WO1998038238A2 - Dispersions polymeres antibacteriennes et fungicides - Google Patents

Dispersions polymeres antibacteriennes et fungicides Download PDF

Info

Publication number
WO1998038238A2
WO1998038238A2 PCT/EP1998/000953 EP9800953W WO9838238A2 WO 1998038238 A2 WO1998038238 A2 WO 1998038238A2 EP 9800953 W EP9800953 W EP 9800953W WO 9838238 A2 WO9838238 A2 WO 9838238A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
dispersion
antibacterial
fungicidal
silver
Prior art date
Application number
PCT/EP1998/000953
Other languages
German (de)
English (en)
Other versions
WO1998038238A3 (fr
Inventor
Robert Rupaner
Gregor Ley
Dieter Zeller
Norbert Gebhardt
Peter Mendera
Gerhart Heinz
Josef Neutzner
Gerhard Bauer
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP98912337A priority Critical patent/EP1018871A2/fr
Priority to AU67217/98A priority patent/AU6721798A/en
Publication of WO1998038238A2 publication Critical patent/WO1998038238A2/fr
Publication of WO1998038238A3 publication Critical patent/WO1998038238A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/025—Preservatives, e.g. antimicrobial agents
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • Polymers and especially polymer dispersions are susceptible to bacterial, yeast or fungal attack. After such an infestation, for example, there is discoloration of the product, a change in the viscosity, the pH and the smell.
  • the bacteria are examples of such microorganisms that attack polymers and polymer dispersions
  • Rhodotorula albicans Rhodotorula albicans
  • EP-A-0 322 814 describes a process for the preparation of polymer dispersions containing antibiotic powder, zeolites or amorphous aluminosilicate being used as the antibiotic powder, the ion-exchangeable ions being replaced by antibiotic metal ions, such as silver, copper or zinc.
  • antibacterial and fungicidal polymers which contain carboxyl groups and antibacterial and fungicidal metal ions, preferably silver ions, which are ionically bound to the carboxyl groups.
  • the antibacterial and fungicidal effect should be maintained over a long period of time.
  • the polymers are used as solids, for example in the form of coatings, or as filters.
  • antibacterial plaster compositions are known which can be used for medical applications.
  • the patches contain silver sulfadiazine, which forms a homogeneous dispersion with a solution of the adhesive used.
  • an amino acid polymer with pendant carboxyl groups neutralized as a copper, zinc and / or silver salt, can be used in resin compositions for coatings.
  • polymer dispersions containing sulfonate groups can be loaded with silver ions via ion exchangers containing silver ions.
  • JP-A-08/151310 a copolymer of styrene and maleic anhydride is first reacted with aqueous sodium hydroxide solution and then with a silver nitrate solution, a polymer precipitate being formed, which is filtered and dried.
  • the polymaleic acid silver salt copolymer thus obtained was effective against Pseudomonas aeruginosa and Staphylocuccus aureus.
  • the object of the present invention is to provide a method and a protective polymer for the preparation of antibacterial and fungicidal polymer dispersions.
  • Another object of the present invention is to provide a method for producing an antibacterial and fungicidal polymer dispersion which is stable over a long period of time.
  • Another object of the present invention is to provide a method for producing an antibacterial and fungicidal polymer dispersion, wherein agglomeration of the dispersion is prevented.
  • Another object of the invention is to provide an antibacterial and fungicidal polymer dispersion, with no protein silver being used.
  • Another object of the present invention is to provide a method for producing an antibacterial and fungicidal polymer dispersion which can be used simply to protect a large number of further polymer dispersions.
  • Another object of the invention is to provide antibacterial and fungicidal polymer dispersions which are stable over a long period of time and can be added to other dispersions without problems.
  • a process for producing an antibacterial and fungicidal polymer dispersion a polymer dispersion being mixed with an amount of a protective polymer which is dispersible in the polymer dispersion and which is sufficient for the antibacterial and fungicidal action 3 to 60% by weight, preferably 10 to 50% by weight, based on the total weight of components a) and b) without metal ions, of at least one alpha, beta-mono-ethylenically unsaturated mono- or dicarboxylic acid, which can be partially or completely neutralized or present as an anhydride, as
  • a) and b) without metal ions at least one a vinyl ester of 1 to 20 carbon atoms containing carboxylic acids, a vinyl aromatic with up to 20 carbon atoms, an ethylenically unsaturated nitrile with 3 to 6 carbon atoms, a vinyl halide or a non-aromatic hydrocarbon with 4 to 8 carbon atoms and at least 2 conjugated double bonds or ethylene or propylene as
  • Polymer dispersions are systems in which polymers are dispersed in a dispersion medium.
  • Water or a water-containing dispersing agent is often used as the dispersing medium.
  • the particles are preferably spherical and generally have an average diameter of 20 to 1000 nm.
  • these polymer dispersions are susceptible to bacterial, yeast and fungal attack and attack by other microorganisms which damage the Polymer dispersion can lead.
  • the metal ions provide protection against bacterial, yeast and fungal attack.
  • polymer dispersions especially aqueous polymer dispersions, tend to coagulate or gel when electrolytes are added.
  • aqueous metal salt-containing electrolyte solution is dropped into an aqueous polymer dispersion, high local electrolyte concentrations occur at the drop-in point. This often results in irreversible coagulation or aggregation of dispersed polymer particles at the dropping point.
  • this can be attributed to the fact that the stabilization of the disperse distribution of the dispersed polymer particles in the polymer dispersions usually takes place by means of electrical charges applied to the polymer particle surface or present there.
  • the electrical charges on the polymer particle surfaces are at least partially compensated, so that the repulsion between polymer particles is at least partially eliminated and the polymer particles can coagulate.
