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WO2007068460A1 - Revêtements biocides - Google Patents

Revêtements biocides Download PDF

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Publication number
WO2007068460A1
WO2007068460A1 PCT/EP2006/011982 EP2006011982W WO2007068460A1 WO 2007068460 A1 WO2007068460 A1 WO 2007068460A1 EP 2006011982 W EP2006011982 W EP 2006011982W WO 2007068460 A1 WO2007068460 A1 WO 2007068460A1
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Prior art keywords
polymer
biocidal
alkyl
polymer according
carbon atoms
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Inventor
Jacobus Antonius Loontjens
Antonia Urmanova
Van Michael Alphonsus Cornelis Johannes Dijck
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DSM IP Assets BV
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DSM IP Assets BV
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    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the invention relates to a polymer with an incorporated biocidal component.
  • the invention also relates to a crosslinker with an incorporated biocidal component, the invention further relates to a composition comprising either the biocidal polymer or crosslinker or both, to a substrate fully or partially coated with a biocidal composition and its use in coatings.
  • Biocidal is here and hereinafter used in its broad sense, so as to encompass anti-bacterial as well as anti-fungal and anti-algae.
  • biocidal additives are widely used in household cleaning products and in cosmetics, their application in plastics and coatings is so far limited. However the potential application area is very broad and covers coatings, engineering plastics as well as fibres. Especially important are the industrial applications in drinking water industry, food and paper industry and in hospitals and other public buildings, outdoor building panels, glass and so forth. Another important area for these materials is biomedical applications. Additionally biocidal additives can advantageously be used in products that everybody touches, for example door handles, telephones and money, because these products are responsible for the fast transfer of bacteria and thus for the transfer of illnesses. Although biocidal coatings can of course not prevent all bacterial infections they can reduce the risk substantially.
  • biocidal materials Often used techniques to obtain biocidal materials are the addition of low molecular weight biocidal additives or photoactive chemicals.
  • An example of a low molecular weight biocidal additive is the addition of transition metal ions, in particular silver ions.
  • An example of a photoactive chemical is non-coated titanium dioxide.
  • a disadvantage of the use of photoactive chemicals in coatings is that they tend to degrade the organic polymer as well, thereby degrading the integrity of the coating.
  • a disadvantage of the use of low molecular weight biocidal additives in coating compositions is that they have a higher ability to leach out when the coating is in contact with for example (rain)water compared to other biocidal additives (see for example "Biomimetic and supramolecular systems", (2002), C20 (1-2), 167-173).
  • This leaching-out gives rise to several problems such as for example the end of the desired biocidal activity but also to environmental problems.
  • a disadvantage of silver ions is that they are leachable just as the other transition metal ions. Moreover, silver ions do not only kill bacteria, but they also denaturize essential human proteins, which is a toxic action. Furthermore, silver ions are easily reduced, forming a grey colour, which is not acceptable in many coating applications.
  • the object of the present invention is to overcome one or more of the above-mentioned problems.
  • the object is to make available a polymer with biocidal properties and which polymer can be used in coating compositions that have biocidal properties and from which coatings can be obtained from which the biocidal component does not leach after contact with water.
  • does not leach is herein meant that the biocidal product in an aqueous solution maintain the biocidal property.
  • This object has been reached by a polymer with an incorporated biocidal component.
  • polymer is here and hereinafter meant a compound in which at least two repeating units are available, thus comprising the generally referred polymers as well as dimers and oligomers.
  • incorporated is thus meant that the biocidal component is chemically built-in in the polymer by covalent bonding or electrostatical bonding.
  • the kind of polymer that is chosen is not particularly critical. Its choice will generally be dictated by the requirements that must be met by the final coating. For example, a coating that is going to be used on a substrate that will be used outdoors needs to fulfil different requirements than a coating on a substrate that will be used indoors. In this respect the polymers that will be used in the two kinds of coatings will most probably be different. Thus the requirements that the final coating must meet will dictate the choice of polymer. Although the choice is not particularly critical, the polymer used in the biocidal coating composition must be obtained by a condensation reaction. The reason for this is that low viscous coating compositions are preferred since they giver better antibacterial properties.
