride (ASA) and mixtures thereof.
  • the biocidal compound based on quaternary ammonium comprises at least didecyl dimethyl ammonium chloride (DD AC).
  • the term “surface treatment” is intended to denote the fact of forming a deposit of a composition on the surface of a substrate, so that the support thus obtained has surface biocidal properties and the hydrophobicity wanted.
  • the surface treatment obtained according to the invention leads to the formation of a localized coating on the surface of said support and/or in the superficial part of the thickness of the support.
  • biocidal agent or “biocide”, equivalent to the terms “anti-microbial agent” designate, in general, any agent effective in regulating and/or inhibiting the growth and/or reduce the density of microorganisms such as viruses, fungi, bacteria, and/or yeasts, etc.
  • cationic bonding agent is intended to denote a bonding agent formulated in the form of a cationic emulsion, a cationic solution or a cationic dispersion.
  • a cationic fining agent can be characterized by a positive zeta potential measurement. The zeta potential can be measured using an electrophoretic mobility meter.
  • a cationic sizing agent can also be characterized by a titration of the cationic sizing agent, in particular with anionic electrolytes such as anionic polyacrylamides.
  • the titration can be measured using a Mütek PCD device.
  • a biocidal compound based on quaternary ammonium and in particular DDAC, of a particular type of fining agent within the surface treatment, makes it possible against all odds to guarantee porous and in particular fibrous substrates thus treated, a significant hydrophobicity while not altering the biocidal properties expected from the biocidal compound based on quaternary ammonium.
  • the present invention relates to a porous support, in particular fibrous, with surface biocidal properties possessing on all or part of at least one of its external surfaces, a surface treatment and preferably a coating formed from of a composition according to the invention.
  • this porous support is chosen from paper and cardboard, in particular cardboard dedicated to forming packaging cardboard, in particular flat or corrugated and for example formed at least in part from recycled fibers.
  • the present invention relates to a process for the manufacture of a porous support with surface biocidal properties, according to the invention, comprising at least the steps consisting in: a) providing a porous substrate, in particular fibrous and preferably formed at least in part from recycled fibers, b) bringing all or part of at least one of the outer surfaces of said substrate into contact with a composition according to the invention under conditions suitable for forming a deposit of said composition thereon and c) drying said deposit to form said porous support endowed with biocidal properties.
  • the subject of the present invention is the use of a composition in accordance with the invention for conferring biocidal, in particular antiviral, properties on a porous substrate, in particular a fibrous substrate.
  • the subject of the present invention is the use of a composition according to the invention for reinforcing the hydrophobicity of a porous substrate, in particular a fibrous substrate, in particular formed at least in part from recycled fibers .
  • the subject of the present invention is the use of a porous support according to the invention to prepare a banknote or a security sheet or a paper for printing, writing or copying.
  • the subject of the present invention is the use of a porous support according to the invention to prepare a packaging cardboard.
  • the subject of the present invention is the use of a porous support according to the invention for preparing papers and non-woven and textile materials, writing printing papers, coated papers and papers for copy.
  • Quaternary ammonium compounds in particular quaternary ammonium salts, are known as antimicrobial and/or microbicidal agents, and more particularly as bacteriostatic (or antibacterial) and/or bactericidal and/or fungistatic (or antifungal) agents. and/or fungicides.
  • Quaternary ammonium salts generally include at least one quaternary ammonium cation with an appropriate anion, X,.
  • the cation is more particularly of the following formula:
  • Ri, R 2 , R 3 and R 4 being able to be of various nature.
  • Ri, R 2 , R 3 and R 4 can be chosen, independently of each other, from alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, heterocyclic aromatic or non-aromatic, or alkenyl groups, said groups possibly being substituted or not, linear or branched, and optionally interrupted by one or more heteroatoms, for example, by one or more oxygen atoms, or by one or more phosphinate groups.
  • the groups Ri, R 2 , R 3 and R 4 can together form, with the nitrogen atom which supports them, a substituted or unsubstituted heterocyclic ring.
  • the groups Ri, R 2 , R 3 and R 4 are alkyl groups, preferably linear, in particular C 1 to C 20 .
  • the groups Ri, R 2 , R 3 and R 4 are saturated, preferably linear, in particular C 1 to C 20 alkyl groups.
  • the Ri, R 2 , R 3 and R 4 groups together comprise at least four carbon atoms.
