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WO2023025671A1 - Composition de glaçure antimicrobienne et photocatalytique - Google Patents

Composition de glaçure antimicrobienne et photocatalytique Download PDF

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Publication number
WO2023025671A1
WO2023025671A1 PCT/EP2022/073161 EP2022073161W WO2023025671A1 WO 2023025671 A1 WO2023025671 A1 WO 2023025671A1 EP 2022073161 W EP2022073161 W EP 2022073161W WO 2023025671 A1 WO2023025671 A1 WO 2023025671A1
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WO
WIPO (PCT)
Prior art keywords
glaze composition
zinc
compound
antimicrobial
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2022/073161
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German (de)
English (en)
Inventor
Jan Interwies
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
N-TEC GmbH
Original Assignee
N-TEC GmbH
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 N-TEC GmbH filed Critical N-TEC GmbH
Priority to EP22768649.0A priority Critical patent/EP4392390A1/fr
Publication of WO2023025671A1 publication Critical patent/WO2023025671A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/32—Burning methods
    • C04B33/34—Burning methods combined with glazing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2092—Resistance against biological degradation

Definitions

  • the invention relates to a glaze composition that can be used to finish the surface of a ceramic article and impart antimicrobial and photocatalytic properties to the surface.
  • the ceramic object can be, for example, sanitary ware, building ceramics or laboratory ceramics, for example a roof tile, a tile, a slab - i.e. a large plate with an edge length of at least 1.5 m, which is used as such or in smaller ones can be divided into pieces - a facade panel, fireclay, a chimney pipe, a kitchen worktop, a kitchen sink or the like.
  • Surface finishing can be carried out on fired, partially fired or unfired ceramic substrates such as green ceramic bodies, clay or loam, as well as engobed, glazed or unglazed substrates.
  • the glaze composition is particularly suitable for the surface finishing of fine stoneware. Since this is mostly not glazed, its surface has a high sensitivity to dirt, which should be reduced with the help of a surface treatment, also known as surface refinement.
  • Known surface finishes usually consist of a mixture of different metal oxides, which are present according to the Seger formula in such amounts to one another that the overall mixture has a neutral pH.
  • at least one metal compound with an antimicrobial effect such as zinc oxide
  • zinc oxide is added to the metal oxide mixture.
  • Such a composition and the corresponding surface finish are described, for example, in EP 3 053 902 A1.
  • a key feature of this and similar metal oxide compositions is a very high proportion of zinc oxide, exceeding 35 percent by weight in the case of EP '902.
  • investigations of such compositions by the applicant have shown that the corresponding surfaces Despite the high zinc oxide content, surface finishes only have very low antimicrobial properties.
  • the high proportion of zinc oxide means that only matt glazes are available, some of which are rough because the zinc oxide forms coarser particles on the surface.
  • the object of the invention is accordingly to specify a glaze composition which gives a ceramic object treated therewith a surface finish with pronounced antimicrobial and photocatalytic properties without noticeably changing the optical properties of the ceramic object.
  • the invention thus relates to a glaze composition with an antimicrobial and photocatalytic effect for the surface finishing of a ceramic object, which comprises at least one silicon compound, at least one aluminum compound, at least one titanium compound and at least one antimicrobial metal compound, the metal of the at least one antimicrobial Metal compound is selected from the group consisting of zinc, tin, copper, calcium, strontium, lanthanum, cerium, iron, nickel, vanadium, molybdenum and tungsten.
  • the weight ratio of aluminum to silicon in the glaze composition is at least 0.3, and the proportion of the metal of the at least one antimicrobial metal compound in the glaze composition is at most 20% by weight.
  • the pH of an aqueous slurry of the glaze composition is in a non-neutral range and deviates from pH 7 by at least 0.2, i.e. it is either acidic (pH ⁇ 6.8) or alkaline (pH > 7.2).
  • Antimicrobial properties are understood in the context of the invention to mean, in particular, antibacterial, antiviral, fungicidal and algicidal properties.
  • an antimicrobial metal compound or an antimicrobial metal refers to substances that are suitable for imparting antimicrobial properties to a surface finish produced using them.
  • a photocatalytic effect is usually understood to mean influencing the kinetics of a chemical reaction under the influence of light, for example in order to start the chemical reaction, accelerate it and/or direct it in a specific direction.
  • the photocatalytic action is mainly aimed at breaking down pollutants and/or pollutants, in particular air pollutants.
  • a catalytic effect is to be included under a photocatalytic effect understand that takes place under the influence of light, and in particular the decomposition of pollution and / or (air) pollutants under the influence of light using at least one photocatalytic metal compound or a photocatalytic metal.
  • the latter refer to substances that are able to achieve a photocatalytic effect.
  • Photocatalytic effects can be detected in a manner known in the prior art, for example by means of a methylene blue test.
  • the antimicrobial metal compound is also simply referred to as "metal compound”.
  • the antimicrobial and photocatalytic properties are summarized under "active properties".
  • the pH of the aqueous suspension of the glaze composition according to the invention deviates by at least 0.2, preferably at least 0.3 or 0.4 or 0.5 or 0.6 or 0.7, in particular by at least 0.8 or 0.9 and more preferably by at least 1.0 from the neutral pH 7.
