Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/58—Metal-containing linkages
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic

Definitions

• the invention concerns an antibacterial layer active against pathogenic bacteria, particularly against the MRSA bacterial strain.
• the invention also concerns the way in which the antibacterial layer active against pathogenic bacteria, particularly against the MRSA bacterial strain, is created, i.e. by applying a sol prepared using the sol-gel method onto the substrate surface and by subsequent polymerization of the layer.
• an antibacterial layer active against pathogenic bacteria has been known from the CZ patent No. 303250; the layer is formed by the hybrid polymer 3-(trialkoxysilyl)propyl methacrylate and titanium(IV) alkoxide with an addition of silver and copper nitrates. Furthermore, the hybrid polymer in its expedient embodiment contains titanium dioxide nanoparticles, and up to 70 mol. % of 3-(trialkoxysilyl)propyl methacrylate is replaced with an equimolar mixture of methyl methacrylate and tetraalkoxysilane. Based on the CZ patent No.
• the way of creating the antibacterial layer active particularly against the MRSA bacterial strain and other pathogenic bacteria consists in applying a sol prepared using the sol-gel method onto the substrate surface and in subsequent heat processing of the layer, while the sol is made of 3-(trialkoxysilyl)propyl methacrylate, titanium(IV) alkoxide, silver nitrate, copper(ll) nitrate, radical catalyst of polymerization, alcohol as the solvent, water and nitric acid as the catalyst of polycondensation of the inorganic part of the hybrid grid so that the molar ratio of 3-(trialkoxysilyl)propyl methacrylate and titanium(IV) alkoxide in the reaction mixture is 95:5 to 50:50, the content of silver and copper compounds (upon conversion as metals in dry mass) is 0.1 to 5 %w of Ag and 0.1 to 10 %w of Cu, the content of the radical catalyst of polymerization 0.2 to 10 %w per dry mass weight, and so that the molar ratio
• the 3-(trialkoxysilyl)propyl methacrylate is 3-(trimethoxysilyl)propyl methacrylate (TMSPM), and the titanium(IV) alkoxide is the titanium(IV) isopropoxide.
• Dibenzoyl peroxide (BPO) is used as the radical catalyst of polymerization.
• Photoactive titanium dioxide nanoparticles are added to the sol during its preparation, in an amount corresponding to the dry mass weight : titanium dioxide nanoparticles weight ratio 99:1 to 25:75.
• the sol is heat processed at 150 °C for 2 to 4 hours. Up to 70 mol. % of 3-(trialkoxysilyl)propyl methacrylate is replaced with an equimolar mixture of methyl methacrylate and tetraalkoxysilane.
• the aim of the invention is to improve antibacterial activity of antibacterial layers active against pathogenic bacteria, particularly against the MRSA bacterial strain, and thus to allow for sufficiently stable application of layers also on materials not very resistant against heat, for example, plastic materials, by expanding the possibilities of polymerizing the layer.
• the aim of the invention has been achieved using an antibacterial layer whose substantial characteristic is that it is formed by the hybrid polymer of 3- (trialkoxysilyl)propyl methacrylate and titanium(IV) alkoxide with an addition of nitrates, acetylacetonates or other salts of silver, copper and zinc.
• soluble salts of chromium(lll) and/or vanadium can also be added besides the aforementioned salts of silver, copper and zinc, which increase antibacterial activity of the prepared layer even further.
• nanoparticles of photoactive titanium dioxide can be added to the layer, which increase even further the already high antibacterial effects of the layer.
• a part of 3- (trialkoxysilyl)propyl methacrylate can be replaced with an equimolar mixture of methyl methacrylate and tetraalkoxysilane.
• the antibacterial layer is formed as follows: the initial sol is prepared using the sol-gel method from 3-(trialkoxysilyl)propyl methacrylate and titanium(IV) alkoxide with an addition of the salts of silver, copper and zinc, and possibly also salts of chromium(lll) and/or vanadium; subsequently, the sol is applied in the form of a layer onto the surface of any object to be protected.
• the layer is stabilized, in terms of mechanical properties and resistance against removal from the surface of the protected object, using heat-initiated polymerization at 80 °C to 200 °C or photoinitiated polymerization.