  • the total number of carbon atoms of the groups Ri, R 2 , R 3 and R 4 can be at least 10.
  • at least one of the groups Ri, R 2 , R 3 and R 4 in particular two of Ri, R 2 , R 3 and R 4 , comprise from 6 to 20 carbon atoms, in particular from 8 to 18 carbon atoms.
  • the anion, X, of the quaternary ammonium salt may in particular be chosen from halide anions, for example chloride, fluoride, bromide or iodide, and sulphonate anions.
  • the anion of the quaternary ammonium salt can be chosen from halide anions.
  • the anion of the quaternary ammonium salt can be a chloride.
  • non-polymeric quaternary ammonium salts can more particularly be of the following formula [Chem 2]
  • the quaternary ammonium salt used as an antimicrobial agent according to the invention may be of formula (CH 3 ) n (A) m N + X ⁇ , in which n is 2 and m is 2 and A , which are identical or different, are as defined above for Ri, R 2 , R 3 and R 4 .
  • A which are identical or different, in particular identical, can represent linear C 8 to C 20 , in particular C s to C 12 , in particular C s to C 12 , linear alkyl groups.
  • A which are identical or different, in particular identical, can represent saturated linear C 8 to C 20 , in particular C s to C 5 , in particular C s to C 12 , alkyl groups.
  • DDAC didecyl dimethyl ammonium chloride
  • dioctyl dimethyl ammonium chloride dioctyl decyl dimethyl ammonium chloride
  • octyl decyl dimethyl ammonium chloride octyl decyl dimethyl ammonium chloride.
  • the biocidal compound based on quaternary ammonium can also be a polymeric quaternary ammonium salt, that is to say a compound whose chemical formula comprises a repetition of “quaternary ammonium” units.
  • Such a so-called polymeric quaternary ammonium salt can be derived from at least one compound of formula (I) of which at least one of Ri, R 2 , R 3 and R 4 carries a polymerizable function, in particular d a function containing ethylenic unsaturation(s) and more particularly chosen from (meth)acrylate and allylic functions.
  • this so-called polymeric quaternary ammonium-based compound can be obtained by polymerization of at least one quaternary ammonium salt of formula (I) above, in which two of Ri, R 2 , R 3 and R 4 are groups bearing an allylic function, in particular, are allylic groups; the others being preferably alkyl groups, in particular C1 to C6, in particular C1 to C4, in particular methyl groups.
  • this compound based on polymeric quaternary ammonium is a homopolymer of diallyldialkylammonium chloride.
  • it may be the polymer of diallyldimethylammonium chloride, denoted polyDADMAC.
  • PolyDADMAC can be synthesized by radical polymerization of DADMAC in the presence of a peroxide as a catalyst; or else be commercially available.
  • a biocidal composition according to the invention uses at least didecyl dimethyl ammonium chloride (DD AC).
  • the biocidal compositions in accordance with the invention contain from 0.05 to 2.5% by dry weight, preferably from 0.25 to 1.5% by dry weight, and more preferably from 0.25 to 1% by dry weight of biocidal compound(s) based on quaternary ammonium, in particular chosen from polymeric or non-polymeric quaternary ammonium salts, in particular from non-polymeric quaternary ammonium salts polymers, and more particularly didecyl dimethyl ammonium chloride (DD AC) relative to their total weight.
  • dry weight also called “weight of active material”, denotes, without indication to the contrary, the mass content of said compound, without any volatile solvents in which it is formulated, for example water.
  • the amount of biocidal compound(s) based on quaternary ammonium, in particular DD AC is adjusted in the composition so that the surface treatment, and preferably the coating formed from the composition, contains less than 10% by dry weight and preferably less than 5% by weight of biocidal compound(s) based on quaternary ammonium and in particular DD AC relative to its total dry weight.
  • a porous support obtained according to the invention advantageously has, after a contact time of 5 hours with the human-infected Coronavirus strains HcoV-229E and HcoV-OC43 according to ISO standard 21702:2019 or ASTME 1093, antiviral activity, good to excellent, according to the criteria of standard ISO 18184:2019-06 appendix 5 and in particular very strong antiviral activity against viruses of the family of enveloped viruses with activities of 2.5 and 3.1 log reduction in viral titer.
