WO2013083057A1 - 抗菌性组合物及抗菌性釉料组合物以及抗菌性物品 - Google Patents

抗菌性组合物及抗菌性釉料组合物以及抗菌性物品 Download PDF

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Publication number
WO2013083057A1
WO2013083057A1 PCT/CN2012/086035 CN2012086035W WO2013083057A1 WO 2013083057 A1 WO2013083057 A1 WO 2013083057A1 CN 2012086035 W CN2012086035 W CN 2012086035W WO 2013083057 A1 WO2013083057 A1 WO 2013083057A1
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WIPO (PCT)
Prior art keywords
silver
antibacterial
powder
composition
glaze
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
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PCT/CN2012/086035
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English (en)
French (fr)
Inventor
堀越秀纪
矢泽孝子
野边正纮
赵振海
魏斯毅
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.)
Sumi Long Nanotechnology Materials Shenzhen Co Ltd
Sumitomo Osaka Cement Co Ltd
Original Assignee
Sumi Long Nanotechnology Materials Shenzhen Co Ltd
Sumitomo Osaka Cement Co Ltd
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Priority to JP2014545081A priority Critical patent/JP2015505832A/ja
Publication of WO2013083057A1 publication Critical patent/WO2013083057A1/zh
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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • 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
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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

Definitions

  • the present invention relates to an antibacterial composition, an antibacterial glaze composition, and an antibacterial article.
  • the present invention relates to a building material suitable for use in sanitary ware, medical supplies, enamel articles, various containers, tableware, and the like.
  • the composition of the material forms a film-coated antimicrobial article. Background technique
  • metals such as silver, copper, and zinc are widely used as antibacterial components. These metals are thought to have an effect of inhibiting the proliferation of bacteria by their ions acting on active enzymes in cells such as bacteria.
  • the concentration of the antibacterial component required to prevent the proliferation of the bacteria is expressed by the minimum inhibitory concentration (MIC).
  • MIC minimum inhibitory concentration
  • the concentration of the antibacterial component required to prevent the proliferation of the bacteria is expressed by the minimum inhibitory concentration (MIC).
  • the concentration of the antibacterial component required to prevent the proliferation of the bacteria is expressed by the minimum inhibitory concentration (MIC).
  • the MIC for Escherichia coli is about 200 ppm.
  • Patent Documents 1 to 3, etc. is known (for example, reference) Patent Documents 1 to 3, etc., and have been actually implemented.
  • a ceramic or enamel product in order to form a strong coating on the surface of the glaze component, it is generally baked at a temperature of 700 ° C or more and 1300 ° C or less for 1 hour or more.
  • metallic silver since the metallic silver diffuses to the surface during the firing and evaporates from the surface, the amount of silver in the obtained coating film becomes smaller than the originally predetermined amount, and as a result, There is a problem that the antibacterial property of the film is lowered.
  • Patent Document 7 Japanese Patent Laid-Open No. Hei 6-340513
  • Patent Document 2 Japanese Patent Laid-Open No. 7-196384
  • Patent Document 3 Japanese Patent Laid-Open No. 7-268652
  • Patent Document 4 Japanese Patent Laid-Open No. 3-38504
  • Patent Document 5 Japanese Patent Laid-Open No. 7-291658
  • Patent Document 6 Japanese Special Report 2004-300086
  • Patent Document 7 Japanese Patent Laid-Open No. Hei 9-173162 SUMMARY OF INVENTION
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide an antibacterial composition, an antibacterial glaze composition, and an antibacterial article which can improve antibacterial properties even when a small amount of metallic silver or a silver compound is used.
  • the present inventors conducted intensive studies to solve the above problems, and as a result, found that if a composition containing a silver-containing powder and a silver-containing vitreous powder is prepared, the silver-containing powder contains any of metallic silver and silver compounds.
  • the silver component of one or both of the composition, the glassy powder containing the silver-containing glassy powder contains 0.01% by mass or more and 50% by mass or less of the metal silver and the silver compound in terms of metal silver.
  • the antibacterial composition of the present invention comprises a silver-containing powder and a silver-containing glassy powder, and the silver-containing powder contains one or both of metallic silver and a silver compound.
  • a silver component, the glassy powder containing silvery glassy powder contains metal
  • the silver component is composed of any one or two of metallic silver and silver compounds in an amount of 0.01% by mass or more and 50% by mass or less.
  • the silver-containing vitreous powder has a softening point of 300 ° C or more and 1500 ° C or less. It is preferable to further contain a second vitreous powder having a softening point of 300 ° C or more and 1500 ° C or less.
  • the silver-containing glassy powder or the second glassy powder contains one or two or more kinds of vitreous powders having a softening point of not more than the melting point of silver.
  • the silver compound is preferably one or more selected from the group consisting of silver phosphate, silver oxide, silver carbonate, silver nitrate, silver chloride, silver sulfide, and silver acetate.
  • the antibacterial glaze composition of the present invention comprises the antibacterial composition of the present invention and a glaze, wherein the antibacterial composition contains a silver-containing powder and a silver-containing vitreous powder, and the silver-containing powder contains metallic silver and
  • the silver component of any one or two of the silver compounds, the glassy powder containing the silver-containing glassy powder contains 0.1% by mass or more and 50% by mass or less of metallic silver and silver in terms of metallic silver.
  • the silver component of any one or two of the compounds, the antibacterial glaze composition is characterized in that the content of the antibacterial composition is 0.01% by mass or more and 5 masses in terms of metal silver in terms of the glaze. %the following.
  • the antibacterial article of the present invention is characterized in that a film is formed by using the antibacterial glaze composition of the present invention. Effect of the invention
  • the silver-containing powder contains a silver component composed of either or both of metallic silver and a silver compound.
  • the glassy powder containing the silvery glassy powder is converted into metal silver
  • the silver component composed of either or both of metallic silver and silver compound is contained in an amount of 0.01% by mass or more and 50% by mass or less. Therefore, the antibacterial property can be improved, and the metallic silver or silver compound contained can be reduced. The amount.