  • the pH value for the acidic range is therefore preferably at most 6.x, where x can be 0, 1, 2, 3, 4, 5, 6 or 7, or at most 5.y or 4.y, where y is 0 in each case , 1, 2, 3, 4, 5, 6, 7, 8 or 9.
  • the pH is preferably at least 7.z, where z can be 3, 4, 5, 6, 7, 8 or 9, or at least 8.y or 9.y, where y is 0, 1, can be 2, 3, 4, 5, 6, 7, 8 or 9.
  • the glaze composition is chosen so that the pH value deviating from pH 7 is not only present in its aqueous suspension, but also remains either in the acidic or in the alkaline range after firing of the composition and accordingly also with the glaze composition finished surface of the ceramic object has a pH value as described above which is not neutral and in particular deviates from pH 7 by at least 0.2.
  • the pH of the finished surface can be determined, for example, using an aqueous bromothymol blue solution, which is suitably applied to the finished surface of the ceramic object.
  • the bromothymol blue solution is known to be green at neutral pH, yellow in the acidic range and blue in the alkaline range.
  • the weight ratio of aluminum to silicon which are present in the form of at least one aluminum compound and at least one silicon compound in the glaze composition according to the invention.
  • a weight ratio based on the metal atoms is defined according to the invention, since the extensive investigations within the scope of the invention have shown that it appears to achieve a good antimicrobial and photocatalytic effect on the production of suitable mixed-crystal structures on the surface of the finishing layer arrives, which in turn requires a certain ratio of aluminum to silicon.
  • This weight ratio of aluminum to silicon in the glaze composition is at least 0.3. This weight ratio is generally in excess of that found in conventional glaze compositions for making surface finishes.
  • the proportion of aluminum relative to silicon is generally higher in the glaze compositions of the present invention than comparable prior art glaze compositions.
  • this can be modified to a glaze composition according to the invention by adding an aluminum compound and optionally further compounds for adjusting the pH value and/or an antimicrobial metal compound.
  • suitable ratios of aluminum to silicon are in particular >0.35, >0.4, >0.45, >0.5, >0.55 and >0.6.
  • the weight ratio of aluminum to silicon in the glaze composition according to the invention is preferably in a range which is selected from the group consisting of from 0.30 to 5.0, from 0.30 to 4.0, from 0.30 to 3, 0, from 0.40 to 5.0, from 0.40 to 4.0, from 0.40 to 3.0, from 0.40 to 1.2, from 0.45 to 5.0, from 0, 45 to 4.0 and from 0.45 to 3.0.
  • the proportion of the antimicrobial metal compound in the glaze composition according to the invention is comparatively low. It is added so that the metal content of the antimicrobial metal compound is at most 20% by weight based on the total glaze composition.
  • the calculation of the proportions by weight of the individual components of the glaze composition and accordingly the total weight of the glaze composition is carried out without taking any solvents into account. Of course, this does not rule out that individual, several or even all components of the glaze composition are added in dissolved or suspended form. In this case, however, the proportion of solvent in which the added component is dissolved or suspended is not included in the calculation of the proportion by weight or the proportion of solvent is deducted from the calculation of the proportion by weight of the corresponding component.
  • the comparatively small proportion of the at least one antimicrobial metal compound, also simply referred to below as the metal compound, that is required to achieve the antimicrobial effect is not only advantageous in terms of the reduced costs, but is actually usually also a prerequisite for this that a sufficient effect is achieved at all.
  • the investigations accompanying the invention have shown that precisely the high proportion of antimicrobial metal compounds used in the prior art contributes to this means that the surface treated with a corresponding glaze composition has a comparatively low antimicrobial effect.
  • the investigations carried out suggest that the metal compounds used, when used in larger amounts, act as fluxing agents in the glaze composition. As a result, they melt together with the other components of the glaze composition and become embedded in the vitreous melts that form.
  • the antimicrobial metal compound is added so that the proportion of the antimicrobial metal is at most 20% by weight of the glaze composition.
  • the proportion of the metal in the antimicrobial metal compound is preferably lower and is, for example, at most 19, 18, 17, 16, 15, 14, 13, 12, 11 or 10 percent by weight, particularly preferably less than 9 or 8 percent by weight and in particular less than 7 or 6 or 5% by weight of the total glaze composition. If several antimicrobial metal compounds are used, the amounts given relate to the totality of the metals of all antimicrobial metal compounds. In principle, any combination of the antimicrobial metal compounds mentioned is possible. Combinations containing a zinc compound are particularly preferred.
  • a zinc compound such as zinc oxide
  • its proportion is preferably at most 10 percent by weight, particularly preferably less than 8 percent by weight and in particular 3 to 7 percent by weight of the entire glaze composition. Glaze compositions of this type generally lead to transparent, colorless glazes.