  • Hydrophobicity is characterized as the resistance to water penetration and is therefore measured using the Cobb test (60 s). This is the quantity of water absorbed by the support in g/m 2 thanks to a cylindrical impregnation template, during a lapse of time of 60 seconds. This is a test conventionally used in the paper industry to characterize the absorption of paper.
  • this cationic sizing agent can be chosen from acrylonitrile, alkenyl ketene dimers (AnKD), alkyl ketene dimers (AKD), styrene-acrylates (SAE), rosins, succinic anhydride alkenyl (ASA) and mixtures thereof.
  • this cationic bonding agent may comprise at least one compound chosen from acrylonitrile, alkenyl ketene dimers (AnKD), alkyl ketene dimers (AKD), styrene acrylates (SAE), rosins, alkenyl succinic anhydride (AS A) and mixtures thereof.
  • this cationic sizing agent comprises at least one alkyl ketene dimer (AKD) and/or one styrene acrylate (SAE) and more preferably comprises at least one alkyl ketene dimer (AKD).
  • this cationic sizing agent comprises at least one styrene acrylate (SAE).
  • SAE styrene acrylate
  • the surface sizing agent of the cationic alkyl ketene dimer type such as that marketed by the company SOLENIS under the name AquapelTM J 215 (AKD) or even the surface sizing agent of the cationic styrene-acrylate type (SAE) such as that marketed by the company SOLENIS under the name Basoplast 270D.
  • the cationic fining agent is distinct from the biocidal compound based on quaternary ammonium used in the composition according to the invention.
  • the cationic fining agent is distinct from a quaternary ammonium salt.
  • a composition according to the invention may in particular comprise from 0.5 to 5% by weight of commercial product, preferably from 1 to 4% by weight of commercial product, and more preferably from 1 to 3% by weight of commercial product, cationic fining agent(s) based on its total weight.
  • the biocidal compound based on quaternary ammonium, and preferably didecyl dimethyl ammonium chloride, and the cationic bonding agent(s) can be used in a composition according to the invention, in a ratio weight dry weight of compound(s) based on quaternary ammonium/weight of commercial product of cationic fining agent(s) varying from 0.1 to 0.5, preferably from 0.25 to 0.375, and more preferably from 0.25 to 0.33.
  • a composition according to the invention may comprise from 0.08 to 1.5% by dry weight, preferably from 0.17 to 1.2% by dry weight, and more preferably from 0.17 at 0.9% by dry weight, of cationic bonding agent(s) relative to its total weight.
  • the biocidal compound based on quaternary ammonium, and preferably didecyl dimethyl ammonium chloride, and the cationic bonding agent(s) can be used in a composition according to the invention.
  • a dry weight ratio of compound(s) based on quaternary ammonium/dry weight of cationic bonding agent(s) ranging from 0.25 to 5.9, in particular from 0.3 to 3.6, preferably from 0.8 to 2.5, and more preferably from 0.8 to 2.2.
  • a porous support obtained according to the invention advantageously has a Cobb of at most 50 g/m 2 , preferably of 20 to 40 g/m 2 measured with the Cobb test carried out according to the standard ISO 535:2014, over a period of 60 s.
  • a composition according to the invention comprises at least one hydrophilic binder.
  • This binder is said to be hydrophilic in view of the fact that it has an affinity for water and therefore for an aqueous medium.
  • this binding agent can be chosen from polyvinyl alcohols, starches, starches, latexes, in particular acrylics or acrylic copolymers, hemicelluloses, carboxymethylcelluloses (CMC), galactomannans, gelatins, polyurethane dispersions and their mixtures.
  • polyvinyl alcohols starches, starches, latexes, in particular acrylics or acrylic copolymers, hemicelluloses, carboxymethylcelluloses (CMC), galactomannans, gelatins, polyurethane dispersions and their mixtures.
  • this binding agent comprises at least one polyvinyl alcohol and/or one starch and more preferentially comprises at least one starch.
  • It may be, for example, potato starch, in particular oxidized, wheat starch or corn starch.
  • composition according to the invention may comprise from 1 to 50% by dry weight, preferably from 2 to 40% by dry weight, and more preferably from 2 to 20% by dry weight of hydrophilic binder(s) relative to its total weight.
  • a composition according to the invention can of course comprise an aqueous solvent, in particular water, and if necessary other compounds conventionally considered for the surface treatment of porous substrates but also with regard to the biocidal activity sought according to the invention.