  • Low viscous and thus low molecular weight polymers suitable for the coating composition are more conveniently made by a step-growth polymerisation technique than with a chain-growth polymerisation technique.
  • polycondensates are most suitable.
  • Polymers that can be obtained via a condensation reaction are for example polyesters, copolyesters, polyethers, polyamides, polyesteramides, polyurethanes and polycarbonates.
  • polyesters or polyesteramides are used. Most preferably polyesters are used as they have excellent properties for fulfilling the requirements of the final coating.
  • any combination can be made between different types of polymers with biocidal properties, as long as the polymers are obtained by a condensation reaction.
  • a combination of a polyester with biocidal properties with a polyamide with biocidal properties, or a polyester with a polyurethane when both have biocidal properties it is possible to use a combination of two polymers of the same kind, for example two different polyesters with biocidal properties or two polyamides with biocidal properties. With different is in this context meant that the two polymers of the same kind have different chemical or physical properties.
  • An example of two polymers of the same kind with different chemical properties is two polyesters wherein the alcohols and/or acids used in the synthesis are different, for example one polyester based on an aliphatic alcohol and the other polyester based on an aromatic alcohol, or one aliphatic acid and the other polyester is synthesized with an aromatic acid.
  • An example of two polymers of the same kind with different physical properties is two polyesters wherein the acid values or the glass transition temperatures are different.
  • non-biocidal polymer is not critical and can be made so as to fulfil the final requirements of the coating, however the biocidal polymer must be chosen from between the polymers obtained by a condensation reaction.
  • a combination of polymers either all of them having biocidal properties or only some of them having biocidal properties, it can sometimes be convenient to refer to the polymer that is present in the largest amount as to the "matrix polymer".
  • any polymer is suitable, it has been found - A -
  • the molecular weight used here is expressed as the number average molecular weight M n .
  • the number average molecular weight is determined by size exclusion chromatography (SEC). The columns used are 3 * PSS, the solvent is hexafluoro isopropanol (HFIP) and the detection is done with refraction index (Rl), ultra violet light (UV), deferential vsicosimetry (DP) and RALLS (light scattering). The data were collected and processed with ThSEC software.
  • the molecular weight of the polymer should be less than 10.000 g/mol.
  • the molecular weight is less than 8.000, most preferably less than 5.000 g/mol.
  • the lower limit of the molecular weight is governed by the mechanical properties, when the crosslink density becomes too high the coating becomes too brittle.
  • the molecular weight is at least 500, more preferably at least 1.000 g/mol.
  • a preferred range for the molecular weight is between 500-8.000 g/mol, more preferably 1.000-5.000 g/mol.
  • the resin will generally have some functional groups through which the resin can react with an optionally present crosslinker upon which a network will be formed. Examples of suitable functional groups are carboxyl-, hydroxyl-, epoxy-, amino groups and combinations of any of them.
  • the coating composition comprising the biocidal polymer will generally comprise at least one crosslinker so as to form a network.
  • the crosslinker present in the coating composition is not particularly critical. The nature of the crosslinker is determined by the nature of the functional groups in the polymer. The functional groups on the crosslinker must be able to react with the functional groups in the polymer. Examples of crosslinkers are epoxy resins, polyamines, (blocked) isocyanates, aminoresins, polycarboxylic acids, acid anhydrides, polyphenols, Primid®- like compounds and combinations of any of them. (Primid®-like compounds are based on ⁇ - hydroxyl alkyl amide).
  • the biocidal component is incorporated as a cation of one of the monomers covalent bonding to the polymer is derived from.
  • the biocidal component is chemically incorporated in the polymer.
  • the biocidal component is incorporated as one of the monomers as described under the first embodiment. However in this embodiment it is the anion that is built-in in the polymer, the cation being the counter ion and bonded electrostatically to the polymer.