  • the antibacterial glaze composition of the present invention the antibacterial composition and the glaze of the present invention are contained, and the content of the antibacterial composition is set to 0.01% by mass or more in terms of metal silver with respect to the glaze.
  • the antibacterial property of the glaze can be improved, and the amount of the metallic silver or silver compound contained can be reduced.
  • the antibacterial article of the present invention since the film is formed by the antibacterial glaze composition of the present invention, the antibacterial property of the surface of the antibacterial article can be improved, and the metal silver or silver compound contained therein can be reduced. The amount.
  • Fig. 1 is a cross-sectional view showing an example of a silver-containing glassy powder according to an embodiment of the present invention.
  • Fig. 2 is a cross-sectional view showing another example of the silver-containing glassy powder according to the embodiment of the present invention.
  • Fig. 3 is a cross-sectional view showing still another example of the silver-containing glassy powder according to the embodiment of the present invention. Label description
  • the antibacterial composition of the present embodiment is a composition containing a silver-containing powder and a silver-containing vitreous powder, wherein the silver-containing powder contains one or both of metallic silver and silver compound.
  • the silver-containing glassy powder is contained in an amount of 0.01% by mass or more and 50% by mass or less in terms of metal silver, and is composed of either or both of metallic silver and a silver compound.
  • Silver composition The ratio (M Ag : M G ) of the mass (M Ag ) of the silver-containing powder in the antibacterial composition to the mass (M G ) of the silver-containing vitreous powder is preferably in the range of 1:0.1 to 1:100.
  • the silver-containing glassy powder when the mass (M Ag ) of the silver-containing powder is 1, if the mass (M Q ) of the silver-containing glassy powder is less than 0.1, the silver-containing glassy powder is too small to lose the antibacterial property. The effect is not preferable.
  • the mass (M Ag ) of the silver-containing powder when the mass (M Ag ) of the silver-containing powder is 1, if the mass (Me) of the silver-containing glassy powder exceeds 100, the total amount of silver is too small to satisfy The amount of silver required for the antibacterial effect is therefore not preferred.
  • the silver-containing powder and the silver-containing glassy powder which are components of the antibacterial composition of the present embodiment will be described.
  • the silver-containing powder is a powder containing a silver component composed of either or both of metallic silver and a silver compound.
  • the silver compound is preferably one or more selected from the group consisting of silver phosphate, silver oxide, silver carbonate, silver nitrate, silver chloride, silver sulfide, and silver acetate.
  • the average primary particle diameter of the silver-containing powder is preferably ⁇ or more and 30 ⁇ or less, and more preferably ⁇ or more and 15 ⁇ or less.
  • the average primary particle diameter of the silver-containing powder is less than ⁇ . ⁇ , the specific surface area of the silver-containing powder is increased, and the bulk density is also lowered. Therefore, when the antibacterial glaze composition described later is produced, Not only may the silver-containing powder be difficult to be uniformly dispersed with the silver-containing vitreous powder and the glaze, but may also promote the baking of the antibacterial composition or the antibacterial glaze due to the increased specific surface area of the silver-containing powder. Evaporation during the course of the composition is therefore not preferred.
  • the silver-containing glassy powder is contained in the metallic silver and the silver compound in an amount of 0.01% by mass or more and 50% by mass or less, preferably 0.05% by mass or more and 30% by mass or less, in terms of metallic silver, in the glassy powder.
  • the reason why the content of the silver component in the silver-containing glassy powder is 0.01% by mass or more and 50% by mass or less in terms of metal silver is as follows: the content of the silver component in the silver-containing glassy powder When it is less than 0.01% by mass in terms of metal silver, the addition of the silver-containing vitreous powder cannot improve the antibacterial effect, which is not preferable.
  • the average primary particle diameter of the silver-containing glassy powder is preferably ⁇ or more and 30 ⁇ or less, and more preferably ⁇ or more and 15 ⁇ or less.
  • the average primary particle diameter of the silver-containing vitreous powder is lower than ⁇ .
  • the specific surface area of the silver-containing vitreous powder is increased, and the bulk density is also lowered, so that after production
  • the antibacterial glaze composition described above may not only make the silver-containing vitreous powder difficult to be uniformly dispersed together with the silver-containing powder and the glaze, but may also be promoted by the increase in the specific surface area of the silver-containing vitreous powder. It evaporates during the baking of the antibacterial composition or the antibacterial glaze composition, and thus is not preferable.
  • the distribution state of the silver component in the glassy powder containing the silvery glassy powder can be variously adopted.
  • the distribution state of the silver component may be a single state of any one of a state of a silver ion, a state of a silver compound, a state of silver fine particles or a crystallite, or a combination of two or more types.
  • the vitreous powder is distributed in any one of a state of a silver compound, a state of fine particles of silver or a state of crystallites, or a combination of two or more types.
  • an example of these distribution states will be described.
  • 1 is a cross-sectional view showing an example of the silver-containing glassy powder of the present embodiment.
  • the silver-containing glassy powder 1 is in a state in which the particulate silver component 3 is dispersed in the vitreous powder 2.
  • FIG. 1 is a cross-sectional view showing an example of the silver-containing glassy powder of the present embodiment.
  • the silver-containing glassy powder 1 is in a state in which the particulate silver component 3 is dispersed in the vitreous powder 2.
  • the silver-containing vitreous powder is a cross-sectional view showing another example of the silver-containing vitreous powder according to the embodiment, wherein the silver-containing vitreous powder 11 is adhered to the surface of the vitreous powder 2 and fixed in a flat shape or a particulate form.
  • the state of the silver component 12. 3 is a cross-sectional view showing still another example of the silver-containing glassy powder of the present embodiment.
  • the silver-containing glassy powder 21 is in a state in which a particulate silver component 22 is embedded in the interior of the vitreous powder 2.
  • the silver-containing vitreous powder may be in various manners as described above.
  • the silver-containing vitreous powder 1 is combined with the silver-containing vitreous powder 11 or the silver-containing vitreous powder 1 1 and the silver-containing glass are used.
  • the combination of the powders 21 and the like can be variously changed in shape or distribution depending on the method and use.
  • these silver-containing glassy powders 1, 1 1 and 21 may contain silver ions.