  • composition according to the invention may comprise one or more bacteriostatic, bactericidal, fungistatic, fungicidal, yeasticidal, virucidal agents distinct from a biocidal compound based on quaternary ammonium.
  • This or these ancillary biocidal agents may in particular be chosen from p-[(Diiodomethyl)sulfonyl]toluol, 3-iodo-2-propynylbutyl carbamate, methyl-1H-benzimidazol-2-ylcarbamate, monolaurin, compounds based on isothiazoline or derivatives of isothiazolone, chitosan or derivatives of chitin, zinc zeolite, silver ions, in particular silver chloride, silver in supported particulate form and triclosan and their mixtures.
  • a composition according to the invention contains at least one bacteriostatic and/or bactericidal agent chosen from compounds based on chitosan or chitin derivatives, zinc zeolite, silver ions, silver in particulate form supported and triclosan and mixtures thereof.
  • a composition according to the invention contains at least one fungistatic and/or fungicidal agent chosen from compounds based on isothiazoline or isothiazolone derivatives, chitosan or chitin derivatives, zinc zeolite, ions silver, silver in supported particulate form and triclosan.
  • a composition according to the invention contains at least one fungistatic agent and/or fungicide based on p-[(Diiodomethyl)sulfonyl]toluol.
  • a composition according to the invention contains at least one fungistatic agent and/or fungicide based on methyl-1H-benzimidazol-2-ylcarbamate.
  • a composition according to the invention contains at least 3-iodo-2-propynylbutyl carbamate (IPBC).
  • composition according to the invention contains at least one virucide, in particular of natural origin.
  • viral designates 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.
  • viruses can be naked viruses or enveloped viruses.
  • retroviruses cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackieviruses, the virus of encephalomyocarditis, picomaviruses including rhinoviruses, DNA or RNA viruses in particular flaviviridae, the AIDS virus, influenza viruses and in particular H1N1, coronaviruses and in particular human-infected coronaviruses Hcov-229E, Hcov -0C43, SARS-COV-2, smallpox virus, yellow fever virus, hepatitis C virus, Ebola viruses, herpes viruses, Epstein-Barr virus, varicella-zoster virus, rubella virus, or even simian virus 40 or SV40.
  • virucide of natural origin we mean any virucide that pre-exists in nature or that can be synthesized from natural compounds that exist in nature.
  • the virucides of natural origin that 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 By way of example of such virucides, mention may in particular be made of monolaurin which can be obtained by synthesis from glycerol and lauric acid.
  • monolaurin is intended to designate both monolaurin that preexists naturally and that obtained by synthesis from glycerol and lauric acid.
  • the virucide of natural origin may in particular be chosen from monolaurin, lactoferrin and essential oils exhibiting antiviral activity, such as for example laurel essential oil.
  • composition 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(s) of natural origin relative to its total weight.
  • the auxiliary biocide is at least monolaurin.
  • composition according to the invention contains at least one in particular mineral filler.
  • Such a component is in particular advantageous for giving the surface treatment formed by the composition according to the invention increased surface qualities and in particular for improving its coefficient of friction.
  • This filler can be chosen from mineral fillers, in particular colloidal silica, sodium silicates, sodium aluminosilicates, natural or precipitated calcium carbonates, talc, natural or calcined kaolin, alumina hydrate, titanium, aluminum silicates, barium sulphate, and mixtures thereof, and from organic fillers, in particular fillers or plastic pigments.
  • a composition according to the invention comprises at least one mineral filler and in particular calcium carbonate.
  • a composition according to the invention may thus comprise from 0.1% to 5% by weight, preferably from 0.1% to 1% by weight, of filler(s), in particular mineral, relative to its total weight.
  • Another object of the invention relates to a porous support of which all or part of one of its external surfaces has been treated using a composition in accordance with the invention, and in particular to form a coating.
  • This porous support can advantageously be fibrous, in particular of the paper or cardboard type, and in particular a cardboard dedicated to forming packaging cardboard, said cardboard being formed of virgin fibers or preferably at least partly or even entirely of recycled fibers.
  • a fibrous substrate suitable for the invention to prepare this support is formed in particular of fibers which can be natural, artificial and/or synthetic. It may also contain mineral fillers.
  • the fibers entering into the composition of the substrate comprise natural fibers.