• nanoparticles of photoactive titanium dioxide can be added to the sol in the process of its preparation, which increases even further the already high antibacterial effects of the layer.
• a part of 3-(trialkoxysilyl)propyl methacrylate can be replaced with an equimolar mixture of methyl methacrylate and tetraalkoxysilane.
• the solution is based on creating an antibacterial layer on the basis of 3- (trialkoxysilyl)propyl methacrylate and titanium(IV) alkoxide.
• photocatalytic nanoparticles of titanium dioxide only supports and extends antibacterial efficacy of the resulting layer while antibacterial efficacy of the resulting layer is given by its primary creation and not by addition of photocatalytic nanoparticles of titanium dioxide.
• the resulting enhanced antibacterial properties are due to the synergic effect of titanium atoms in the inorganic grid of the hybrid polymer and ions or nanoparticles, respectively, of silver, copper, zinc, chromium(lll) and vanadium, possibly supported by the photocatalytic effect of titanium dioxide nanoparticles.
• the intensive antibacterial properties are manifested when the layer is irradiated with UV-A in the region of 315 nm to 380 nm; however, only the light of fluorescent tubes in the visible region suffices to maintain antibacterial properties of the surfaces.
• This layer can be applied on surfaces of glass, ceramics, metals and plastic materials.
• the antibacterial properties remain preserved also upon repeated washing or sterilization (verified after 50 cycles of washing and 20 cycles of extreme sterilization at 125 °C for 1 hour, respectively), which is another very important property of the layers.
• the invention will be described using an example of the technological procedure of creating the layer, and also using examples of antibacterial activity of the layer based on the invention.
• the initial sol is prepared using a modified sol-gel method based on dissolving 3-(triaikoxysilyl)propyl methacrylate (it is expedient to use 3- (trimethoxysilyl)propyl methacrylate TMSPM) and titanium(IV) alkoxide (it is expedient to use titanium(IV) isopropoxide IPTI) with an addition of soluble silver, copper and zinc salts (nitrates are expedient) and with an addition of the radical catalyst of polymerization (dibenzoyl peroxide BPO is expedient for heat-initiated polymerization, while for photoinitiated polymerization, bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide is expedient) in a suitable alcohol (ethanol or isopropyl alcohol is expedient), with subsequent addition of an acid (nitric acid is expedient) with water so thai, the molar ratio of 3- (trialkoxysilyl)propyl methacrylate and
• nanoparticles of titanium dioxide with photocatalytic activity can be added to the prepared sol.
• up to 90 mol.% of 3-(trialkoxysilyl)propyl methacrylate in the reaction mixture can be replaced with an equimolar mixture of methyl methacrylate and tetraalkoxysilane.
• the prepared sol (possibly with nanoparticles of titanium dioxide dispersed in the sol using ultrasound) is then applied on the surface of any substrate intended for antibacterial adaptation as a layer (by pulling up, centrifugation or spraying), and when the solvent evaporates, the created layer is polymerized using heat- or photoinitiated polymerization.
• the heat-initiated polymerization is done at 80 °C to 200 °C (the temperature of 150 °C is expedient) for 30 min to 6 hours (the duration of 3 hours is expedient).
• the choice of heat- or photoinitiated polymerization depends on heat resistance of the substrate to which the layer has been applied, i.e. on thermal resistance of the object to be protected by the antibacterial layer created.
• photoinitiated polymerization is more suitable for polypropylene with thermal resistance up to 80 °C, while heat-initiated polymerization at 150 °C can be chosen for more resistant substrates, etc.
• a fluorescent tube or lamp that irradiates (besides others also) UVA or UVB light can be used as a source of radiation for photoinitiated polymerization for 1 s to 3 hours, while the necessary time of exposure is given by the used catalyst .specific distribution of energies of the used source of radiation, and by radiation intensity at the place of the layer.
• Porosity of the prepared layer is necessary for its functionality (antibacterial properties) because if the metal particles (ions, atoms or nanoparticles) and titanium dioxide nanoparticles are completely enclosed in the volume of the material of the layer, the layer would show virtually no or very low antibacterial activity.
• the initial sols were prepared using a modified sol-gel method. See Table 1 for the overview of reaction mixtures for sol preparation based on the invention and for the composition of comparative reaction mixtures for Example 1.