  • EP-B-0 318 258 shows that aggregation and destruction of a stable latex dispersion system takes place even when silver carbonate, which has an extremely low solubility in water, is introduced into the dispersion.
  • the coagulation or aggregation of the polymer particles in the dispersion can be prevented if the metal ions having an antibacterial and fungicidal action are introduced into the polymer dispersion by means of a protective polymer.
  • the protective polymer contains the antibacterial and fungicidal metal ions bound to the polymer which, when the protective polymer is added to a polymer dispersion to be protected, are distributed throughout the dispersion in such a way that coagulation or aggregation of dispersed polymer particles is prevented.
  • the protective polymer is in such an amount is used that is sufficient to provide a sufficient amount of metal ions in the entire dispersion for the antibacterial and fungicidal action.
  • the protective polymer is preferably also used as a dispersion which can be distributed particularly well in the starting dispersion.
  • the protective polymer consists of a neutralized polymer which has only an insignificant effect on the pH of the end product. Since the metal ions are already bound to the protective polymer, they only negligibly impair the surface of the dispersion particles during the addition process to a polymer dispersion. As a result, no more coagulation is observed.
  • the protective polymers can be incorporated into other colloidal systems and their end uses. Due to the small particle size ( ⁇ 1 ⁇ m) of the dispersion polymers, there are no visible inhomogeneities in the end product, for example a coating.
  • the protective polymer acts as a depot for the metal ions, especially silver ions.
  • the dispersant is preferably the same dispersant as is present in the polymer dispersion to be protected. Water or a water-containing dispersant is preferred.
  • the protective polymer can be used in the form of a fine spray-dried powder which forms a dispersion or solution when introduced into the polymer dispersion to be protected. The systems do not lose their stabilizing effect if they are spray dried or melt extruded under conditions in which conventional preservatives volatilize or decompose.
  • the protective polymer By suitable choice of the protective polymer, this can be adapted to the desired properties of the polymer dispersions to be protected, so that the properties of the finished antibacterial and fungicidal polymer dispersions and their filming are not significantly changed by the addition of the protective polymer, as is the case, for example with the addition of protein silver, as described in EP-B-0 318 258, is the case.
  • the addition of a protein susceptible to bacterial and fungal attack in the polymer dispersions to be protected is avoided.
  • metal ions, such as Ag also show no antibiotic resistance (cf. MM Gabriet et al., Curr. Microbiol. 30 (1) (1995) 17-22). The invention is explained in more detail below.
  • any antibacterial and fungicidal metal ions can be used in the protective polymers used according to the invention.
  • Suitable ions are those from groups 3 to 12 of the periodic table of the elements (groups IIIA-VIIIA according to the previous IUPAC version), such as Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Hg, Cd, Cr, Ni, Pb, preferably ions of the group IB, IIB and VHIB, preferably of silver, copper, gold, platinum and the other representatives of the platinum group, and also Cd, Hg. Ions of silver, copper and mercury are preferred. Silver ions are particularly preferred because of their high antibacterial and fungicidal activity and low human toxicity.
  • the metal ions are preferably used as oxides, hydroxides, carbonates or hydrogen carbonates.
  • these basic salts after the salt formation with acid groups of the protective polymer, no free counterions remain in the dispersant or solvent used. Salt formation takes place with the binding of water or carbon dioxide / carbonic acid.
  • Any other suitable salts can also be used. Examples of these are the formates, acetates or others Salts of carboxylic acids, salts of sulfonic or phosphonic acid, or salts of mineral acids, such as nitrates, sulfates, halides, sulfides, nitrides, but also mixed salts thereof, such as hydroxycarbonates.
  • Higher molecular anions such as polyphosphates, aluminosilicates, heteropolyphosphates and silicates are also suitable.
  • the cations can also be used as oxocations, such as PtO 2 2 + , or as complexes.
  • labile complexes are the amine complexes, such as the silver diamine or the copper tetramine complex, examples of stable complexes, for example cis-platinum complexes.
  • AgOH, Ag 2 CO 3 or Ag 2 O are preferably used, optionally as an aqueous solution complexed with NH 3 .
  • the metal compounds are preferably used as fine-grained powders with a BET surface area of 2 to 5 m 2 / g.
  • the metal oxides, hydroxides or salts can be used as a solid, but preferably as an aqueous solution or suspension.
  • Those polymers which are capable of salt formation with the antibacterial and fungicidal metal ions are used as the protective polymer.
  • the metal ion-free protective polymer comprises the following components as basic building blocks:
  • the proportion of component a) is 3 to 60% by weight, preferably 10 to 50% by weight, of component b) 97 to 40% by weight, preferably 90 to 50% by weight and the component c) 0 to 50 wt .-%, preferably 0 to 20 wt .-%, based on the total weight of components a) and b).
  • the amount of component d) is 0 to 20% by weight, preferably 0.1 to 5% by weight, based on the total weight of components a), b) and c).
  • the weight information does not include the weight of the metal ions.
  • Monomers a can optionally be present or used in partially or completely neutralized form.
  • NR ⁇ R 2 R 3 R 4 + with R 1 to R 4 C 1 to C 10 alkyl or hydroxyalkyl groups, which are optionally interrupted by oxygen atoms, alkali metals, alkaline earth metals, but also the antibacterial and fungicidal acting metal ions.
  • the neutralization process can also take place during the actual polymerization of the protective polymer by adding suitable metal compounds one or more times or also continuously.
  • suitable metal compounds for example, acrylic acid, methacrylic acid, maleic acid, fumaric can accordance acid, crotonic acid, itaconic acid, acrylamidoglycolic acid, acrylamidopropanesulfonic acid (AMPS) and maleic or fumaric monoesters, j in particular C ⁇ -.