  • the inventive combination of the features of a suitable ratio of aluminum to silicon, the adjustment of the pH such that it is not neutral, and a suitable and relatively small amount of an antimicrobial metal compound in the glaze composition leads to the result that the Metal compound when firing the glaze composition does not lose its antimicrobial activity, but in an active form on the surface of the on the Ceramic object formed finishing layer is present. It is essential that the metal compound does not form a vitreous melt with other components of the glaze composition and is not embedded in such a melt. Rather, mixed crystals are formed on the surface of the finishing layer, in the crystal lattice of which metal atoms of the at least one antimicrobial metal compound are incorporated. This mixed crystal formation is only possible if the parameters described above are observed at the same time.
  • the desired mixed crystal formation can be promoted in a targeted manner by a suitable choice of the components of the glaze composition.
  • the selection is made in particular taking into account the conditions under which the firing process of the glaze composition is to take place on the ceramic object to be finished, in particular taking into account the firing temperature and the firing time.
  • the components and in particular the antimicrobial metal compound are expediently selected in such a way that they form a melt at the selected firing temperature in the specified firing time, from which crystallization and the formation of the desired mixed crystals can take place.
  • Frits can be used, for example, to set a suitable viscosity in the melt of the glaze composition, which enables crystallization of the desired mixed crystals from the melt.
  • frits containing at least one antimicrobial metal in the glaze composition it is possible and sometimes even advantageous to use frits containing at least one antimicrobial metal in the glaze composition, and it has been observed that the antimicrobial effect of the composition can be improved even further as a result.
  • such frits are preferably used only in addition to an antimicrobial metal compound that is not present in the form of a frit.
  • the metal of the antimicrobial metal compound used according to the invention is selected from the group consisting of zinc, tin, copper, calcium, strontium, lanthanum, cerium, iron, nickel, vanadium, molybdenum and tungsten.
  • the tin compounds are those that can be used to produce glazing compositions and surface finishes whose pH is in the acidic range.
  • Tin oxide, tin hydroxide and tin chloride or any mixtures thereof are used as preferred tin compounds.
  • Tin hydroxide and tin chloride are converted into tin oxide during firing and, like tin oxide itself, form oxidic - i.e.
  • the other antimicrobial metal compounds i.e. those of zinc, copper, calcium, strontium, lanthanum, cerium, iron, nickel, vanadium, molybdenum and tungsten - are suitable for the production of basic glaze compositions, which lead to refined surfaces with an alkaline pH value.
  • compounds of zinc, strontium, iron, copper and nickel are preferred, with zinc compounds being particularly preferred in the present invention.
  • Combinations of the metal compounds mentioned can also be used. For example, combinations of zinc and strontium compounds produce very good results. Even tin compounds can be used to form alkaline glaze compositions when combined with a sufficient amount of alkaline components. However, this is not preferred according to the invention, also because tin compounds usually lead to clouding and thus to an optical impairment of the surface finish obtained.
  • the metal compounds are preferably selected from the group consisting of oxides, hydroxides, carbonates, nitrates, sulfates, chlorides or mixtures thereof. Sulfates and chlorides are preferably only used in combination with other naturally basic metal compounds in order to be able to reliably adjust the pH of the glaze composition to at least 7.2.
  • Metal compounds which are particularly preferred according to the invention are zinc oxide, zinc hydroxide or zinc carbonate and mixtures thereof. As mentioned, these can also be combined with other antimicrobial metal compounds, such as those of strontium, in particular strontium hydroxide and/or strontium carbonate, the latter also giving good results on their own—without zinc compounds.
  • the metal compounds that are not initially present as oxides are converted into oxides during the firing process.
  • other metal compounds can in principle also be used can be converted into the corresponding oxides during firing, such as oxalates.
  • Oxidic mixed crystals are formed from the oxides in combination with elements of the other components of the glaze composition during the firing process. Here, too, it can be seen that these mixed crystals accumulate on the surface of the finishing layer, where they develop a high antimicrobial effect.
  • the components of the glaze composition at least partially in the form of naturally occurring rocks. These are ground up before addition and added in powder form.
  • Carbonate minerals for example, are suitable for use in a basic pH glaze composition.
  • rocks that are low in silicate and/or rocks that are rich in aluminum are preferably used, which are found among other things among igneous rocks. Suitable examples are bentonite, calcite, diabase, dolomite, foil syenite, kaolin, melilite, montmorillonite, mullite, nepheline, olive, plagioclase, pyroxene and syenite.
  • the parameters pH value, Al:Si ratio and proportion of the antimicrobial metal compound specified according to the invention can be adjusted by suitable selection of the minerals and their proportions by weight—if necessary by supplementing missing proportions by adding pure individual compounds.
  • composition of the components of the glaze composition according to the invention it has proven advantageous to select only those with a basic pH if a glaze composition is to be produced with a pH in the alkaline range, and - apart from the required Silicon compound - to avoid acidic and especially strongly acidic components if possible.
  • a glaze composition with an acidic pH if possible only those components are used which have an acidic pH, while alkaline and in particular strongly alkaline components are not used if possible - apart from the required at least one aluminum compound.
  • the invention deviates from the generally customary procedure in which, according to the Seger formula, components from the basic, neutral and acidic groups are put together in such a way that a neutral pH results.
  • the at least one aluminum compound which must be contained in the glaze composition according to the invention is preferably selected from the group consisting of aluminum oxide, aluminum hydroxide, aluminum nitrate and aluminum alcoholates.
  • the latter can be fully or partially hydrolyzed.