• the term dry mass shall be understood as the material of the hybrid polymer layer created, which remains upon application to, and subsequent polymerization on the substrate - any protected object, thus without volatile ingredients. The weight of any added nanoparticles of photoactive titanium dioxide is not calculated in the dry mass.
• TMSPM 3-(trimethoxysilyl)propyl methacrylate
• IPTI titanium(IV) isopropoxide
• the sols were ready to be applied to substrates. If any nanoparticles of photoactive titanium dioxide were to be added, the weighed amount of nanoparticles was poured in the finished sol and dispersed using ultrasound.
• Antibacterial properties of the prepared layers were tested using MRSA bacterial strains (Methicillin-Resistant Staphylococcus Aureus ATCC 33591 , ATCC 33592), and also on the bacterial strains of Escherichia Coli (ATCC 9637), Staphylococcus Aureus (ATCC 1260), Acinetobacter baumanii (ATCC 17978), Pseudomonas aeruginosa (ATCC 31480), Proteus vulgaris (ATCC 29905) and Proteus mirabilis (ATCC 35659).
• MRSA bacterial strains Metal-Resistant Staphylococcus Aureus ATCC 33591 , ATCC 33592
• ATCC 9637 Staphylococcus Aureus
• ATCC 1260 Staphylococcus Aureus
• Acinetobacter baumanii ATCC 17978
• Pseudomonas aeruginosa ATCC 31480
• Proteus vulgaris ATCC
• the bacterial inoculum prepared in advance, in the physiological solution with the concentration of 10 8 CFU/ml of bacterial suspension, was used to prepare the concentration of 10 5 CFU/ml of bacterial suspension by its dilution using the physiological solution. Subsequently, a drop of this bacterial suspension, 250 ⁇ , was applied onto the sample. The tested samples with applied bacterial suspension were then irradiated under the fluorescent tube Philips special (Actinic BL F15T8, UV-A region of radiation, range 315-400 nm). The samples of the bacterial cultures were inoculated into Petri dishes containing blood agar. The dishes with inoculated bacterial cultures were incubated in a thermostat at 37.5 °C for 24 hours.
• Table 1 Composition of reaction mixtures used for sol preparation (layers A to K were comparative; layers 1 to 7 were based on the invention).
• TMSPM [w% in [w% in [w% in dry mass IPTI dry dry dry : nano ⁇ mass] mass] mass] particles
• Layers 1 to 3 were subsequently subjected to heat-initiated polymerization in the dryer (glass and stainless steel at 150 °C for 3 hours, poly(methyl methacrylate) at 100 °C for 3 hours).
• Layers 1 UV to 3UV were subjected to photoinitiated polymerization using UV-A radiation emitted by the fluorescent tube Philips special (Actinic BL F15T8, UV-A region of radiation, range 315-400 nm) for 2 hours.
• Table 2 Results of determining the time for 100% inhibition after UV-A irradiation (layers A to K were comparative; layers 1 to 7 were based on the invention).
• IPTI in dry in dry in dry nano- 100% inhibition mass] mass] mass] particles [min]
• Table 3 Results of determining the time for 100% inhibition for samples on glass after UV-A irradiation.
• Table 4 Results of determining the time for 100% inhibition for samples on glass after irradiation using common fluorescent tube light.
• Initials sols based on the invention were prepared using a modified sol-gel method, using the procedure as described in Example 1.
• the sol for layer 1 in Table 1 was used as initial; in addition, chromium(lll) nitrate and/or vanadyl acetylacetonate were added to the reaction mixture in an amount corresponding to the content (converted to the element) as presented in Table 5.
• the sol had been applied to glass by immersion, the samples were left in the laboratory setting to let isopropyl alcohol evaporate, and subsequently, they were subjected to heat-initiated polymerization in the dryer at 150 °C for 3 hours.

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• 2012
  • 2012-05-23 CZ CZ20120339A patent/CZ2012339A3/cs not_active IP Right Cessation
  • 2012-12-10 EP EP12818873.7A patent/EP2852630A1/fr not_active Withdrawn
  • 2012-12-10 WO PCT/CZ2012/000129 patent/WO2013174356A1/fr not_active Ceased

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