  • Alkanols used become.
  • the anhydrides of the dicarboxylic acids can also be used.
  • methacrylic acid or acrylic acid is used.
  • C ⁇ Q - in particular C ⁇
  • C ⁇ can be used as monomers of component b) .
  • ⁇ o-alkyl (meth) acrylates are used, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • n-butyl acrylate is used.
  • Styrene is preferably used as the vinyl aromatic compound having up to 20 carbon atoms.
  • Examples of usable vinyl esters of carboxylic acids having 1 to 20 carbon atoms are vinyl acetate and vinyl propionate or vinyl formamide.
  • Compounds with two conjugated double bonds that can be used as component b) are, for example, butadiene, isoprene or chloroprene.
  • N-Butyl acrylate is particularly preferably used.
  • the monomers of component c) can be any ethylenically unsaturated
  • the monomers of component c) are selected from
  • the monomers of component d) used are monomers which contain two or more functional groups, in particular double bonds which are capable of copolymerization, and which contain are preferably not conjugated in the 1,3 positions.
  • Suitable monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, dialyl phthalate, divinyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyla acrylate, allyl methacrylate, allyl methacrylate, allyl methacrylate.
  • Methallyl methacrylate is preferably used.
  • the cross-linking polyfunctional monomers d are used to cross-link the polymer to three-dimensional polymer particles. They are used in particular when simply charged metal ions, such as Ag + , are used as metal ions with an antibacterial and fungicidal action. When two or more charged antibacterial and fungicidal metal ions are used, the metal ions can have a crosslinking action if they form salts with two or more acid groups in different polymer chains, so that in one embodiment of the invention it is possible to dispense with monomers of component d). If no two- or multiply charged metal ions are used in the protective polymer, at least one crosslinking polyfunctional monomer is preferably used according to one embodiment of the invention.
  • the protective polymer can be prepared by any known polymerization process. According to one embodiment of the invention, it is carried out by anionic, cationic or preferably free-radical polymerization, such as bulk, solution, suspension, mini-suspension, mini-emulsion or emulsion polymerization. This polymerization process are known to the person skilled in the art.
  • the monomers can be polymerized as usual in the presence of a water-soluble initiator and an emulsifier at preferably 20 to 140 ° C., optionally under elevated pressure in water as an emulsifier.
  • Suitable initiators are, for example, sodium, potassium and ammonium peroxodisulfate or peroxosulfate, tert-butyl hydroperoxide, hydrogen peroxide, water-soluble azo compounds or redox initiators.
  • the emulsifiers used are, for example, alkali metal salts of longer-chain fatty acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated diphenyl ether sulfonates.
  • reaction products of alkylene oxides in particular ethylene or propylene oxide with fatty alcohols, come as emulsifiers,
  • acids or phenol or alkylphenols which can be sulfated and neutralized.
  • Buffer substances can optionally be used in the polymerization to adjust the pH to a certain value.
  • the acid groups or acid anhydride groups in the polymer can be converted into salt groups after the polymer has been prepared.
  • the protective polymer is preferably obtained in the form of a protective polymer dispersion during emulsion polymerization, the mean particle size being 20 to 1000 nm, preferably 50 to 500 nm, in particular 100 to 300 nm.
  • the solids content of the protective polymer dispersion is 5 to 70% by weight, preferably 20 to 55%, particularly preferably 30 to 50%.
  • a low viscosity is set, ie the dynamic viscosity of the dispersion is below 500 mPas, preferably below 100 mPas according to Brookfield, DIN 53019, dynamically at 25 ° C. in a Contraves Rheomat 115 (MS DIN 145) measured.
  • composition of the polymer is chosen so that a glass transition temperature in the range from -40 to + 120 ° C, preferably -30 to + 60 ° C, very preferably between -20 and + 30 ° C results (calculated according to the method of TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956)).
  • the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
  • the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972), pages 782-796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample.
  • the particle size distribution of the protective polymer dispersion is preferably narrow and monomodal, so that all particles are evenly loaded with the metal ions. Widely distributed or polymodal dispersions can also be used to achieve lower viscosities.
  • components a) to d) are first reacted to form a polymer dispersion by means of the emulsion polymerization process, and the polymer particles obtained are then reacted with the metal ions to form the protective polymer.
  • the protective polymer consists of the following monomers:
  • nBA 70 to 95% nBA, 8 to 25% MAS, 5 to 3% MAMA
  • 40 to 70% nBA 10 to 30% MMA, 8 to 25% MAS, 0 to 5% MAMA, butanediol dimethacrylate or divinylbenzene
  • 20 to 70% nBA 70 to 20% S, 8 to 25% MAS, 0 to 5% MAMA
  • n-butyl acrylate can also be partially replaced by ethyl acrylate.
  • nBA n-butyl acrylate
  • S styrene
  • EHA ethylhexyl acrylate
  • MMA methyl methacrylate
  • MAMA methallyl methacrylate
  • AN acrylonitrile
  • MAS methacrylic acid
  • MEMO trimethoxysilylpropyl methacrylate. (Percentages are% by weight).
  • metal compounds such as oxides or basic salts, by means of which the acid groups are converted into salt groups, can be added. These metal compounds are described above under "metal ions”.
  • the metal compound is generally incorporated into the dispersion or solution of the polymer with stirring for several hours at a pH of preferably below 7, in particular below 3, and a reaction temperature above the dynamic glass transition temperature of the polymer.
  • auxiliaries such as wetting agents or surfactants can also be used, which increase the colloidal stability of the system.