  • the softening point of the silver-containing glassy powder is preferably 300 ° C or more and 1500 ° C or less, and more preferably 500 ° C or more and 1300 ° C or less.
  • the silver-containing glassy powder may also contain a second glassy powder having a softening point of 300 ° C or more and 1500 ° C or less.
  • the reason why the softening point of each of the silver-containing glassy powder and the second glassy powder is limited to 300 ° C or more and 1500 ° C or less is that if the softening point is lower than 300 ° C, the glass itself The water resistance is inferior, and therefore it is not preferable.
  • the softening point exceeds 1500 ° C the baking temperature of a commonly used ceramics or the like may be exceeded, and the glass may not melt, in particular, the silver-containing vitreous powder is used.
  • the body is a component of the glaze, the glassy substance in the glaze does not melt and remains, which may adversely affect the quality of the glaze, which is not preferable.
  • a vitreous powder and a second vitreous powder it is possible to use only a glass selected from the group consisting of phosphoric acid glass (softening point: 300 to 500 ° C) and borosilicate glass (softening point: 400 to 1000 ° C).
  • a glass of zinc borosilicate glass softening point: 500 to 800 ° C
  • soda lime glass softening point: 500 to 700 ° C
  • aluminosilicate glass softening point: 800 to 1000 ° C
  • a powder composed of two or more kinds of glass selected from the above-mentioned glass is used in combination with the powder.
  • the glassy powder or the second glassy powder may further comprise a glass material such as feldspar, silica sand, borax or silicate mineral, and any one or two of metallic silver and silver compounds.
  • a glass material obtained by mixing and melting silver components.
  • the silver-containing glassy powder or the second glassy powder preferably contains one or two or more kinds of vitreous powders having a softening point of silver (961.93 ° C) or less.
  • a melting point of silver is exemplified.
  • a metallic silver powder is used as the silver-containing powder
  • the following glassy powder is required: among the plurality of vitreous powders having different softening points and components, the softening point of at least one of the vitreous powders is The melting point of the metallic silver powder (961.93 ° C) or less.
  • a combination of phosphoric acid glass having a softening point of 350 ° C and a silicate mineral having a softening point of 1200 ° C can be given.
  • a production process of a glass powder (glass frit) which is usually performed can be applied.
  • a glassy powder or a raw material thereof is mixed with a predetermined amount of a silver component composed of any one or two of metallic silver and a silver compound using a mixing device such as a ball mill, and then a heating device such as an electric furnace is used.
  • a heating device such as an electric furnace is used.
  • After heating at a temperature of °C or more and 1200 ° C or lower for 10 minutes or more and 10 hours or less it is melted, and then cooled, and the obtained cake is pulverized by a mixing/pulverizing apparatus such as a ball mill to have an average particle diameter of ⁇ . ⁇ and above and 30 ⁇ or less.
  • a silver-containing vitreous powder having a desired average particle diameter was obtained.
  • a silver component composed of either or both of metallic silver and a silver compound as a raw material of the silver-containing powder is pulverized by a mixing/pulverizing device such as ball milling to have an average particle diameter of ⁇ . ⁇ or more. And 30 ⁇ or less. Thereby, a silver-containing powder having a desired average particle diameter is obtained.
  • the silver-containing powder and the silver-containing vitreous powder are weighed so that the ratio of the mass of the silver-containing powder (M Ag ) to the mass of the silver-containing vitreous powder (Me) ( ⁇ ⁇ : ⁇ ( ⁇ ) In the range of 1:0.1 to 1:100, the mixture is mixed using a mixing device such as a ball mill.
  • a mixing device such as a ball mill.
  • the antibacterial glaze composition of the present embodiment is an antibacterial glaze composition containing an antibacterial composition and a glaze, and the antibacterial composition contains a silver-containing powder and a silver-containing vitreous powder, and the silver-containing powder
  • the glassy powder containing the silver-containing glassy powder is contained in an amount of 0.01% by mass or more and 50% by mass or less in terms of metal silver.
  • the content of the antibacterial composition is preferably 0.01% by mass or more and 5% by mass or less, more preferably 5% by mass or less, based on the silver content of the silver glaze. 0.05% by mass or more and 3% by mass or less.
  • the antibacterial composition used in the antibacterial glaze composition is the same as the antibacterial composition described above, and thus the description thereof is omitted.
  • the reason why the content of the antibacterial composition is 0.01% by mass or more and 5% by mass or less in terms of metal silver relative to the glaze is that the content of the antimicrobial composition is less than 0.01 in terms of metallic silver.
  • the mass is %, the amount of silver contained in the antibacterial composition is too small, and the antibacterial property is lowered. As a result, the required antibacterial property cannot be exhibited, and the antibacterial property of the antibacterial composition is lowered, which is not preferable.
  • the antibacterial composition is contained in an amount of 0.01% by mass or more and 5% by mass or less in terms of metal silver, and the antibacterial property can be imparted to the glaze, and the glaze can be provided with an antibacterial property.
  • the antibacterial article of the present embodiment is an article in which a film is formed by the antibacterial glaze composition of the present embodiment, and as such articles, contamination by bacteria should be mentioned in a bathroom, a toilet, a kitchen, a bathroom, and the like. Places or hospitals, food processing facilities, public facilities, etc., which need to protect life from the threat of bacteria, such as: sanitary ware, containers, tableware, ceramic tiles, pottery and other ceramic products, containers, panels, cookware, electrical Enamel products such as products and building materials.
  • the antibacterial glaze composition of the present embodiment By using the antibacterial glaze composition of the present embodiment to form a film on at least a necessary portion of the surface of the ceramic article or the enamel article, the antibacterial property of the surface of the article can be improved, and the metallic silver or silver contained therein can be reduced.
  • the amount of the compound As described above, according to the antimicrobial composition of the present embodiment, since the silver-containing powder and the silver-containing glassy powder are contained, the silver-containing powder contains any one of metallic silver and silver compounds or In the silver-based glass powder, the silver-containing glassy material contains, in terms of metal silver, 0.01% by mass or more and 50% by mass or less, of any one of metallic silver and silver compounds.