  • the biocidal component is incorporated in a crosslinker and hence being bonded either electrostatically or covalently to the final cured coating.
  • a combination of embodiments is used.
  • the biocidal component is incorporated as a cation of one of the monomers the polymer is derived from.
  • the biocidal component is chemically incorporated in the polymer.
  • the polymer must be obtained by a condensation reaction.
  • An example of how the biocidal component can be incorporated in the polymer is the following. Where the biocidal polymer is a polyester and the polyester is formed in the reaction between an alcohol component and an acid component, the biocidal component can be either in the form of the alcohol component (see left-hand side of Formula I) or in the form of the acid component (see right-hand side of Formula I).
  • the polyester with incorporated biocidal component can for example be represented, without being limited to the exact structure, by one of the versions of Formula I. It is also possible within the scope of the invention that both versions of Formula I are present within one polyester polymer, thus that both part of the alcohol components and part of the acid components are used to incorporate the biocidal component.
  • alcohol component is here and hereinafter meant the component in the polyester synthesis that is an alcohol or behaves functionally the same as an alcohol in the polyester synthesis.
  • suitable alcohol components are quaternary onium salts of alcohols, hydroxy-functional derivatives, such as for example di-(2-hydoxy ethyl) amine, di-(2-hydroxy propyl) amine, di-(3- hydroxy propyl) amine, tri-(2-hydroxy ethyl) amine.
  • Alcohol components should have at least two hydroxyl groups to be able to react to a polyester as defined above.
  • the "alcohol” could also be hidden in an ester of a low molecular weight acid and one of the alcohols mentioned above. The low molecular weight acid could be removed during the polycondensation.
  • acid component is here and hereinafter meant the component in the polyester synthesis that is an acid or behaves functionally the same as an acid in the polyester synthesis.
  • suitable acid components are acids, acid anhydrides, esters, for example quaternary onium salts of imino acetic acid, 3,5- pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4 -pyridine dicarboxylic acid.
  • Acid components should have at least two acid (or acid derived) groups to be able to react to a polyester as defined above. As known to the man skilled in the art of polyester synthesis, the exact nature of the components that are used in the polyester synthesis depends on the requirements the polyester must meet.
  • the biocidal component has a structure that can be represented by formula II:
  • Z 1 , Z 2 , Z 3 may independently of one another, be the same or different functional endgroups at the branches, a,b,c may independently of one another, be the same or different integers and represent the number of functional endgroups per branch,
  • R 1 , R 2 may, independently of one another, be the same or different hydrogen, alkyl- or alkenyl groups with 1-10 carbon atoms
  • R 3 is hydrogen, alkyl- or alkenyl groups with 1-10 carbon atoms or the same as R 4
  • R 4 is an alkyl- or alkenyl group with 6-36 carbon atoms
  • X + is a quaternary nitrogen- or phosphorus-containing cation
  • Y ' is a counter ion of the quaternary cation.
  • Z 1 , Z 2 , Z 3 are functional endgroups at the branches. These functional endgroups make it possible to build in the biocidal component covalently in the polymer.
  • a, b, c may independently of one another be chosen to be the same or different integers, with the proviso that at least one of them has a value greater than 0.
  • a + b + c is at least two (i.e. at least two functional endgroups in one branch or at least two branches each having at least one functional endgroup).
  • functional endgroup is meant a group that is different from the alkyl- or alkenyl groups R and that is capable to react with groups in the polymer.
  • the nature of the functional endgroups can vary widely as long as they are able to react with groups on the polymer.
  • Examples of functional endgroups are hydroxyl-, carboxyl-, amine-, (blocked) isocyanate, ⁇ -hydroxy alkyl amide, and epoxy groups.
  • the functional endgroups are hydroxyl- or carboxyl- groups.
  • the R 4 group in the biocidal component according to formula Il can be an alkyl- or alkenyl group with 6-36 carbon atoms.
  • the maximum length of this kind of groups is 36 carbon atoms.