  • metal compounds having an antibacterial and fungicidal action are incorporated, it is also possible, according to one embodiment of the invention, to start from polymers which, for example, initially only contain anhydride groups instead of the acid groups. Depending on the conditions, the anhydride ring can be opened during the incorporation, so that a protective polymer with the desired metal salt content is obtained.
  • the amount of metal compounds introduced is chosen so that the desired metal ion content is set in the protective polymer.
  • the amount of metal ions used is selected so that 1 to 100 mol% of the acid groups present in the polymer or groups which can be converted into acid groups, such as anhydride groups, at least component a), are converted into metal salt groups. 10 to 100 mol%, in particular 30 to 100 mol%, of the acid groups of component a) are preferably converted into metal salt groups of the metal ions which have an antibacterial and fungicidal action.
  • the pH is preferably adjusted to about 7 with ammonia.
  • AgOH or Ag 2 O can also be used as a complexed aqueous solution with NH 3 .
  • the protective polymer used according to the invention can be used in any suitable form for the preparation of antibacterial and fungicidal polymer dispersions, provided that this form permits the formation of a protective polymer dispersion in a mixture with or in the polymer dispersion to be protected.
  • the protective polymer is used in the form of a dispersion.
  • concentration of the protective polymer with metal ions in the dispersant is preferably 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the total protected dispersion.
  • the protective polymer dispersion is preferably present in the same dispersant as the polymer dispersion to be protected. Any suitable dispersant can be used. Water or water-containing dispersants are preferably used.
  • the protective polymer is in the form of a finely divided powder in the one to be protected Polymer dispersion entered. Pre-moistening, dissolving or dispersing is also possible. This finely divided powder can be obtained, for example, by spray drying from the reaction mixture used to prepare it. Spray drying processes are known.
  • the fine protective polymer powder can be mixed with a powder of the polymer to be protected in a dry or moistened state, after which the mixture is dispersed or dissolved in a suitable dispersant, preferably water.
  • the protective polymer can be introduced into the polymer dispersion to be protected in any manner which ensures intensive mixing of the protective polymer with the polymer dispersion to be protected.
  • the rate at which the protective polymer is added is not critical, so that a sufficient amount of the protective polymer or the protective polymer dispersion can be added to a polymer dispersion to be protected and stirred until the protective polymer is homogeneously distributed in the polymer dispersion to be protected. Aggregation or coagulation of the polymer particles to be protected in the polymer dispersion does not occur.
  • the antibacterial and fungicidal polymer dispersions obtained in this way have a long shelf life and do not tend to agglomerate or coagulate.
  • the distribution of the antibacterial and fungicidal metal ions in the finished, protected polymer dispersion is quickly established.
  • the protective polymers used according to the invention can be used to protect any suitable polymer dispersions from bacterial, yeast or fungal attack or from other microorganisms.
  • the protective polymers containing metal ions according to the invention can be introduced into any colloidal systems. These can include polymer dispersions which are obtained by emulsion polymerization of monomers and monomer mixtures of acrylates, stryol-acrylate, styrene-butadiene, styrene-butadiene-acrylonitrile, vinyl and / or vinylidene chloride, butadiene-isoprene, vinyl acetate, ethylene-vinyl acetate, etc. . They can also be secondary dispersions, ie systems which are obtained by solution or bulk polymerization and which are emulsified in a subsequent step.
  • polymers which are obtained by polycondensation or polyaddition for example polyesters, polyamides, polyepoxides, polysulfones, polyketones, polyurethanes, polyethylene, polypropylene, polyethers, polyimines, etc.
  • the Prepolymers are already self-emulsifying in water and lead, for example, to polyurethane dispersions or polyethylene dispersions.
  • Products of other polymerization technologies that are too lead systems that differ in terms of the final particle size for example miniemulsion, microemulsion, suspension, microsuspension polymerization, lead to disperse systems which can be protected against attack.
  • Inorganic systems are also not protected against microbial attack.
  • suspensions and slurries of inorganic pigments, fillers such as calcium carbonate or titanium dioxide, iron oxide can be microbially infected and only develop their harmful effects after application conditions.
  • Transparent, water-soluble protective polymer metal salts can also be used to stabilize solutions such as polyacrylic acid solutions or maleic acid copolymer solutions or else emulsifier solutions and other water-soluble components which are required for the production of such colloidal systems.
  • stabilized systems do not detract from their stabilizing effect if they are spray-dried or melt-extruded, if appropriate, with conventional preservatives evaporating.
  • Suitable polymer dispersions to be protected are, for example, those of natural rubber, latex or synthetically produced rubber latex or polymer latex. These dispersions are used, for example, for the production of latex products which are used, for example, in medical or cosmetic applications, in the sanitary or food sector.
  • polymer dispersions which are used as paints in the exterior or interior, and polymer dispersions which can be used as adhesives, impregnants, binders or coating agents.
  • the protective polymers used according to the invention can also be used in those polymer dispersions which are used for the production of impact-modified plastics, such as for the production of ABS or ASA plastics or filter materials.
  • polymer dispersions to be protected are those of polyvinyl acetate, polyacrylate, epoxy resins or urethane resins.
  • thermoplastic or thermosetting systems After addition to thermoplastic or thermosetting systems, the microbial attack on them is made more difficult. Examples of this are all types of plastics such as packaging containers, foils, kitchen appliances, synthetic fibers, (latex) mattresses. It can also be added to fluid systems such as coolants or lubricants.