  • the antibacterial property can be improved, and the amount of metallic silver or silver compound contained can be reduced as compared with the conventional antibacterial composition.
  • the antibacterial glaze composition of the present embodiment the antibacterial composition and the glaze of the present embodiment are contained, and the content of the antibacterial composition is set to 0.01% by mass in terms of metal silver relative to the glaze. Since the amount is 5% by mass or less, the antibacterial property of the glaze can be improved, and the amount of metallic silver or silver compound contained can be reduced as compared with the conventional antibacterial glaze composition.
  • the antibacterial property of the surface of the antibacterial article can be improved, and the antibacterial article can be compared with the conventional antibacterial article. It is possible to reduce the amount of metallic silver or silver compound contained.
  • Silver phosphate was used as the silver compound, and a vitreous powder containing a borosilicate glass component having a softening point of 650 ° C as a glassy powder was used, and 45 g of silver phosphate and 1455 g of vitreous powder were put into a ball mill and mixed. After that, it was heated by heating in an electric furnace at 1000 ° C for 4 hours, and then cooled, and the obtained cake was placed in a ball mill and pulverized for 25 hours to obtain a softening point of 650 ° C and an average particle diameter of 8 ⁇ , silver. The content is 2.3% by mass of the silver-containing vitreous powder in terms of metal silver.
  • silver phosphate was put into a ball mill and pulverized for 15 hours to obtain a silver phosphate powder having an average particle diameter of ⁇ . Then, the silver phosphate powder and the silver-containing glassy powder were weighed at a mass ratio of 1:2, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 1.
  • the antibacterial composition had an average particle diameter of 8 ⁇ m and a silver content of 27% by mass in terms of metal silver.
  • a glaze raw material having the following composition was used as the glaze raw material.
  • the antibacterial composition is added to the glaze raw material in an amount of 0.30% by mass in terms of metal silver, and the amount of water is 40 parts by mass relative to the total amount of these materials.
  • the mass fraction was then dispersed in a ball mill for 15 hours to obtain an antibacterial glaze composition of Example 1.
  • a ceramic plate having a length of 50 mm, a width of 50 mm, and a thickness of 5 mm was prepared, and the antibacterial glaze composition was sprayed on the ceramic plate at a coating amount of 30 g/m 2 , and after drying, calcined at a temperature of 1200 ° C for 1 hour.
  • the antibacterial ceramic plate of Example 1 was obtained.
  • a t Average value of viable cells after 24 hours of antibacterial processing test piece
  • Escherichia coli and Staphylococcus aureus were tested to evaluate whether or not the two bacteria had antibacterial properties.
  • the evaluation was carried out in accordance with Japanese Industrial Standard JIS Z 2800 "Antibacterial processed products - Antibacterial test method and antibacterial effect".
  • JIS Z 2800 Antibacterial processed products - Antibacterial test method and antibacterial effect.
  • the antibacterial activity values of both Escherichia coli and Staphylococcus aureus were 2.0 or more, it was evaluated as qualified for Escherichia coli and When the antibacterial activity value of either or both of S. aureus was less than 2.0, it was evaluated as unacceptable.
  • Table 1 "Appearance evaluation"
  • lg silver and 1499 g of the vitreous powder were put into a ball mill and mixed for 3 hours, and then, After heating at 1100 ° C for 1 hour in an electric furnace and melting, the mixture was cooled, and the obtained cake was placed in a ball mill and pulverized for 25 hours to obtain a softening point of 950 V, an average particle diameter of 10 ⁇ m, and a silver content in terms of metallic silver.
  • the content was 0.05% by mass of the silver-containing vitreous powder.
  • Example 2 metallic silver was placed in a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 ⁇ m. Then, the silver powder and the silver-containing glassy powder were weighed at a mass ratio of 1:2, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 2.
  • the antibacterial composition had an average particle diameter of 7 ⁇ m and a silver content of 33% by mass in terms of metal silver.
  • the antibacterial glaze composition of Example 2 and the antibacterial ceramic plate were prepared in accordance with Example 1, and evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • silver phosphate was put into a ball mill and pulverized for 15 hours to obtain a silver phosphate powder having an average particle diameter of ⁇ . Further, a vitreous powder containing aluminosilicate glass component having a softening point of 950 ° C as a main component was used as the second vitreous powder. Then, the silver phosphate powder, the silver-containing vitreous powder, and the second vitreous powder were weighed in a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 3. The antibacterial composition had an average particle diameter of 7 ⁇ m, and the silver content was 25% by mass in terms of metal silver. Using the antibacterial composition, the antibacterial glaze composition of Example 3 and the antibacterial ceramic plate were produced in accordance with Example 1, and evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • metallic silver was placed in a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 ⁇ m. Further, a vitreous powder containing a phosphoric acid glass component having a softening point of 350 ° C as a main component was used as the second vitreous powder. Then, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed at a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 4.
  • the antibacterial composition had an average particle diameter of 8 ⁇ m, and the silver content was 25% by mass in terms of metal silver.
  • Example 4 The antibacterial composition of Example 4 was produced according to Example 1, except that the glaze material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.10% by mass in terms of metal silver with respect to the glaze material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 2 a silver-containing glassy powder and a silver powder were obtained. Further, a vitreous powder containing a soda lime glass component having a softening point of 500 ° C as a main component was used as the second vitreous powder. Then, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed at a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 5.
  • the antibacterial composition had an average particle diameter of 7 ⁇ m and a silver content of 25% by mass in terms of metal silver.
  • Example 5 The antibacterial composition of Example 5 was produced according to Example 1, except that the glaze raw material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.05% by mass in terms of metal silver with respect to the glaze raw material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 3 a silver-containing vitreous powder was obtained.
  • silver nitrate was put into a ball mill and pulverized for 15 hours to obtain a silver nitrate powder having an average particle diameter of 15 ⁇ m.
  • the silver nitrate powder and the silver-containing glassy powder were weighed at a mass ratio of 1:2, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 6.
  • the antibacterial composition had an average particle diameter of ⁇ , and the silver content was 21% by mass in terms of metal silver.