  • the alcohol residue is preferably selected from aliphatic, saturated, branched or unbranched alcohol residues having 1 to 8 and in particular 1 to 4 carbon atoms. preferred Examples are methanol, ethanol, n-propanol, isopropanol, n-, sec- or tert-butanol or mixtures thereof.
  • the aluminum compound is particularly preferably selected from aluminum oxide or aluminum hydroxide.
  • the at least one silicon compound that must also be present is expediently selected from the group consisting of frits, clay minerals and quartz powder, with the latter being less preferred.
  • the metal compound therefore expediently has an average particle diameter D 50 of 1 nm to 30 ⁇ m, preferably 50 nm to 500 nm, particularly preferably 50 nm to 200 nm and in particular 50 to 100 nm.
  • the at least one aluminum compound such as aluminum oxide or aluminum hydroxide this preferably has an average particle diameter D 50 of 1 nm to 30 ⁇ m and in particular of 1 to 6 ⁇ m.
  • a maximum particle size of 30 ⁇ m for the aluminum compound is also preferred because with larger particle diameters the aluminum compound no longer forms eutectics with other components of the glaze composition under the usual firing conditions.
  • the formation of a eutectic can lower the melting point of the glaze composition, which in turn affects the viscosity of the melt and thus the ability to form the desired mixed crystals.
  • the interaction of aluminum compounds such as aluminum oxide with zinc compounds such as zinc oxide promotes mixed crystal formation.
  • the formation of mixed crystals, in the crystal structure of which metal atoms of the at least one antimicrobial metal compound are incorporated, is important in order to achieve high photocatalytic and antimicrobial activity of the surface finish of a ceramic object produced from the glaze composition according to the invention.
  • Crystal formation can be promoted by suitably adjusting the viscosity of the melt formed during the firing process.
  • a possibility of adjusting the viscosity of the melt, which is known per se, consists in a suitable choice of the concentration of the melt phase formers or fluxes in the glaze composition.
  • the glaze components used as antimicrobial metal compounds such as zinc oxide in higher amounts of, for example, more than about 8 and in particular more than 10 percent by weight, themselves act as fluxes.
  • a suitable choice of the amount of the at least one antimicrobial metal compound can therefore in some cases mean that no further fluxing agents have to be added to the glaze composition.
  • at least one melt phase former/flow agent is additionally added to the glaze composition.
  • Preferred melt phase formers/fluxes are, for example, alkali metal and/or alkaline earth metal compounds, since it has been found that they can also improve the photocatalytic effect of surface treatment.
  • alkali and alkaline earth metals of which sodium, potassium, magnesium, calcium and barium are preferred, promote the formation of the mixed crystals and are incorporated into the crystal structure themselves to form active basic silicates, thereby increasing the antimicrobial and photocatalytic properties evoke activity.
  • melt-phase formers/fluxes which of these melt-phase formers/fluxes are actually used depends, among other things, on whether a glaze composition with an alkaline or an acidic pH value is to be produced. As already mentioned, it is preferable, if possible, to use acidic or at least neutral components for acidic glaze compositions, but preferably alkaline or at least neutral components for alkaline glaze compositions.
  • acidic or at least neutral components for acidic glaze compositions but preferably alkaline or at least neutral components for alkaline glaze compositions.
  • alkali metal and/or alkaline earth metal halides, in particular chlorides are suitable.
  • suitable basic melt phase formers or fluxes are preferably selected from alkali metal or alkaline earth metal oxides, hydroxides, carbonates, phosphates, silicates or tungstates.
  • melt phase formers/fluxing agents can also be used.
  • the quantity with which the melt phase former/the flux is added to the glaze composition is - as mentioned - selected in such a way that oxidic mixed crystals can form in the melt of the glaze composition at the selected firing temperature within the firing time, the dissolution of the antimicrobial metal compound(s) in a glassy melt, on the other hand, is prevented.
  • melt phase former/flux promote such an undesirable dissolution of the antimicrobial metal compound in the glass matrix.
  • Appropriate amounts of melt phase former/fluxing agent can be readily determined by simple experimentation.
  • Glaze compositions that are to be fired at a comparatively low temperature and/or in rapid firing generally require a higher proportion of melt phase formers/fluxes than those that are fired at a higher temperature.
  • a frit can also be added to the glaze composition. This can take place as an alternative to or in addition to the addition of the melt phase former.
  • a frit containing the metal of the at least one antimicrobial metal compound is preferably added.
  • the frit then serves not only to adjust the viscosity of the melt, but is also suitable for improving the antimicrobial effect of the surface finish produced.
  • the frit will usually be present in the glaze composition in an amount of up to 65% by weight, in particular at most 60, 50, 40, 30 or 25% by weight.
  • the appropriate amount can easily be determined by simple experiments. In all cases, when adding further compounds, care must be taken to ensure that the specified ratio of aluminum to silicon of at least 0.3 is not shifted outside the specified range as a result of the addition.
  • the invention may also be practiced by modifying glaze compositions known in the art to have the above-described properties of a suitable aluminum to silicon ratio, a pH differing from pH 7 by at least 0.2, and have a proportion of metal of at least one antimicrobial metal compound of at most 20 percent by weight, so that they are able to form the desired mixed crystals and thus a high photocatalytic and antimicrobial activity on the ceramic object to be refined during the firing process.