  • the length is at least 10 carbon atoms long and preferably the maximum length is 24 carbon atoms. Most preferably the length is between 12 and 20 carbon atoms.
  • the group R 3 can be the same as R 4 . In that case two relatively long branches are available. However it is preferred to have only one "relatively long" group R 4 . In that case R 3 is a hydrogen, alkyl- or alkenyl group with 1-10 carbon atoms.
  • the groups R 1 , R 2 are independently from each other either hydrogen or alkyl- or alkenyl groups with 1-10 carbon atoms. Preferably the length of the alkyl- or alkenyl- groups is at most 8 carbon atoms, more preferably at most 4 carbon atoms.
  • R 3 is either the same as R 1 or as R 4 . Thus R 3 is either hydrogen or alkyl- or alkenyl groups with 1-10 carbon atoms or an alkyl- or alkenyl group with 6-36 carbon atoms. It is highly preferred that no more that one of R 1 , R 2 , R 3 are hydrogen, since this was found to provide the strongest biocidal effect.
  • R 1 , R 2, R 3 are independently from each other methyl, methylene, ethyl or ethylene.
  • R 1 , R 2, and R 3 are all an alkyl- or alkylene group, thus it is preferred not to have hydrogen as one of the R 1 , R 2, and R 3 groups or in other words it is preferred not to have a protonated quaternary cation as they are less effective than the tetra alkyl biocidal component.
  • X + in formula Il is a quaternary nitrogen- or phosphorus-containing cation.
  • the nitrogen or phosphorus can be present as such or in an organic moiety.
  • an organic moiety is meant that the nitrogen or phosphorus is part of a organic structure.
  • the organic moiety has an aromatic character.
  • An example of a moiety with an aromatic character is pyridine.
  • X + is a quaternary phosphorus-containing cation as the quaternary P-cation is more thermally stable than the quaternary N-cation and can therefore more easily be used in a polymer synthesis, such as for example a polyester synthesis. Additionally it was found that under certain conditions the quaternary P-cation is more effective in its biocidal activity than the quaternary N-cation.
  • the counter ion of the quaternary cation is represented by Y " in formula II.
  • the nature of the anion Y is not particularly critical. Suitable examples for Y in the embodiment where the cation is covalently bonded to the polymer can be chosen from the list halogenide, carboxylate, phosphate, phosphonate, nitrate, hydroxide. Preferably iodide, chloride, bromide or a combination of any of them is used as the synthesis of the biocidal polymer appeared to be more successful with a halogenide. Most preferably bromide is used as the counter ion.
  • the biocidal component is still incorporated as one of the monomers as described under the first embodiment.
  • it is the anion that is built-in covalently in the polymer, the cation being the counter ion.
  • the biocidal component is also in this embodiment chemically incorporated in the polymer by electrostatically means.
  • the polymer must be obtained by a condensation reaction.
  • biocidal component can be incorporated in the polymer.
  • the biocidal polymer is a polyester and the polyester is formed in the reaction between an alcohol component and an acid component
  • the biocidal component can be either in the form of the alcohol component (see left-hand side of Formula III) or in the form of the acid component (see right-hand side of Formula III).
  • the polyester with incorporated biocidal component can for example be represented, without being limited to the exact structure, by one of the versions of Formula III. It is also possible within the scope of the invention that both versions of Formula III are present within one polyester polymer, thus that both part of the alcohol components and part of the acid components are used to incorporate the biocidal component.
  • a, b, c, Z 1 , Z 2 , Z 3 , R 1 , R 2 , R 3 , R 4 are the same as described above, d, e may independently of one another, be the same or different integers and represent the number of functional endgroups per branch,
  • R 5 is alkyl chain or aromatic ring
  • R 6 , R 7 is, independently of one another, the same or different hydrogen, alkyl- or alkenyl groups with 1-10 carbon atoms,
  • R 8 is hydrogen, alkyl- or alkenyl groups with 1-10 carbon atoms or the same as R 4 Z 4 , Z 5 is, independently of one another, the same or different functional endgroups at the branches,
  • a ' is SO 3 " , COO “ , O “ , P(O)(OR 9 )O “ , P(O)(O) 2 " , and
  • Rg is alkyl group with 1-6 carbon atoms or phenyl. It should be observed that even though a, b, c, d and e for the individual unit is an integer, the average values of these constants are typically not an integer for a practical resin consisting of a high number of individual units.