  • Example 6 The antibacterial composition of Example 6 was prepared according to Example 1, except that the glaze material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.10% by mass in terms of metal silver with respect to the glaze material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1. [Embodiment 7]
  • Example 4 the silver-containing vitreous powder of Example 6 and the silver powder were obtained. Further, a vitreous powder containing a silicate mineral having a softening point of 1200 ° C as a main component was used as the second vitreous powder. Then, the silver powder, the silver-containing vitreous powder and the second vitreous powder were weighed at a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 7. The average particle size of the antimicrobial composition 15 ⁇ , the silver to metallic silver content in terms of mass 25 0/0.
  • Example 7 The antibacterial composition of Example 7 was prepared according to Example 1, except that the glaze material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.30% by mass in terms of metal silver with respect to the glaze material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • a vitreous powder containing a silicate mineral having a softening point of 1200 ° C Using metallic silver and a vitreous powder containing a silicate mineral having a softening point of 1200 ° C as a vitreous powder, 450 g of silver and 1050 g of vitreous powder were put into a ball mill and mixed for 5 hours, and then used. The electric furnace was heated at 1500 ° C for 1 hour to be melted, and then cooled. The obtained cake was placed in a ball mill and pulverized for 25 hours to obtain a softening point of 1200 V, an average particle diameter of 15 ⁇ m, and a silver content in terms of metal silver. It is 30% by mass of silver-containing vitreous powder.
  • the metal silver is put into a ball mill and pulverized for 15 hours to obtain an average particle size of 6 ⁇ m.
  • Silver powder Further, a vitreous powder containing borosilicate glass having a softening point of 650 ° C as a main component was used as the second vitreous powder. Then, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed at a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 8.
  • Example 8 The antibacterial composition of Example 8 was produced according to Example 1, except that the glaze material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.30% by mass in terms of metal silver with respect to the glaze material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 3 a silver-containing vitreous powder and a silver phosphate powder were obtained. Then, the silver phosphate powder and the silver-containing glassy powder were weighed in a mass ratio of 1:2, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 9.
  • the antibacterial composition had an average particle diameter of 8 ⁇ m and a silver content of 26% by mass in terms of metal silver.
  • Example 9 The antibacterial composition of Example 9 was prepared according to Example 1, except that the glaze material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.10% by mass in terms of metal silver with respect to the glaze material. Sex glaze composition and antibacterial ceramic plate, and according to Example 1 was evaluated. The evaluation results are shown in Table 1. [Embodiment 10]
  • Example 10 The antibacterial composition of Example 10 was obtained in accordance with Example 9. Then, Example 10 was prepared according to Example 1, except that the glaze raw material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 3.0% by mass in terms of metal silver with respect to the glaze raw material.
  • the antibacterial glaze composition and the antibacterial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1. [Embodiment 1 1]
  • Example 9 the antibacterial composition of Example 11 was obtained. Then, Example 1 was prepared according to Example 1, except that the glaze raw material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 5.0% by mass based on the metal silver in terms of the glaze raw material.
  • the antibacterial glaze composition of 1 and the antimicrobial ceramic board were evaluated in accordance with Example 1. The evaluation results are shown in Table 1. [Embodiment 12]
  • Silver nitrate was used as the silver compound, and a vitreous powder containing a borosilicate glass component having a softening point of 650 ° C as a glassy powder was used, and 35 g of silver nitrate and 1465 g of vitreous powder were put into a ball mill and mixed. After that, it is heated by heating in an electric furnace at 1000 ° C for 4 hours, and then cooled, and the obtained cake is put into a ball mill and pulverized for 25 hours. At that time, a silver-containing vitreous powder having a softening point of 650 ° C, an average particle diameter of 6 ⁇ m, and a silver content of 1.5% by mass in terms of metal silver was obtained.
  • Example 12 was prepared according to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added in an amount of 0.3% by mass based on the metal glaze of the glaze raw material.
  • the antibacterial glaze composition and the antibacterial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1. [Example 13]
  • vitreous powder as a glassy powder having a borosilicate glass component having a softening point of 650 ° C as a main component
  • 22 g of silver, 20 g of silver phosphate, and 1458 g of vitreous material were used.
  • the powder was placed in a ball mill and mixed for 3 hours, and then heated in an electric furnace at 1000 ° C for 4 hours to be melted, and then cooled, and the obtained cake was placed in a ball mill and pulverized for 25 hours to obtain a softening point of 650 ° C.
  • the silver-containing vitreous powder having an average particle diameter of 6 ⁇ m and a silver content of 2.0% by mass in terms of metal silver.
  • metallic silver was placed in a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 ⁇ m.
  • a vitreous powder containing phosphoric acid glass having a softening point of 350 ° C as a main component is used as the second vitreous powder.
  • the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed in a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 13.
  • the antibacterial composition has an average particle diameter of 8 ⁇ m, and the silver content is 26 mass in terms of metal silver.
  • Example 13 The antibacterial composition of Example 13 was produced according to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added in an amount of 0.30% by mass in terms of metal silver with respect to the glaze raw material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 3 a silver-containing vitreous powder was obtained.
  • metallic silver and silver phosphate were weighed in a mass ratio of 1:1, and these materials were placed in a ball mill and pulverized for 15 hours to obtain a silver-containing powder having an average particle diameter of 8 ⁇ m.
  • a vitreous powder containing borosilicate glass having a softening point of 650 ° C as a main component was used as the second vitreous powder.
  • the silver-containing powder, the silver-containing vitreous powder, and the second vitreous powder were weighed in a mass ratio of 1:2:1, and mixed in a ball mill for 5 hours to obtain an antibacterial composition of Example 14.
  • the antibacterial composition had an average particle diameter of 6 ⁇ m, and the silver content was 25% by mass in terms of metal silver.
  • Example 14 The antibacterial composition of Example 14 was produced according to Example 1, except that the glaze material of Example 1 was used as the glaze material, and the above-mentioned antibacterial composition was added in an amount of 0.30% by mass in terms of metal silver with respect to the glaze material.
  • the glaze composition and the antimicrobial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 1 The glaze raw material of Example 1 was used as a glaze raw material, and a silver phosphate powder of 0.30% by mass in terms of metal silver was added to the glaze raw material to prepare an antibacterial glaze composition.