  • preservatives such as isothiazolinones
  • polymer dispersions by oxidizing compounds, by reducing compounds, by strong nucleophiles such as mercaptans.
  • the effectiveness of the (silver-containing) dispersions according to the invention is not impaired by residual proportions of oxidizing agents such as active oxygen. Active oxygen is the excess of peroxidic oxidizing agent, which is determined by iodometric titration and converted into oxygen.
  • the protective polymer used according to the invention or the protective polymer dispersion is incorporated in an amount of the polymer dispersion to be protected which is sufficient for the antibacterial and fungicidal action.
  • the polymer dispersion to be protected is mixed with such an amount of the protective polymer or the protective polymer dispersion that in the finished dispersion 0.1 to 5000 ppm, preferably 5 to 1000 ppm of antibac terial and fungicidal metal ions are present, based on the total weight of polymer.
  • the polymer dispersions according to the invention are stable in storage over a long period of time and do not tend to agglomerate or coagulate. They are protected against fungal or bacterial attack over a long period of time, which also contributes to the stability of the dispersions.
  • the invention further relates to the protected polymer dispersions which can be prepared as described above and which comprise a mixture of a polymer dispersion to be protected and a protective polymer dispersion as described above.
  • the metal content is determined by atomic absorption spectroscopy.
  • the proportion is given, for example, as the Ag concentration in ppm, regardless of the oxidation state of the metal.
  • Emulsifier 1 35 wt. -% solution of a sodium salt of a sulfated C12 / C14 fatty alcohol ether sulfate with about 30 mol EO.
  • Emulagator 2 35% by weight solution of the sodium salt of a sulfated p-nonylphenol ethoxylate with 25 mol EO.
  • Emulsifier 3 15 wt .-% solution of the sodium salt of a sec. CIO to C16 alkylbenzenesulfonates.
  • a quantity of water (840 g) and 10% of the monomer emulsion ME1 below are heated to 85 ° C. under nitrogen and 10% of a solution of 4.8 g of sodium persulfate in 200 g of water are added. After 15 minutes, the remaining amounts of the monomer emulsion and the initiator solution are continuously fed in over 2 hours. The mixture is then kept at the polymerization temperature for a further 90 min. The resulting dispersion is filtered after cooling. A coagulum-free and speck-free polymer dispersion with a pH of 1.8, an LD of 88%, ie an average particle size of 133 nm (light scattering) and a solids content of 39.7% is obtained.
  • Example 1 DA1 is reworked analogously to DE 40 04 915, with the difference that the polymer composition is 85.5% n-butyl acrylate, 7% acrylonitrile and 7.5% methacrylic acid.
  • 450 g of the dispersion (51.2% by weight) are diluted with 68.7 g of water, mixed with 11.3 g of emulsifier solution 2 and a slurry of 10.8 g of silver oxide in 132 g of water, for 4 hours at room temperature and Stirred at 80 ° C for 3 h. After cooling, filter through a 120 ⁇ m filter, no residue is obtained.
  • the dark brown dispersion has a pH of 5.4, a solids content of 36.5% by weight and a particle size of 137 nm (light control). The silver content was determined to be 1.50 g / 100 g of dispersion.
  • the polymer dispersion from Example 1 of EP-A-0 557 694 (composition: 36% styrene, 30% n-butyl acrylate, 20% methyl methacrylate, 14% methacrylic acid) is adjusted to a pH of 8 with aqueous ammonia.
  • the polymer had an average particle size of about 80 nm, the light transmission was 94% (0.01% by weight, 2.5 cm layer thickness).
  • the dispersion was dried by the spray drying method under nitrogen in a laboratory spray dryer. A slightly free-flowing, fine dusty, non-hygroscopic, white powder was obtained, which has an average particle size of 5 to 25 ⁇ m and a bulk density (after shaking and settling) of 0.4 to 0.5 g / cm 3 .
  • a quantity of water (1740 g), 80 g of emulsifier solution 2, 680 g of the monomer emulsion ME 5A and half of a solution of 23 g of sodium persulfate in 300 g of water are heated to 85 ° C. under nitrogen. After the reaction has started, the rest of the emulsion ME5 and the rest of the initiator solution are added in 3 h and then polymerized for 1 h. After cooling, the pH is concentrated with about 55 g. Ammonia adjusted to about 8 and the dispersion filtered through a 200 ⁇ m filter. A polymer dispersion with an LD value of 87%, an average particle size of 140 nm (light scattering) and a solids content of 40% is obtained. The residual monomer proportions were each ⁇ 10 ppm determined (gas chromatography). The active oxygen content of the dispersion was determined to be 37 ppm.
  • a quantity of sodium pyrophosphate (5 g), water (1100 g), 20 g of emulsifier solution 3, 170 g of the monomer emulsion ME 5B, and 10% of a solution of 12 g of sodium persulfate in 500 g of water are heated to 83 ° C. under nitrogen. After the reaction has started, the rest of the emulsion ME5 are added in 3 hours and the rest of the initiator solution in 5 h and then polymerized for 1 h. After cooling, the pH is concentrated with about 20 g. Ammonia set to 6.5 and the dispersion filtered through a 200 ⁇ m filter.
  • a polymer dispersion with an LD value of 60%, an average particle size of 235 nm (light scattering) and a solids content of 50% is obtained.
  • the active oxygen content is determined to be 10 ppm, a gas chromatographic analysis provides 1500 ppm butyl acrylate and 400 ppm butyl propionate.
  • Example 1 DA1 is reworked from DE-A-40 04 915 (polymer composition 78.5% n-butyl acrylate, 7% acrylonitrile and 14.5% methacrylic acid). A 49.5% by weight dispersion having a pH of 2.8 and a particle size of approximately 170 nm (light scattering) is obtained.
  • 240 g of a 10% strength by weight aqueous solution of silver nitrate are added to 75 g of a 10% strength by weight aqueous solution of sodium carbonate at 30 ° C. while stirring. After 30 minutes, the silver carbonate formed is filtered off and washed. The silver carbonate is introduced in portions into 50 g of the mixed dispersion AD3, which has been diluted with 50 g of water and mixed with 5 g of emulsifier 2, with vigorous gas evolution occurring. The dispersion is stirred for a further 3 h at 50 ° C. and then has a violet color.