  • a suitable component to be used in the synthesis of the biocidal polymer under this embodiment is the anion of sulfo-isophthalic acid, neutralized with an onium cation.
  • Other suitable acids are the mono anion of phosphoric acid with the onium ion as counter ion.
  • An example of a suitable alcohol is the anion of 2,2-diethylol propionic acid, which is neutralized with an onium ion.
  • the biocidal component is incorporated in a crosslinker.
  • a crosslinker is a component that is used in the binder of a coating composition, next to the film forming resin.
  • Binder is generally defined as the resinous part of a paint consisting of polymer and crosslinker. The function of the crosslinker is to react with the resin in the binder upon which a crosslinked network is formed. To obtain a three-dimensional network it is necessary that the resin and crosslinker are equal to or more than 2-functional. With “more than 2-functional” is meant that the resin or crosslinker, just as the case may be, has at least partly three groups available for reaction with the other component in the binder composition.
  • the functionality of a compound is an average value for the functionality of all separate molecules, the functionality need not be an integer. With “more than 2-functional” is thus meant that at least part of the molecules have a functionality higher than 2.
  • the average value for the functionality is at least 2,1. More preferably the average functionality is at least 2,3.
  • a higher value is preferred as with a higher value for the functionality the properties of the coating finally obtained are better.
  • the crosslinker should at least be more than 2-functional to obtain a three-dimensional network.
  • the crosslinker is two- functional
  • the resin should at least be more than 2-functional to realise a three- dimensional network. It is preferred that the crosslinker is at least three-functional.
  • the in the crosslinker incorporated biocidal component can be represented by formula V:
  • the three functional groups of the crosslinker that are available for reaction with the resin are represented by Z, which need not be the same but can be different.
  • X is the quaternary cation and Y is the counter anion. It is also possible that Y is in the centre and that X is the counter ion as shown in Formula Vb.
  • the functional groups need not be arranged on separate branches as shown in Formula Va and Vb but may alternatively be arranged with two functional groups on one branch as shown in Formula Vc or even more functional groups on one of the branches (not shown).
  • X and Y can be the same as described under Embodiment I or II.
  • the value of the functionality could be considered as the sum of a + b + c or a + b + c + d + e, respectively.
  • Preferred embodiments corresponds to a + b + c >1 and 4 > a + b + c > 2 or a + b + c + d + e >1 and 4 > a + b + c + d + e > 2, respectively.
  • An example hereof is the combination of a biocidal polymer according to Formula I (incorporated cation) with a biocidal polymer of Formula III (incorporated anion).
  • a coating composition or paint composition will generally comprise a binder composition (or short a binder) and additives.
  • additive is here and hereinafter meant a substance that is generally added in a small quantity and that has a particular chemical or technological effect.
  • pigments and/or colorants and/or other additives will be present in the coating or paint composition.
  • the pigment present in the coating composition can be of an inorganic or organic nature.
  • pigment is here and hereinafter meant a substance consisting of particles, which is practically insoluble in the binder and is used as a colorant (DIN 55943).
  • a colorant is a color-imparting substance.
  • the binder composition is generally defined as the resinous part of the coating or paint composition consisting of polymer and crosslinker.
  • the coating composition is then generally applied to a suitable substrate and subsequently cured to form a coating on the substrate.
  • the substrate can be fully or partially coated with the coating composition and thus after curing fully or partially be coated with the coating.
  • the curing process to obtain a cured coating can proceed in various stages. It is possible to fully cure the coating composition at once or it is possible to first partially cure and in a second stage complete the curing process. In the last situation, where the cure is effected in two or even more stages, it is possible to use different curing mechanisms.