  • the antibacterial ceramic plate of Comparative Example 1 was prepared in accordance with Example 1, and evaluated in accordance with Example 1. The evaluation results are shown in Table 1. [Comparative Example 2]
  • Example 3 Comparative Example 3 was prepared according to Example 1, except that the glaze material of Example 1 was used as the glaze material, and the above-mentioned antibacterial composition was added in an amount of 0.50% by mass in terms of metal silver with respect to the glaze material.
  • the antibacterial glaze composition and the antibacterial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 1 The glaze raw material of Example 1 was used as a glaze raw material, and metallic silver was added as a silver powder in an amount of 0.30% by mass based on the metal glaze of the glaze raw material to prepare an antibacterial glaze composition.
  • the antibacterial ceramic plate of Comparative Example 1 was prepared in accordance with Example 1, and evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Example 5 Bacterial composition.
  • the antibacterial composition had an average particle diameter of ⁇ , and the silver content was 25% by mass in terms of metal silver.
  • Comparative Example 5 was prepared according to Example 1, except that the glaze raw material of Example 1 was used as the raw material of the glaze, and the above-mentioned antibacterial composition was added in an amount of 0.30% by mass based on the metal silver in terms of the glaze raw material.
  • the antibacterial glaze composition and the antibacterial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 1.
  • Silver-containing glassy powder at °C.
  • the silver-containing vitreous powder was visually observed, and it was found that silver disappeared by evaporation and did not exist in the quartz glass.
  • the antimicrobial ceramic plates of Examples 1 to 14 have good antibacterial properties from any of the antibacterial activity values against Escherichia coli and the antibacterial activity values against S. aureus.
  • the antibacterial ceramic plates of Comparative Examples 1 to 4 are in compliance with either one of the antibacterial activity value of Escherichia coli and the antibacterial activity value against Staphylococcus aureus.
  • the antibacterial property was inferior to those of the antibacterial ceramic plates of Examples 1 to 14 in addition to or outside the acceptable range.
  • foreign matter was deposited on the surface, and the appearance was remarkably impaired.
  • a vitreous powder containing a borosilicate glass component having a softening point of 650 ° C as a vitreous powder as a main component 22 g of silver and 1478 g of the vitreous powder were put into a ball mill and mixed for 3 hours, and then, After heating in an electric furnace at 1000 ° C for 4 hours to melt, the mixture was cooled, and the obtained cake was placed in a ball mill and pulverized for 25 hours to obtain a softening point of 650 V, an average particle diameter of 6 ⁇ , and a silver content in terms of metallic silver.
  • the silver-containing vitreous powder was 1.0% by mass.