  • cellulosic fibers such as wood fibers, for example hardwood fibers, resinous fibers or their mixture, cotton fibers, bamboo, straw, abaca, asperto, hemp, jute, flax, sisal and their mixtures.
  • the pulp used to form paper or board can be bleached, semi-bleached or unbleached, commonly referred to as bleached, semi-bleached or unbleached fibers respectively.
  • the fibers entering into the composition of the substrate comprise cellulosic fibers, in particular cotton fibers.
  • said cellulosic fibers are a mixture of cotton fibers and wood fibers.
  • this substrate is formed at least in part or even essentially from recycled fibers, for example from the trituration of waste paper.
  • the fibers entering into the composition of the substrate may comprise synthetic fibers.
  • the presence of synthetic fibers, mixed with cellulosic fibers, in the substrate according to the invention makes it possible to improve the properties of resistance to tearing of said substrate.
  • the porous and more particularly fibrous substrate can of course contain other components usually considered in the paper or cardboard industry and in particular chosen from humectants such as, for example, compounds of the polyol type, such as , for example, glycerin, also called glycerol, propylene glycol, polyethylene glycol, butylene glycol, glyceryl triacetate, or even sorbitol; fillers in particular such as those defined above and anionic or cationic bulk bonding agents, for example intended to develop part of the hydrophobicity of the finished substrate.
  • humectants such as, for example, compounds of the polyol type, such as , for example, glycerin, also called glycerol, propylene glycol, polyethylene glycol, butylene glycol, glyceryl triacetate, or even sorbitol
  • fillers in particular such as those defined above and anionic or cationic bulk bonding agents, for example intended to develop part of the hydrophobicity of the
  • the porous support obtained according to the invention is a fibrous support of paper for banknotes or security documents or a wrapping paper, or a paper for copying or a cardboard support for making packaging cartons, in particular cartons dedicated to forming packaging cartons, in particular flat or corrugated.
  • the porous support can also be a leather or a surface-treated wood according to the invention.
  • At least one of the external surfaces of the porous substrate considered is brought into contact with a composition according to the invention, under conditions suitable for forming thereon a deposit of said composition, and the deposit thus obtained is dried to form the expected porous support.
  • the drying step can in particular be carried out at a temperature greater than or equal to 80°C, for example greater than or equal to 90°C, preferably greater than or equal to 100°C.
  • This contacting step can be carried out according to different variants.
  • the formation of the deposit can be carried out according to different modes of application of the composition.
  • the fibrous substrate is immersed in a solution containing at least the composition according to the invention.
  • the surface of at least one face of the substrate is sprayed with a solution containing at least the composition according to the invention.
  • at least one of the external surfaces of the substrate is coated using a coating solution containing at least the composition according to the invention.
  • the coating or coating can be done by an air knife system, a curtain coating, by a pencil system, blade or doctor blade, rollers, in particular pre-dosed, engraved or transfer, by a press gluing machine (or "size-press"), by an impregnator, or by a film transfer press (“film-press").
  • the surfacing of at least one of the outer surfaces of the substrate is carried out with a surfacing bath containing at least the composition according to the invention.
  • the porous substrate having been coated and/or surfaced beforehand is printed, partially or totally on the surface, using an ink containing at least the composition according to the invention.
  • an overprint varnish containing at least one composition according to the invention can be flexographic, gravure or spray application.
  • These embodiments are particularly advantageous insofar as their implementation is compatible with a conventional process for manufacturing a porous, in particular fibrous, support, in particular of the paper type, that is to say concomitantly with the conventional manufacturing steps. .
  • the present invention relates to the use of a porous support, in particular fibrous according to the invention for preparing papers, for covers ("kraft liner” or “test liner”) and/or corrugated paper used in the composition of cardboard boxes. 'packaging.
  • the present invention also relates to the use of a porous support according to the invention for preparing a banknote or a security document.
  • the banknote, security document or cardboard packaging according to the invention has the same properties as the porous support according to the invention, measured according to the characterization methods defined for this fibrous support.
  • the present invention also relates to the use of a porous support according to the invention for preparing papers and non-woven and textile materials, writing printing papers, coated papers and copy papers.
  • the porous support according to the invention is dedicated to forming 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, known as OVDs, holograms, lenticular devices, interference effect elements, in particular iridescent elements, liquid crystals, effect pigments magnetically orientable and interference multilayer 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.