  • the curing process is well known to the man skilled in the art of making coatings. Examples of curing processes are thermal curing, curing with electromagnetic radiation, such as for example UV- or electron beam curing. It is also possible to use two (dual-cure) or more types of curing processes.
  • the substrate is not particularly critical and can be chosen depending on the mechanical and/or aesthetical requirements.
  • suitable substrates are organic and inorganic materials such as for example wood, metal, plastic, paper, cardboard, brick, stone and composite material.
  • biocidal polymers and the biocidal coating compositions can be used in all kinds of coatings, such as for example can and coil coatings, powder coatings as well as in dispersions and emulsions.
  • E-coli Escherichia CoIi
  • Staphylococcus Aureus The E-coli bacteria (E.coli ATCC 11105) was supplied by ATCC (Middlesex, UK) and stored in a refrigerator at -18 0 C. A stock solution containing 2-5 * 10 9 bacteria/ml was prepared.
  • Tests are performed by immersing coatings obtained from the polymers and crosslinkers with incorporated biocidal component, in a diluted buffer solution containing 2-5 * 10 6 bacteria/ml.
  • the concentration of the buffer solution is important as well. The ion concentration should not be too low to create the right conditions for bacteria to survive, and not too high to mask the action of antibacterial agents.
  • the substrate on which the coating is applied must be inert. We found that this is not always the case.
  • aluminium panels A-46 and Alcan can be used but AI-36 not, since then all the bacteria are killed due to the specific treatment of the substrate.
  • parts of them After having applied the coatings on substrate, parts of them are immersed in 25 ml of the bacteria solution (in a plastic centrifuge vial) containing 2-5*10 6 bacteria/ml and incubated at 25 0 C while gently shaking. After several time intervals samples are taken out of the vial, diluted with buffer solution (1000 times) and spread over an agar breeding medium in a petri dish (LB-agar per liter: 1O g Bacto Trypton, 5 g Bacto Yeast extract, 5 g NaCI, 15 g Agar).
  • the phosphonium compounds (dimethyl sulfoisophthalic acid salt of (tributyl, dodecyl- phosphonium)) and (dimethyl sulfoisophthalic acid salt of (tributyl, cetyl-phosphonium)) (referred to respectively as C12 SIP-P and C16 SIP-P compounds) were obtained from Nippon Kagaku Kogyo Co.
  • the ammonium compound (dimethyl sulfoisophthalic acid salt of cetyl trimethyl ammonium compound; C12 SIP-N) were prepared as follows:
  • polyester resins were prepared following a standard polyester synthesis recipe.
  • modified polyester resins were prepared that resembled the commercially available resins Uralac® SN844 or Uralac® P5263 (powder) resin wherein part of the normally used acid was replaced with the ammonium- or phosphonium- salt.
  • the polyester synthesized can be schematically represented by the following structure, without being limited to the exact structure:
  • the coatings were applied on aluminium panels.
  • Echerichia CoIi E-coli
  • Staphylococcus Aureus Staphylococcus Aureus were used.
  • the test is similar to the ASTM E2149-01 standard test method for "Determining the biocidal activity of immobilized antimicrobial agents under dynamic contact conditions".
  • the bacteria E CoIiATCC 11105
  • a stock solution containing 2-5*10 9 bacteria per ml was prepared.
  • the coatings were immersed in a diluted buffer solution, containing 2-5 * 10 6 bacteria/ml.
  • Coated substrates (2*5 cm; 5 samples) were immersed in 25 ml of the bacteria solution (in a plastic centrifuge vial) containing 2-5 * 10 6 bacteria/ml and incubated at 25 0 C for 24 hours while gently shaking. After several selected time intervals, samples were taken out of the vial, diluted with buffer solution (1000 times) and spread over an agar breeding medium in a petri dish (LB-agar per liter: 10g Bacto Trypton; 5gr Bacto Yeast extract; 5gr. NaCI; 15gr Agar). After the petri dishes were stored at 37 0 C overnight the number of bacteria colonies were counted (every single bacteria forms one colony). When all bacteria survive one can count > 1000 colonies, when all bacteria die a log 3 reduction is obtained. A log 3 reduction is often taken as a measure for good antibacterial behaviour, and a log 5 reduction as an excellent behaviour. Coating preparation
  • Table 1 1 st series of experiments with 20 wt % C12- or C16 SIP-P-polyesters. (Number of bacteria surviving the test; starting with 3-5*10 3 E coli bacteria.) Coatings contain common 30 wt% pigments (coated TiO 2 ).