  • Example 8 (copper dispersion)
  • a quantity of water (1300 g) and 10 g of hydrogen peroxide (30% by weight) are heated to 60 ° C., 5% of the monomer emulsion ME 8 and 10% of the reducing agent solution from 6 g of ascorbic acid in 250 g of water are added. After 15 minutes, the remaining amounts are started to be fed continuously in 2 hours. The mixture is then kept at the polymerization temperature for a further 90 min. The resulting dispersion is filtered after cooling. A coagulum-free and speck-free polymer dispersion with a pH of 1.4, an LD of 77%, an average particle size of 150 nm (light scattering) and a solids content of 30.2% is obtained.
  • Example 6 Analogously to Example 6, 500 g of AD3 mixed dispersion are treated with freshly precipitated lead carbonate, so that 80% of the acid groups are neutralized. After adding lead carbonate in portions and the evolution of gas has subsided, the dispersion is stirred for a further 3 h at 70 ° C., then cooled and filtered.
  • Example 5c 250 g of the mixed dispersion AD 3 (Example 5c) are mixed with stirring with 0.58 g of the silver dispersion B from Example 2 with stirring and stirred for 1 hour. A white dispersion free of coagulum and specks is obtained. The silver content is determined to be 34 ppm.
  • test organisms are used to represent the individual groups of organisms. Pseudomonas aeruginosa (ATCC 9027, DSM 1128), Candida albigans (ATCC 10231, DSM 1386), Aspergillus niger (ATCC 16404, DSM 1988). A caseipeptone soybean flour peptone agar (corresponds to agar medium B according to DAB 10, Appendix VIII. 10, pH 7.3) is used as the nutrient medium.
  • the efficacy data refer to Ag.
  • Mixing dispersion AD1 (Example 5a) is mixed with the silver dispersion A from Example 1 in such an amount that the silver concentrations given below are obtained. These formulations are inoculated with bacteria, yeast and mold in a preservation exposure test (6 exposures, each one week apart) and the corresponding growth is examined.
  • Pseudomonas aeruginosa Pseudomonas aeruginosa, Candida albicans and Aspergillus niger are used as test germs.
  • Mixing dispersion AD2 (Example 5b) is mixed with the silver dispersion A from Example 1 in such an amount that the silver concentrations given below are obtained. These formulations are inoculated with bacteria, yeast and mold in a preservation load test (6 loads, each after one week) and the corresponding growth is examined.
  • Pseudomonas aeruginosa Pseudomonas aeruginosa, Candida albicans, Aspergillus niger are used as test germs and the following growth is observed after the end of the test cycle:
  • Mixing dispersion ADl (Example 5A) is mixed with the silver dispersion A from Example 1 in such an amount that the silver Concentrates are obtained after the dispersion has been adjusted to the specified pH.
  • These formulations are inoculated with bacteria, yeast and mold in a preservation load test (6 loads, each after one week) and the corresponding growth is examined.
  • Example 14 (Preservation Load Test: Influence of Added Reducing Agents)
  • Mixing dispersion AD2 (Example 5B) is mixed with the silver dispersion A from Example 1 in such an amount that the silver concentrates given below are obtained after appropriate amounts of reducing agents have been added to the dispersion.
  • These formulations are inoculated with bacteria, yeast and mold in a preservation load test (6 loads, each after one week) and the corresponding growth is examined.
  • Mixing dispersion AD2 (Example 5B) is mixed with the silver dispersion A from 15 Example 1 in the amount that the silver concentrations given below are obtained after corresponding amounts of polymerization regulators have been added to the dispersion. These formulations are inoculated with bacteria, yeast and mold in a preservation load test (2 loads, each after one week) and examined for growth.
  • Rl tert-dodecyl mercaptan (tDMK)
  • R2 ethylhexylthioglycolate
  • Mixing dispersion AD2 (Example 5B) is mixed with the dispersion A from Example 8 in such an amount that the copper concentrations given below are obtained. These formulations are inoculated with bacteria, yeast and mold in a preservation load test and examined for appropriate growth.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Afin de préparer une dispersion polymère antibactérienne et fungicide, une dispersion polymère est mélangée avec un polymère protecteur dispersible dans la dispersion polymère, dans une quantité suffisante pour produire un effet antibactérien et fungicide. Ce polymère protecteur comprend: entre 3 et 60 % en poids par rapport au poids total des constituants a) et b) sans ions métalliques, d'au moins un acide mono- ou dicarboxylique insaturé alpha-béta-monoéthyléniquement contenant entre 3 et 7 atomes de C, pouvant être partiellement ou entièrement neutralisé ou être présent sous forme d'anhydride, comme constituant a); entre 97 et 40 % en poids, par rapport au poids total des constituants a) et b) sans ions métalliques, d'au moins un alkyle(méth)acrylate C1-C20, d'un vinylester d'acides carboxyliques contenant entre 1 et 20 atomes de C, d'un nitrile insaturé éthyléniquement ayant entre 3 et 6 atomes de C, d'un halogénure de vinyle ou d'un hydrocarbure non aromatique ayant entre 4 et 8 atomes de C et au moins 2 liaisons doubles conjuguées ou éthylène ou propylène, comme constituant b); entre 0 et 50 % en poids, par rapport au poids total des constituants a) et b) sans ions métalliques, d'au moins un autre monomère insaturé éthyléniquement, comme constituant c) et entre 0 et 20 % en poids, par rapport au poids total des constituants a), b) et c) sans ions métalliques, d'au moins un monomère polyfonctionnel à action réticulante, comme constituant d), entre 1 et 100 % en moles des groupes acides étant convertis en sels d'au moins un ion métallique à action antibactérienne et/ou fungicide.
PCT/EP1998/000953 1997-02-24 1998-02-19 Dispersions polymeres antibacteriennes et fungicides WO1998038238A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98912337A EP1018871A2 (fr) 1997-02-24 1998-02-19 Dispersions polymeres antibacteriennes et fungicides
AU67217/98A AU6721798A (en) 1997-02-24 1998-02-19 Antibacterial and fungicidal polymer dispersions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997107221 DE19707221A1 (de) 1997-02-24 1997-02-24 Antibakterielle und fungizide Polymerisatdispersionen
DE19707221.6 1997-02-24