  • OVDs optically variable devices
  • holograms holograms
  • lenticular devices lenticular devices
  • interference effect elements in particular iridescent elements
  • liquid crystals effect pigments magnetically orientable and interference multilayer structures.
  • these 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.
  • watermarks produced during the manufacturing process of the fibrous substrate.
  • said security element is chosen from so-called luminescent elements, which can be revealed under UV or under IR, these luminescent elements possibly being in the form of particles, fibres, planks, security thread integrated at least in part into the fibrous substrate, bands or patches affixed or printed on the fibrous substrate.
  • said security element is chosen from elements that can be detected automatically, in particular optically or magnetically, these detectable elements commonly called markers or taggants being integrated into the fibrous support or into visual or luminescent security elements.
  • a security sheet can also include a radio frequency identification device, called RFID, also providing an identification and traceability function to the security sheet.
  • the security sheet considered according to the invention is or forms part of a security document.
  • the security document considered according to the invention is an official document, in particular an identity document, a passport, a residence permit or a visa.
  • the porous support according to the invention can be dedicated to form a driving license, an access card, a loyalty card, a photocopy card, a canteen card, a playing card, a collectible card, a means of payment, in particular a payment card, a banknote, a purchase voucher or a receipt, a ticket for access to cultural or sporting events, a certificate of authenticity, a book or a magazine.
  • SAE cationic styrene-acrylate
  • DDAC Didecyl dimethyl ammonium chloride
  • IPBC 3-iodo-2-propynylbutyl carbamate
  • % by weight are expressed as % by weight of the commercial products which are sources of compounds according to the invention.
  • This test aims to determine the weight of bath taken during the coating/surfacing step by weighing the paper before then after the coating/surfacing without practicing drying. It is expressed in grams of wet coating applied per unit area (m 2 ) or in % by weight.
  • results, expressed in log, correspond to the reduction in viral load for the contact times considered compared to a reference without antimicrobial treatment.
  • Example 1 Preparation of biocidal compositions in accordance and not in accordance with the invention
  • the starch bath is produced by cooking for 20 min at 90°C an aqueous starch composition of the carboxylated potato starch type (Perfectamyl P 255SH).
  • compositions 1 and 2 in accordance with the invention are prepared from this starch bath in which the surface sizing agent in question is mixed. After obtaining a homogeneous mixture, the DDAC and, where appropriate, the IBPC are added to the bath.
  • Control compositions 3 to 5 are also prepared in this way.
  • Example 2 Preparation of porous substrates conforming and not conforming to the invention by treatment of a substrate based on recycled pulp
  • Porous substrates are prepared according to a conventional papermaking process and from a recycled pulp composed of 100% recycled cardboard fibers, incorporating or not the bulk sizing agent of the cationic styrene acrylate type Fennosize KD 860D, of which the content is expressed in Table 2 as % by weight of commercial product relative to the dry matter weight of the recycled pulp.
  • the substrates have a basis weight of 160 g/m 2 .
  • the substrates obtained then undergo surfacing in a size press (“siz.e-press” in English) with some of the compositions detailed in Example 1.
  • composition in accordance with the invention like those of tests A and B makes it possible to achieve an interesting compromise between the hydrophobic properties and the biocidal activity of the paper.
  • test A shows that the implementation of a composition 1 according to the invention significantly reduces the Cobb value and therefore causes a gain in hydrophobicity for recycled paper. This same advantageous result is verified with test B.
  • the two supports obtained according to tests A and B have very strong antiviral activity against the Coronavirus HcoV-229 E strain, representative of enveloped viruses, with a value of 2.5 log. Finally, the comparison of the supports obtained according to tests A and B shows an improvement in the antifungal activity when IPBC is added to composition A.
  • Example 3 Preparation of porous substrates conforming and not conforming to the invention from a substrate based on non-recycled pulp.
  • Fibrous substrates are prepared from a noble pulp composed of 80% bleached softwood fibers and 20% eucalyptus kraft pulp and by incorporating therein the mass sizing agent of the cationic styrene-acrylate type Fennosize KD 860D the content of which is expressed in Table 3 as % by weight of commercial product relative to the dry matter weight of the recycled pulp.
  • the substrates thus obtained undergo surfacing according to the method described in Example 2, with one of the compositions detailed in Table 3 below.