  • SN844 stands for Uralac® SN844 polyester resin commercially available from DSM
  • SIP-P stands for sulfo isophthalic acid with tributyl alkyl (C 12 or C 16 ) quaternary phosphonium ion as counter ion.
  • the reference samples did not kill any bacteria, as expected.
  • the coatings containing the phosphonium ions were all biocidal.
  • the C12 phosphonium cations (with C 12 alkyl tail) are more effective than the C16 (with C 16 alkyl tail). It should be emphasized that these biocidal compounds are built-in, and still active.
  • Table 3 Antibacterial properties of coatings panels before and after immersing them in an aqueous buffer system (Number of bacteria surviving the test; starting with 3-5*10 3 E coli bacteria).
  • the ammonium salt of sulfoisophthalic acid (C12-SIP-N) was prepared by starting from the sodium salt of dimethylisophthtalic acid and trimethyl- cetyl ammonium bromide (see above). Both starting compounds are commercially available. This biocide was built-in in a SN844 recipe. The synthesis was comparable with the phosphonium salts. The results are given in table 4.
  • the coatings containing quaternary ammonium ions performed very well.
  • Phosphonium containing coatings (C12-SIP-P SN844) have also been tested.
  • Figure 1 shows that these coatings kill the Staphylococcus Aureus effectively. It can be seen that the panel is free of bacteria and that there is no halo around the panel, indicating that no biocidal compound is depleted into the solution.
  • the coatings were tested with Staphylococcus Aureus according to the procedure as described above and the results are given in Table 5.
  • the panels coated with C12-SIP-P SN844 are also biocidal for Staphylococcus Aureus bacteria according to that test.
  • the coated panels remain biocidal after an aqueous extraction at 121 0 C.
  • Resins with more mobile biocidal compounds have been prepared and tested.
  • the structures of these resins are as below.
  • n 0 - 20

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Abstract

La présente invention concerne un polymère comprenant un composant biocide. L'invention concerne également un agent de réticulation comprenant un composant biocide, ainsi qu'une formule comprenant soit le polymère biocide, soit l'agent de réticulation, soit les deux, et un substrat entièrement ou partiellement revêtu d'une formule biocide et son utilisation dans le domaine des revêtements.
PCT/EP2006/011982 2005-12-13 2006-12-13 Revêtements biocides Ceased WO2007068460A1 (fr)

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EP05112031 2005-12-13
EP05112031.9 2005-12-13

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CN114057615A (zh) * 2021-11-11 2022-02-18 浙江大学 耐高温可聚合抗菌剂及其制备和在合成抗菌聚酯中的应用
DE102016206831B4 (de) 2015-05-07 2022-08-04 Xerox Corporation Wässrige Druckfarbenzusammensetzung und Prozess
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Publication number Priority date Publication date Assignee Title
DE102016206831B4 (de) 2015-05-07 2022-08-04 Xerox Corporation Wässrige Druckfarbenzusammensetzung und Prozess
CN114057615A (zh) * 2021-11-11 2022-02-18 浙江大学 耐高温可聚合抗菌剂及其制备和在合成抗菌聚酯中的应用
CN114057615B (zh) * 2021-11-11 2022-08-02 浙江大学 耐高温可聚合抗菌剂及其制备和在合成抗菌聚酯中的应用
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CN117089058B (zh) * 2023-10-18 2024-04-02 上海洁宜康化工科技有限公司 抗菌聚酯的制备方法和抗菌纤维的生产方法

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