  • a suitable aluminum compound such as aluminum oxide or aluminum hydroxide.
  • a shift in the pH value into the alkaline range can also be achieved in this way.
  • Aluminum compounds such as aluminum oxide in particular also have an influence on the viscosity of the melt of the glaze composition formed during firing and prevent the melt from melting too early or being too liquid, in which crystallization and formation of the desired mixed crystals cannot take place. If necessary, the proportion of the antimicrobial metal compound can be reduced by increasing the other components of the glaze composition, whereby a suitable viscosity of the melt can also be adjusted by means of components such as fluxes in order to promote the formation of the mixed crystals, if this should be necessary.
  • the active properties of the surface finishing layers produced using the glaze composition according to the invention can be adjusted in such a way that the photocatalytic or the antimicrobial properties predominate.
  • the use of calcium compounds enhances the photocatalytic properties, while zinc compounds produce both photocatalytic and antimicrobial properties.
  • compounds of the metals lanthanum, molybdenum and tungsten also lead to photocatalytic properties of the surface finishes produced with the glaze compositions according to the invention. In some cases, however, these photocatalytic properties are not quite sufficient, so that, according to the invention, titanium compounds are additionally used in order to impart pronounced photocatalytic properties to the glaze composition and the surface finish produced from it.
  • the titanium compound can be added to the glaze composition, for example, in the form of titanium dioxide. In some cases, however, this leads to a milky clouding of the finish layer formed. According to the invention it is therefore preferred to add the titanium compound in the form of a titanium alcoholate.
  • the addition usually takes place in an aqueous or alcoholic solvent, so that the titanium alcoholate is optionally present in at least partially hydrolyzed form.
  • all suitable alcoholic solvents are those which are suitable for dissolving the selected titanium alcoholate. Aliphatic saturated, branched or unbranched alcohols, preferably having 1 to 8 and in particular 1 to 4 carbon atoms, are preferred.
  • the alcoholic residues of the titanium alcoholate are preferably derived from the alcohols already mentioned as solvents.
  • a single titanium alcoholate compound is preferably used in the composition, but mixtures of different titanium alcoholates can also be used in the process according to the invention, particularly if non-hydrolyzed, partially hydrolyzed and/or completely hydrolyzed titanium alcoholates are present side by side.
  • an amount of the titanium compound of up to 5% by weight, based on the total glaze composition is usually sufficient.
  • the glaze composition contains preferably 0.01 to 4.5% by weight, expediently 0.02 to 3% by weight, particularly preferably 0.02 to 2.5% by weight and in particular 0.02% up to 2% by weight titanium. As mentioned at the beginning, the quantity is calculated without taking the solvent into account.
  • the titanium contained in the glaze composition is integrated into the crystal structure of the mixed crystals that are formed during the firing process.
  • the extraordinarily good photocatalytic properties of the coating according to the invention are again attributed to the fact that the titanium, like the other active components, is present in the form of mixed crystals and not in rutile or anatase form and is enriched on the surface of the coating layer.
  • the glaze composition according to the invention can in principle be applied in any manner known in the prior art.
  • the glaze composition is preferably slurried in a suitable solvent before application to the substrate surface to be finished.
  • Aqueous solvents such as water-alcohol mixtures and in particular pure water are preferred.
  • the slurry can be applied to the substrate surface in any suitable manner, for example by steam atomization, pouring, spinning, flow-coating, dipping, rolling or printing or, which is preferred according to the invention, by spraying. By spraying, particularly even applications can be achieved with a very small layer thickness.
  • the spraying can take place, for example, by means of airless or HVLP spraying.
  • the airless spraying method is carried out, for example, with a membrane pump and a pressure of up to 300 kPa or also with high pressure of up to 30,000 or 40,000 kPa, the slurry being applied to the substrate without the action of an atomizing agent.
  • the atomization pressure is generally in the range of 700 to 1300 kPa and in particular around 1000 kPa.
  • the basic procedure is known to those skilled in the art. Since only a small layer thickness has to be achieved, a single spraying process is usually sufficient. However, if necessary, several spraying processes can be carried out one after the other. 1
  • Application is generally made to a ceramic object that has not yet been fired (green compact) or to a pre-fired ceramic object, for example after biscuit firing. It is also possible to finish the surface of a ceramic object that has already been completely fired, but this is not preferred from the point of view of costs, since when applied to a green compact or a pre-fired ceramic object, the object and the glaze composition can be fired simultaneously, thus saving energy.
  • the slurry of glaze composition applied to the surface of the ceramic article to be finished is then fired evaporate very quickly during the firing process.
  • the firing process itself takes place in a manner customary in the prior art for glaze compositions and generally at a temperature between 650 and 1350°C, preferably at 800 to 1250°C.
  • the glaze composition can be fired both in short firing and in long firing, with the duration of firing usually being between 0.5 and 5 hours for short firing and between 5 and 40 hours for long firing.