  • Comparative Example 9 Antibacterial composition.
  • the antibacterial composition had an average particle diameter of 6 ⁇ m and a silver content of 25 mass% in terms of metal silver.
  • Comparative Example 9 was prepared according to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added in an amount of 10.0% by mass in terms of metal silver with respect to the glaze raw material.
  • the antibacterial glaze composition and the antibacterial ceramic plate were evaluated in accordance with Example 1. The evaluation results are shown in Table 2. Table 2
  • the antibacterial ceramic plate of Comparative Example 8 showed no antibacterial activity against the antibacterial activity value of Escherichia coli and the antibacterial activity value against Staphylococcus aureus.
  • the coating film was colored, and the transparency was lowered.

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Abstract

本发明提供抗菌性组合物及抗菌性釉料组合物以及抗菌性物品。本发明的抗菌性组合物含有含银粉体和含银玻璃质粉体，所述含银粉体含有由金属银及银化合物中的任意一种或两种构成的银成分，所述含银玻璃质粉体的玻璃质粉体中含有以金属银换算计为0.01质量%以上且50质量%以下的由金属银及银化合物中的任意一种或两种构成的银成分。根据该抗菌性组合物，可以提高抗菌性，而且，可以减少所含的金属银或银化合物的量。

Description

抗菌性组合物及抗菌性釉料组合物以及抗菌性物品 技术领域
本发明涉及抗菌性组合物及抗菌性釉料组合物以及抗菌性物品， 特别详细而言， 涉及适合用于卫生陶具、 医疗用品、 搪瓷用品、 各种 容器、 餐具等厨房用品、 瓷砖等建材、 汽车的各种构件、 电气设备的 面板等各种构件的、 具有优良的抗菌性的抗菌性组合物及含有该抗菌 性组合物和釉料的抗菌性釉料组合物以及利用该抗菌性釉料组合物形 成覆膜的抗菌性物品。 背景技术
目前， 作为抗菌成分， 广泛使用银、 铜、 锌等金属。 认为这些金 属通过其离子对细菌等的细胞中的活性酶起作用而具有妨碍细菌增殖 的作用。 阻止该细菌增殖所需的抗菌成分的浓度用最低抑菌浓度 (MIC)表 示， 一般而言， 在含有银的抗菌成分的情况下， 例如， 对大肠杆菌的 MIC约为 200ppm。 为了对陶瓷器或搪瓷制品赋予抗菌性， 目前已知的是使用包含金 属银、 氧化银、 金属铜、 氧化铜、 金属锌、 氧化锌等金属或金属氧化 物的釉料的方法 (例如， 参照专利文献 1〜3等)， 并且已实际施行。 为了对这些陶瓷器或搪瓷制品赋予良好的抗菌性， 需要使金属银 等具有抗菌性的金属或金属氧化物均匀地分散在形成于陶瓷器或搪瓷 制品的表面的釉料层中， 并使这些金属或金属氧化物在陶瓷器或搪瓷 制品的表面溶出。 例如， 作为使银离子有效地在陶瓷器或搪瓷制品的表面溶出的方 法， 提出了使磷酸成分和含银化合物共存的方法 (专利文献 4)， 还提出 了将该磷酸成分和含银化合物共存得到的材料用于陶瓷器或搪瓷用釉 料等的技术方案 (专利文献 5、 6)。 另外， 就陶瓷器或搪瓷制品而言， 为了使釉料成分在表面溶解而 形成坚固的覆膜， 一般在 700°C以上且 1300°C以下的温度下焙烧 1 小 时以上。 但是， 在使用金属银作为抗菌剂的情况下， 由于金属银在焙烧过 程中扩散到表面并从该表面蒸发， 因此， 得到的覆膜中银的量变得比 当初预定的量少， 其结果是， 存在覆膜的抗菌性下降的问题。 因此， 作为使覆膜的抗菌性不下降的方法， 提出了使用预估蒸发 所致的减少量而增加银量的釉料的方法或者下述抗菌性陶瓷器品的制 造方法： 通过在陶瓷器素坯的表面以层状施加釉料并进行焙烧而得到 施釉陶瓷器品时， 在陶瓷器素坯的表面和最表层的釉料层之间， 以层 状施加以银为抗菌成分的抗菌剂并在该状态下进行焙烧， 由此制造在 陶瓷器素坯的表面以层状施加了釉料的抗菌性陶瓷器品 (专利文献 7)。 专利文献 1 日本特开平 6-340513号公报
专利文献 2 日本特开平 7-196384号公报
专利文献 3 日本特开平 7-268652号公报
专利文献 4 日本特开平 3-38504号公报
专利文献 5 日本特开平 7-291658号公报
专利文献 6 日本特开 2004-300086号公报
专利文献 7 日本特开平 9-173162号公报 发明内容
在使用金属银或银化合物作为抗菌剂的釉料的情况下， 为了利用 金属银或银化合物来表现抗菌性， 例如， 在大肠杆菌的情况下， 需要 使表面的银浓度为 50〜200ppm左右 (最低抑菌浓度 (MIC))。 按道理说， 只要添加相对于釉料总量以金属银换算计约为 0.01-0.02 质量％的金属银或银化合物即可， 但实际上， 如上所述， 因 银成分蒸发或者银成分向陶瓷器的基底 (素坯)扩散等而导致覆膜中所 含的银量比当初预定的量减少。 因此， 存在为了使覆膜得到规定的抗 菌性而需要当初预定量的数十倍以上的银的问题。 由于这样的理由且银本身昂贵， 因此， 从使用该包含银的覆膜会 导致制品的制造成本上升等理由考虑， 暂缓在本来需要抗菌性的场所 采用， 或者使用银含量少的覆膜， 由此会损害实际环境中的清洁性， 其结果是， 会产生由源于细菌增殖的病原性大肠杆菌等而导致发病等 社会性问题。 本发明是鉴于上述情况而完成的， 其目的在于提供即使使用与目 前相比少量的金属银或银化合物也能够提高抗菌性的抗菌性组合物及 抗菌性釉料组合物以及抗菌性物品。 本发明人为了解决上述问题进行了潜心研究， 结果发现， 如果制 成含有含银粉体和含银玻璃质粉体的组合物， 所述含银粉体含有由金 属银及银化合物中的任意一种或两种构成的银成分， 所述含银玻璃质 粉体的玻璃质粉体中含有以金属银换算计为 0.01质量％以上且 50质量 %以下的由金属银及银化合物中的任意一种或两种构成的银成分，则该 组合物中使用与目前相比少量的金属银或银化合物， 即可表现出比目 前更好的抗菌性， 从而完成了本发明。 即， 本发明的抗菌性组合物， 其特征在于， 含有含银粉体和含银 玻璃质粉体， 所述含银粉体含有由金属银及银化合物中的任意一种或 两种构成的银成分， 所述含银玻璃质粉体的玻璃质粉体中含有以金属 银换算计为 0.01质量％以上且 50质量％以下的由金属银及银化合物中 的任意一种或两种构成的银成分。 本发明的抗菌性组合物，优选上述含银玻璃质粉体的软化点为 300 °C以上且 1500°C以下。 优选还含有软化点为 300°C以上且 1500°C以下的第二种玻璃质粉 体。 上述含银玻璃质粉体或上述第二种玻璃质粉体含有一种或两种以 上软化点为银的熔点以下的玻璃质粉体。 上述银化合物优选为选自磷酸银、 氧化银、 碳酸银、 硝酸银、 氯 化银、 硫化银、 醋酸银中的一种或两种以上。 本发明的抗菌性釉料组合物，含有本发明的抗菌性组合物和釉料， 上述抗菌性组合物含有含银粉体和含银玻璃质粉体， 上述含银粉体含 有由金属银及银化合物中的任意一种或两种构成的银成分， 上述含银 玻璃质粉体的玻璃质粉体中含有以金属银换算计为 0.01 质量％以上且 50 质量％以下的由金属银及银化合物中的任意一种或两种构成的银成 分， 上述抗菌性釉料组合物的特征在于， 上述抗菌性组合物的含量相 对于上述釉料以金属银换算计为 0.01质量％以上且 5质量％以下。 本发明的抗菌性物品， 其特征在于， 利用本发明的抗菌性釉料组 合物形成覆膜。 发明效果