Publications (2)

Publication Number Publication Date
WO1998038238A2 true WO1998038238A2 (fr) 1998-09-03
WO1998038238A3 WO1998038238A3 (fr) 1999-05-14

Family

ID=7821239

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/000953 WO1998038238A2 (fr) 1997-02-24 1998-02-19 Dispersions polymeres antibacteriennes et fungicides

Country Status (4)

Country Link
EP (1) EP1018871A2 (fr)
AU (1) AU6721798A (fr)
DE (1) DE19707221A1 (fr)
WO (1) WO1998038238A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2367244A (en) * 2000-07-07 2002-04-03 David Peter House Hygiene control arrangement
CN115478440A (zh) * 2021-06-15 2022-12-16 贝内克-长顺汽车内饰材料（张家港）有限公司 水性油漆及由其制备而成的抗菌皮革

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10109447A1 (de) 2001-02-27 2002-09-05 Basf Ag Antibakteriell und fungizid ausgerüstete Polymerdispersionen und Polymerlösungen
US20030185889A1 (en) * 2002-03-27 2003-10-02 Jixiong Yan Colloidal nanosilver solution and method for making the same
DE102006056284A1 (de) * 2006-11-29 2008-06-05 Helling, Günter, Dr. Polymere mit nanoscaligen Teilchen antimikrobieller Metalle oder Metallverbindungen
DE102007020523A1 (de) * 2007-05-02 2008-11-06 Helling, Günter, Dr. Metallsalz-Nanogel enthaltende Polymere
PL214152B1 (pl) * 2009-09-29 2013-06-28 Ekopak Plus Spolka Z Ograniczona Odpowiedzialnoscia Tektura o wlasciwosciach biobójczych i sposób otrzymywania tektury o wlasciwosciach biobójczych