  • the glaze composition according to the invention is suitable for finishing practically any conceivable ceramic object whose surface is to be given improved surface properties, so that it offers protection against aggressive environmental or chemical influences, for example, is water, dirt or lime-repellent or easy to clean becomes.
  • the surface can be completely or only partially provided with a surface finish.
  • Surface finishing can be carried out on fired, partially fired or unfired ceramic substrates such as green ceramic bodies, clay or loam, as well as engobed, glazed or unglazed substrates.
  • Suitable ceramic substrates come from the field of sanitary ceramics, building ceramics or laboratory ceramics. Concrete examples are roof tiles, tiles (both for floors and walls), slabs, facade panels, fireclay, chimney pipes, kitchen worktops, kitchen sinks or the like.
  • a particularly preferred ceramic substrate is fine stoneware, for example in the form of wall or floor tiles, which - like the other coated ceramic objects - is given a hard-wearing and, in particular, dirt-repellent surface thanks to the surface finishing layer according to the invention, which is also self-cleaning due to the photocatalytic properties.
  • the antimicrobial and photocatalytic properties of the surface finishing layer produced using the glaze composition according to the invention are largely based on the formation of mixed crystals of titanium and/or the metal of the antimicrobial metal compound with silicon and/or aluminum and oxygen. If compounds containing alkali or alkaline earth metals were also added to the glaze composition as melt phase formers or fluxes, the mixed crystals formed also contain the corresponding alkali or alkaline earth metal elements. elements in the crystal lattice.
  • the antimicrobial metal compound is a zinc compound
  • mixed crystals are formed which correspond to the formula 2 ZnO • SiO 2 , with other metal atoms such as the already mentioned alkali or alkaline earth metals and/or titanium possibly being added - depending on the overall composition of the glaze composition the crystal lattice are built in.
  • mixed crystals of different composition are usually formed, distributed over the surface finishing layer. The formation of uniform mixed crystals of the same composition over the entire surface is rather the exception.
  • the metal of the antimicrobial metal compound is zinc, various zinc-titanium-silicon-aluminium oxide crystals and/or alkali/alkaline earth zinc-titanium-silicon are formed -Alumina- crystals.
  • zinc titanium silicon aluminum hydroxide crystals and/or alkali/alkaline earth zinc titanium silicon aluminum hydroxide crystals are also formed.
  • the mixed crystals generally form with a concentration gradient of the active metal elements such as zinc and titanium, which are essentially concentrated in an area that faces the outer surface of the layer indicates. In the lower lying areas from about 1 pm depth of the finishing layer, the concentration of the metal atoms then decreases.
  • the photocatalytically and/or antimicrobially active metal elements are therefore present in the mixed crystals exactly where they are supposed to develop their activity, namely on the outermost surface of the finished ceramic object.
  • the cause of this concentration gradient of the active metal is assumed to be that during the firing process the material on the surface of the ceramic object initially forms a vitreous layer with components of the glaze composition.
  • a dedicated layer boundary between the surface of the ceramic object and the finishing layer can hardly or not at all be discerned in the finished ceramic object.
  • the active mixed crystals then grow out of this vitreous layer formed on the surface of the ceramic object and are enriched with the active metal during the crystallization process.
  • the height at which the mixed crystals grow out of the vitreous layer is usually at most 100 ⁇ m, in particular at most 50 ⁇ m and predominantly not more than 25 ⁇ m, measured perpendicularly to the surface of the ceramic object.
  • Example 1 Calcium Containing Active Glaze Composition
  • MgO was first modified by adding a flux (magnesium oxide) and then by adding an antimicrobial metal compound (zinc oxide) and a titanium compound (titanium isopropoxide), resulting in the following modified glaze composition: a) Glaze composition modified with zinc, titanium and magnesium
  • the glaze composition a) After being slurried in water, the glaze composition a) is applied to the surface of a ceramic object to finish it and, after firing, results in a finish with a basic pH value (pH > 8, measured with an aqueous bromothymol blue solution) and antimicrobial and photocatalytic properties.
  • a basic pH value pH > 8, measured with an aqueous bromothymol blue solution
  • the antimicrobial metal compound is added in the form of zinc carbonate:
  • Example 3 Barium and calcium containing active glaze composition
  • barium and calcium containing glaze composition which also contains zinc in the form of a zinc containing frit and which has the following components:
  • an active glaze composition is produced by adding titanium isopropoxide and a zinc compound that is not in the form of a frit. Specifically, 6% zinc oxide is added, which leads to an active glaze composition with the following components:
  • a surface finish produced using this glaze composition exhibits high antimicrobial and photocatalytic activity.
  • Example 4 Barium and calcium containing active glaze composition
  • barium- and calcium-containing glaze composition which contains zinc in the form of a zinc-containing frit and, in addition, magnesium oxide and which has the following components:
  • an antimicrobial and photocatalytic glaze composition is prepared by adding a zinc compound that is not in the form of a frit, namely zinc oxide, as well as titanium isopropoxide.
  • An active glaze composition is obtained with the following ingredients:
  • the components of the glaze compositions mentioned in the above examples do not necessarily have to be added in the form of the oxides mentioned.
  • titanium was added in the form of titanium isopropoxide in isopropanol/water.
  • the amounts used (without solvent) were converted into the corresponding amounts of titanium dioxide in the examples.