  • Example 4 Preparation of biocidal compositions in accordance and not in accordance with the invention
  • Compositions 6 to 10 which follow are prepared according to the protocol already specified in Example 1 with cooked wheat starch, and Table 4 gives the proportions of their various components.
  • composition 10 in accordance with the invention, the CaCCL is first incorporated into the starch bath and the stirring is prolonged until it is dispersed before adding the other compounds.
  • compositions are applied to one side of a fibrous substrate of the paper type with a basis weight of 160 g/m 2 based on non-recycled pulp and having a mass bond.
  • a fibrous substrate of the paper type with a basis weight of 160 g/m 2 based on non-recycled pulp and having a mass bond.
  • Such a substrate is conventionally used for packaging cartons.
  • the surfacing is done using a pencil application process.
  • Each of the coatings is then analyzed for its hydrophobic properties as described above and the values measured are given in Table 4 below.
  • the antiviral activity is measured for test M with the Coronavirus OC43 strain according to the method described in the Materials and Methods chapter.
  • the reduction in viral load obtained is 3.1 log compared to the reference fibrous substrate without antimicrobial treatment. It is therefore found that the compositions according to the invention do indeed confer effective antiviral protection on the fibrous substrate.
  • Test M also reveals that the support treated with composition 10, also containing calcium carbonate, advantageously has an improved coefficient of friction compared to that observed for test K.
  • Example 5 Preparation of a biocidal composition in accordance with the invention
  • An aqueous starch bath is first prepared from 11.4% by weight of cooked corn starch and the whole is heated to 65°C until a homogeneous mixture is obtained.
  • composition 11 is then prepared comprising 96.5% by weight of this cooked corn starch bath, 3.9% by weight of an Aquapel J 215 surface sizing agent at 15% by weight of MA, and 0.5% by weight of a solution of DD AC at 50% by weight of DD AC according to a protocol similar to that described in example 1,
  • This composition 11 is deposited by surfacing in a size press (or “size press”) on a 190 g/m 2 recycled pulp paper.
  • the dry deposit is 9.5 g/m 2 .
  • the Cobb value obtained according to the method detailed in the Materials and Methods chapter is 49.2 g/m 2 .
  • the reduction in viral load, with the Coronavirus HcoV-229E strain, according to the method described in the Materials and Methods chapter, is 1.6 log compared to the reference fibrous substrate without antimicrobial treatment.
  • Example 6 Preparation of a biocidal composition in accordance with the invention
  • a composition 12 is prepared comprising 96% by weight of the commercial product Mowiol 10-98 at 7.8% by weight of polyvinyl alcohol, 2% by weight of a solution of DD AC at 80% by weight of DDAC, and 1.5% by weight of Basoplast 270D surface sizing agent with 30% by weight of MA and 0.5% by weight of the commercial product Lennostrength XO (PAE resin).
  • the composition 12 thus formed is then deposited by surfacing in a size press on a paper produced in unbleached kraft pulp of 115 g/m 2 .
  • the dry deposit is 1.8 g/m 2 .
  • the Cobb value measured according to the method detailed in the Materials and Methods chapter is 42 g/m 2 .
  • the viral load evaluated with the Coronavirus OC43 strain according to the method described above, it is greater than 3 log compared to the reference fibrous substrate devoid of antimicrobial treatment.

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  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP22728626.7A 2021-05-17 2022-05-13 Supports poreux à propriétés biocides Pending EP4340611A1 (fr)

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FR2105125A FR3122805B1 (fr) 2021-05-17 2021-05-17 Supports poreux à propriétés biocides
PCT/EP2022/063027 WO2022243189A1 (fr) 2021-05-17 2022-05-13 Supports poreux à propriétés biocides

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US6315824B1 (en) * 1996-02-02 2001-11-13 Rodrigue V. Lauzon Coacervate stabilizer system
FR2838025B1 (fr) 2002-04-08 2005-08-05 Arjo Wiggins Support d'information presentant des proprietes biocides et son procede de fabrication
US20060060814A1 (en) * 2002-12-17 2006-03-23 Lucyna Pawlowska Alkenylsuccinic anhydride surface-applied system and method for using the same

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WO2022243189A1 (fr) 2022-11-24
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FR3122805A1 (fr) 2022-11-18
FR3122805B1 (fr) 2024-04-05

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