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2809244A1 (de) * 1977-03-04 1978-09-21 Nitto Electric Ind Co Antibakterielles und fungizides material
EP0253639A1 (fr) * 1986-07-14 1988-01-20 Nippon Paint Co., Ltd. Particules résineuses et leur préparation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03179063A (ja) * 1989-09-27 1991-08-05 Saiden Kagaku Kk 水性防藻，防黴，防汚塗料組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2809244A1 (de) * 1977-03-04 1978-09-21 Nitto Electric Ind Co Antibakterielles und fungizides material
EP0253639A1 (fr) * 1986-07-14 1988-01-20 Nippon Paint Co., Ltd. Particules résineuses et leur préparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 9137 Derwent Publications Ltd., London, GB; Class A18, AN 91-270962 XP002097195 & JP 03 179063 A (SAIDEN KAGAKU KK) , 5. August 1991 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2367244A (en) * 2000-07-07 2002-04-03 David Peter House Hygiene control arrangement
GB2367244B (en) * 2000-07-07 2005-01-19 David Peter House Hygiene control arrangements
CN115478440A (zh) * 2021-06-15 2022-12-16 贝内克-长顺汽车内饰材料（张家港）有限公司 水性油漆及由其制备而成的抗菌皮革
CN115478440B (zh) * 2021-06-15 2024-05-03 贝内克-长顺汽车内饰材料（张家港）有限公司 水性油漆及由其制备而成的抗菌皮革

Also Published As

Publication number Publication date
EP1018871A2 (fr) 2000-07-19
AU6721798A (en) 1998-09-18
DE19707221A1 (de) 1998-08-27
WO1998038238A3 (fr) 1999-05-14

Similar Documents

Publication Publication Date Title
EP1931197B1 (fr) Preparation contenant au moins un fongicide du groupe des conazoles, un autre fongicide et un copolymere stabilisant
EP2515660B1 (fr) Formulations avec des nanoparticules d'argent
EP1778736B1 (fr) Dispersions aqueuses de polymerisats anioniques solubles dans l'eau et/ou expansibles dans l'eau, procede de fabrication et utilisation
EP1651693B1 (fr) Dispersions aqueuses de polymerisats hydrosolubles de monomeres anioniques ethyleniquement insatures, leur procede de fabrication et leur utilisation
DE3935137A1 (de) Urethangruppen enthaltende copolymerisate auf der basis von ethylenisch ungesaettigten monomeren, verfahren zu ihrer herstellung und ihre verwendung
DE19833062A1 (de) Redispergierbares Pulver und dessen wäßrige Dispersion, Verfahren zur Herstellung sowie Verwendung
EP1874833A1 (fr) Polymeres utilises pour la dispersion de pigments et des pigments de charge
WO2006087344A1 (fr) Dispersions aqueuses de complexes de polyelectrolytes essentiellement a charge anionique, procedes de realisation et utilisation associes
EP0867455A2 (fr) Dispersions aqueuses de polymères dérivés de monomères hydrosolubles avec un groupe N-vinylique et des monomères hydrosolubles
DE102005023799A1 (de) Wässrige Dispersionen von wasserlöslichen und/oder in Wasser quellbaren anionischen Polymerisaten, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2008138485A1 (fr) Additifs hydrosolubles non ioniques
EP2654429A1 (fr) Procédé de fabrication d'une dispersion contenant des nanoparticules d'argent ainsi qu'utilisation d'un mélange contenant des nanoparticules d'argent en tant qu'agent de revêtement
EP0770640B1 (fr) Procédé pour préparer des poudres polymères rédispersables dans des milieux aqueux
DE3035375A1 (de) Emulgiermittelfreie waessrige kunststoffdispersion
EP1018871A2 (fr) Dispersions polymeres antibacteriennes et fungicides
DE69408306T3 (de) Latex für lacke ohne lösungsmittel mit verbesserter auswaschbarkeit
EP0765379B1 (fr) Inhibiteurs de migration des couleurs pour produits de lavage et de nettoyage
EP0442370B1 (fr) Utilisation de dispersions polymères aqueuses
DE3539118A1 (de) Biozidpaste
DE3442800C2 (de) Stabilisierte Fungicide auf der Basis von Aluminiumfosetyl und eines Produkts auf Kupferbasis
DE3924527A1 (de) Mikrobizid-formulierungen und deren verwendung
DE19654168A1 (de) Verfahren zur Herstellung wäßriger Polymerisatdispersionen durch radikalische, wäßrige Emulsionspolymerisation
DE4344391A1 (de) Polymerdispersionen
EP1373384A1 (fr) Dispersions polymeres et solutions polymeres antibacteriennes et fongicides
EP1553830B1 (fr) Procedes pour detruire des micro-organismes

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AL AU BG BR BY CA CN CZ GE HU IL JP KR KZ LT LV MX NO NZ PL RO RU SG SI SK TR UA US VN

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
AK Designated states

Kind code of ref document: A3

Designated state(s): AL AU BG BR BY CA CN CZ GE HU IL JP KR KZ LT LV MX NO NZ PL RO RU SG SI SK TR UA US VN

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

WWE Wipo information: entry into national phase

Ref document number: 09355994

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1998912337

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998537266

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1998912337

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1998912337

Country of ref document: EP