  • Individual, several or all of the other components mentioned can also be added in the form of other metal compounds that can be converted into the corresponding oxides during the firing process. Examples of suitable metal compounds have already been mentioned in the previous description, in particular carbonates, halides, hydroxides, nitrates, phosphates, sulfates, etc. It is also possible to add the components of the glaze composition at least partially in the form of naturally occurring rocks that have previously been ground to powder.
  • suitable rocks are carbonate rocks and low-silicate and/or aluminum-rich rocks, particularly magmatic rocks such as bentonite, calcite, diabase, dolomite, foidsyenite, kaolin, melilite, montmorillonite, mullite, nepheline, olive, plagioclase, pyroxene and syenite . These are used in amounts such that conversion into the oxides gives the percentages given in the examples.
  • the glaze compositions are slurried in water. About 0.2 to 5.0, preferably 0.4 to 3.0, in particular 0.5 to 1.8 parts by volume of water are added per part by volume of glaze composition.
  • a raw and unfired green tile body produced in a manner customary in the prior art is dried until its water content is at most 1 to 8%. This is followed, if appropriate, by decoration and the application of the suspended glaze composition according to the invention to the green tile compact.
  • the application is done in a single layer. A multi-layer application is possible, but - apart from sanitary glazes - not preferred in order to obtain the thinnest possible layer.
  • the temperature of the green tile body during application is 15 to 150 °C, preferably 40 to 80°C.
  • the slurried glaze composition is applied by spraying according to the following parameters:
  • Spraying spraying pressure 100 - 1000 kPa, preferably 400 - 700 kPa
  • Needle variable diameter 0.3 to 2.5 mm, preferably 0.5 to 1.5 mm
  • the amount of the composition is 10 to 350 g/m 2 , preferably 150 to 250 g/m 2 .
  • the green body is optionally dried again, in which case it is then heated to a temperature in the range from room temperature (20°C) to 300°C, preferably from 35 to 150°C. Drying and heating of the green compact is not necessary, especially in cases where the kiln has a drying zone in the heating zone at the beginning of the kiln section.
  • the green compact is transported into a kiln in a heated state or alternatively at room temperature in order to be fired. The burning process takes place in a manner that is customary in the prior art, for example in accordance with one of the following alternatives:
  • the tile After leaving the oven, the tile is ready and can be packaged, optionally after allowing it to cool to room temperature.
  • the height at which the mixed crystals protrude over the adjacent surface is less than 25 ⁇ m.
  • the finishing layer cannot be seen with the naked eye and, in comparison to an unfinished tile, does not cause any visual impairment.
  • Elemental analyzes of the crystalline surface by means of energy-dispersive X-ray spectroscopy were carried out for some surface finishing layers produced according to the invention.
  • the results for glazes A, B and C are summarized in Table 1 below. All glazes have an antimicrobial and pronounced photocatalytic effect.
  • FIGS. 5 to 13 Electron micrographs, which are attached as FIGS. 5 to 13, were taken of the outer surfaces of surface finishing layers produced according to the invention.
  • FIGS. 1 to 4 show electron micrographs of conventional surface finishes.
  • the image section corresponds to 150 pm by 100 pm in the actual surface structure. Show in detail:
  • Fig. 2 shows another example of a conventional barium-containing glaze
  • Fig. 3 shows a conventional calcium-containing glaze
  • FIG. 5 shows a surface treatment according to the invention from a calcium-containing glaze composition with titanium isopropoxide and zinc oxide;
  • FIG. 6 shows a surface treatment according to the invention from a barium-containing glaze composition with titanium isopropoxide and zinc carbonate;
  • FIG. 7 shows a sanitary glaze made from a glaze composition according to the invention with titanium isopropoxide and zinc oxide;
  • FIG. 8 shows a surface treatment according to the invention from a barium-containing glaze composition with titanium isopropoxide and zinc oxide;
  • FIG. 10 shows a further surface treatment according to the invention from a barium-containing glaze composition with titanium isopropoxide and zinc oxide;
  • FIG. 11 shows a further surface treatment according to the invention from a barium-containing glaze composition with titanium isopropoxide and zinc oxide;
  • FIG. 12 shows a surface treatment according to the invention from a barium-containing glaze composition with titanium isopropoxide, zinc oxide and strontium carbonate, and
  • FIG. 13 shows a surface treatment according to the invention from a barium-containing glaze composition with titanium isopropoxide, zinc oxide and eithium tungstate.
  • the photographs of the surface finishes according to the invention show a strong crystallization which is caused by the mixed crystals formed according to the invention.
  • These mixed crystals are structures of the formula 2 ZnO • SiO 2 and other oxygen-containing crystals, which in addition to silicon, titanium and zinc other metals contained in the glaze composition incorporated into the crystal lattice.
  • these are zinc titanium silicon aluminum oxide crystals, alkali metal/alkaline earth metal zinc titanium silicon aluminum oxide crystals, zinc titanium silicon aluminum hydroxide crystals and/or alkali metal/alkaline earth metal zinc Titanium silicon aluminum hydroxide crystals.
  • mixed crystals of different compositions are distributed side by side over the finished surface. These structured and differentiated surfaces are held responsible for the outstanding antimicrobial and photocatalytic properties of the surface finishing of ceramic objects according to the invention.
  • FIG. 5 shows a surface finish which was produced from glaze compositions containing calcium and which was modified by the addition of titanium isopropoxide and zinc oxide.
  • the surface finish of FIG. 5 has the composition of glaze B from the table
  • FIG. 7 shows a sanitary glaze whose composition corresponds to glaze C in Table 1. It was made from a glaze composition of the invention modified with titanium isopropoxide and zinc oxide.
  • the surface finish shown in Figure 8 was created from a barium containing glaze composition modified with 4.9% by weight zinc oxide and 2.8% by weight titanium isopropoxide. Similar surface finishes are shown in Figures 9 through
  • All surface finishes have photocatalytic properties in addition to antimicrobial properties.
  • the crystal structures seen in Figures 5 to 13 have grown out of a vitreous layer which is formed during the firing process by reaction of the glaze composition with constituents on the surface of the ceramic article.
  • the height at which the mixed crystals that form grow out of the vitreous layer and protrude over the vitreous layer in the finished surface finish is in all cases below 100 ⁇ m and is generally less than 50 ⁇ m and in particular at most 25 ⁇ m, measured in a vertical direction Direction to the surface of the ceramic object.

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Abstract

L'invention concerne une composition de glaçure présentant un effet antimicrobien et photocatalytique pour la finition de surface d'un article en céramique, ladite composition de glaçure comprenant au moins un composé de silicium, au moins un composé d'aluminium, au moins un composé de titane et au moins un composé métallique antimicrobien, le métal dudit composé métallique antimicrobien étant choisi dans le groupe constitué par le zinc, l'étain, le cuivre, le calcium, le strontium, le lanthane, le cérium, le fer, le nickel, le vanadium, le molybdène et le tungstène. Dans la composition de glaçure, le rapport pondéral de l'aluminium au silicium est d'au moins 0,3, la proportion du métal dudit composé métallique antimicrobien dans la composition de glaçure est d'au plus 20 % en poids et une suspension aqueuse de la composition de glaçure présente un pH qui s'écarte d'au moins 0,2 par rapport à pH 7. L'invention concerne également un procédé d'application d'un revêtement sur un article en céramique avec la composition de glaçure agissant de manière antimicrobienne et photocatalytique et un article en céramique revêtu produit selon le procédé.
PCT/EP2022/073161 2021-08-25 2022-08-19 Composition de glaçure antimicrobienne et photocatalytique Ceased WO2023025671A1 (fr)

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CN118344008A (zh) * 2024-05-17 2024-07-16 潮州市欧博瓷业有限公司 一种耐高温抗氧化陶瓷釉料及其制备方法

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WO2006061367A1 (fr) * 2004-12-06 2006-06-15 Colorobbia Italia S.P.A. Procede de preparation de dispersions de tio2 sous forme de nanoparticules, dispersions obtenues a l'aide du procede et fonctionnalisation de surfaces par l'application de dispersions de tio2
US20090104459A1 (en) * 2007-02-20 2009-04-23 Microban Products Company Ceramic glaze having antimicrobial property
WO2011108472A1 (fr) * 2010-03-01 2011-09-09 株式会社 オハラ Verre pour glaçure, glaçure et élément photocatalytique
EP2759524A1 (fr) * 2011-09-20 2014-07-30 Consejo Superior De Investigaciones Científicas (CSIC) Combinaison et procédé d'obtention d'émaux céramiques bactéricides pour des produits en céramique
EP3053902A1 (fr) 2015-02-04 2016-08-10 Duravit Aktiengesellschaft Objet en ceramique et procede de fabrication d'un tel objet

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DE102019006135A1 (de) 2019-08-30 2021-03-04 N-Tec Gmbh Verfahren zum Erzeugen von katalytisch aktiven Oberflächen
DE102019007756A1 (de) 2019-11-08 2021-05-12 N-Tec Gmbh Verwendung von Titanverbindungen

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WO2006061367A1 (fr) * 2004-12-06 2006-06-15 Colorobbia Italia S.P.A. Procede de preparation de dispersions de tio2 sous forme de nanoparticules, dispersions obtenues a l'aide du procede et fonctionnalisation de surfaces par l'application de dispersions de tio2
US20090104459A1 (en) * 2007-02-20 2009-04-23 Microban Products Company Ceramic glaze having antimicrobial property
WO2011108472A1 (fr) * 2010-03-01 2011-09-09 株式会社 オハラ Verre pour glaçure, glaçure et élément photocatalytique
EP2759524A1 (fr) * 2011-09-20 2014-07-30 Consejo Superior De Investigaciones Científicas (CSIC) Combinaison et procédé d'obtention d'émaux céramiques bactéricides pour des produits en céramique
EP3053902A1 (fr) 2015-02-04 2016-08-10 Duravit Aktiengesellschaft Objet en ceramique et procede de fabrication d'un tel objet

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118344008A (zh) * 2024-05-17 2024-07-16 潮州市欧博瓷业有限公司 一种耐高温抗氧化陶瓷釉料及其制备方法

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