根据本发明的抗菌性组合物， 由于其含有含银粉体和含银玻璃质 粉体， 所述含银粉体含有由金属银及银化合物中的任意一种或两种构 成的银成分， 所述含银玻璃质粉体的玻璃质粉体中含有以金属银换算 计为 0.01质量％以上且 50质量％以下的由金属银及银化合物中的任意 一种或两种构成的银成分， 因此， 能够提高抗菌性， 而且， 能够减少 所含的金属银或银化合物的量。 根据本发明的抗菌性釉料组合物， 由于其含有本发明的抗菌性组 合物和釉料， 且设定该抗菌性组合物的含量相对于釉料以金属银换算 计为 0.01质量％以上且 5质量％以下， 因此， 能够提高釉料的抗菌性， 而且， 能够减少所含的金属银或银化合物的量。 根据本发明的抗菌性物品， 由于其利用本发明的抗菌性釉料组合 物形成了覆膜， 因此， 能够提高该抗菌性物品表面的抗菌性， 而且， 能够减少所含的金属银或银化合物的量。 附图说明
图 1 是表示本发明的一个实施方式的含银玻璃质粉体的一例的剖 面图。
图 2是表示本发明的一个实施方式的含银玻璃质粉体的另一例的 剖面图。
图 3是表示本发明的一个实施方式的含银玻璃质粉体的又一例的 剖面图。 标号说明
1 含银玻璃质粉体
2 玻璃质粉体
3 微粒状的银成分
1 1 含银玻璃质粉体
12 扁平状或微粒状的银成分
21 含银玻璃质粉体
22 颗粒状的银成分 具体实施方式
对本发明的抗菌性组合物及抗菌性釉料组合物以及抗菌性物品的 实施方式进行说明。 需要说明的是， 该方式是为了更好地理解发明的主旨而进行具体 说明的， 只要没有特别指定， 并不用于限定本发明。
[抗菌性组合物]
本实施方式的抗菌性组合物为含有含银粉体和含银玻璃质粉体的 组合物， 其中， 所述含银粉体含有由金属银及银化合物中的任意一种 或两种构成的银成分， 所述含银玻璃质粉体的玻璃质粉体中含有以金 属银换算计为 0.01质量％以上且 50质量％以下的由金属银及银化合物 中的任意一种或两种构成的银成分。 该抗菌性组合物中的含银粉体的质量 (MAg)与含银玻璃质粉体的 质量 (MG)之比 (MAg:MG)优选在 1 :0.1〜1 : 100的范围内。 在此， 设含银粉体的质量 (MAg)为 1时， 如果含银玻璃质粉体的质 量 (MQ)低于 0.1， 则含银玻璃质粉体过少而失去提高抗菌性的效果， 因 此不优选， 另一方面， 设含银粉体的质量 (MAg)为 1时， 如果含银玻璃 质粉体的质量 (Me)超过 100， 则银的总量过少， 不能满足抗菌效果所需 要的银量， 因此不优选。 下面， 对作为本实施方式的抗菌性组合物的成分的含银粉体及含 银玻璃质粉体进行说明。
"含银粉体"
该含银粉体为含有由金属银及银化合物中的任意一种或两种构成 的银成分的粉体。 在此， 作为银化合物， 优选为选自磷酸银、 氧化银、 碳酸银、 硝酸银、 氯化银、 硫化银、 醋酸银中的一种或两种以上。 特 别是通过使用熔点比较高的金属银粉体 (m.p. = 961.93 °C)、 磷酸银粉体 (m.p. = 849°C), 能够表现稳定的抗菌性， 因此更优选。 该含银粉体的平均一次粒径优选为 Ο. ΐμηι以上且 30μηι以下， 更 优选为 Ιμηι以上且 15μηι以下。 在此， 如果含银粉体的平均一次粒径低于 Ο.ΐμηι, 则含银粉体的 比表面积增大， 并且， 体积密度也降低， 因此， 制作后述的抗菌性釉 料组合物时， 不仅可能会使含银粉体难以与含银玻璃质粉体及釉料一 起均匀分散， 而且可能会因含银粉体的比表面积增大而促进其在焙烧 抗菌性组合物或抗菌性釉料组合物的过程中的蒸发， 因此不优选。
"含银玻璃质粉体"
该含银玻璃质粉体是在玻璃质粉体中含有以金属银换算计为 0.01 质量％以上且 50质量％以下、 优选 0.05质量％以上且 30质量％以下的 由金属银及银化合物中的任意一种或两种构成的银成分的粉体。 在此， 将该含银玻璃质粉体中的银成分的含量设为以金属银换算 计 0.01质量％以上且 50质量％以下的理由在于： 该含银玻璃质粉体中 的银成分的含量以金属银换算计低于 0.01 质量％时， 含银玻璃质粉体 的添加不能获得抗菌效果的提高， 因此不优选。 另一方面， 该含银玻 璃质粉体中的银成分的含量以金属银换算计超过 50质量％时， 玻璃质 粉体的银含量超出稳定状态， 会产生很多银以银单质的状态析出等问 题， 并且， 会浪费很多银， 因此不优选。 该含银玻璃质粉体的平均一次粒径优选为 Ο. ΐμηι以上且 30μηι以 下， 更优选为 Ιμηι以上且 15μηι以下。 在此， 如果含银玻璃质粉体的平均一次粒径低于 Ο. ΐμηι, 则含银 玻璃质粉体的比表面积增大， 并且， 体积密度也降低， 因此， 制作后 述的抗菌性釉料组合物时， 不仅可能会使含银玻璃质粉体难以与含银 粉体及釉料一起均匀分散， 而且可能会因含银玻璃质粉体的比表面积 增大而促进其在焙烧抗菌性组合物或抗菌性釉料组合物的过程中的蒸 发， 因此不优选。 该含银玻璃质粉体的玻璃质粉体中的银成分的分布状态可以采取 各种方式。 作为该银成分的分布状态， 可以举出： 银离子的状态、 银 化合物的状态、 银的微粒或微晶的状态中任意一种的单独状态， 或者 两种以上的组合的状态。 在此， 在玻璃质粉体中， 以银化合物的状态、 银的微粒或微晶的 状态中的任意一种状态或者两种以上的组合的状态分布的情况下， 存 在各种分布状态。 在此， 举出这些分布状态的例子进行说明。 图 1 是表示本实施方式的含银玻璃质粉体的一例的剖面图， 该含 银玻璃质粉体 1为在玻璃质粉体 2中分散有微粒状的银成分 3的状态。 图 2是表示本实施方式的含银玻璃质粉体的另一例的剖面图， 该 含银玻璃质粉体 1 1为在玻璃质粉体 2的表面上附着、 固定有扁平状或 微粒状的银成分 12的状态。 图 3是表示本实施方式的含银玻璃质粉体的又一例的剖面图， 该 含银玻璃质粉体 21为在玻璃质粉体 2的内部嵌入有颗粒状的银成分 22 的状态。 该含银玻璃质粉体可以采取上述各种方式， 因此， 例如， 将含银 玻璃质粉体 1与含银玻璃质粉体 1 1组合或者将含银玻璃质粉体 1 1与 含银玻璃质粉体 21组合等， 可以根据方法及用途对其形状或分布状态 进行各种变更。 另外， 这些含银玻璃质粉体 1、 1 1、 21也可以包含银离子。 该含银玻璃质粉体的软化点优选为 300°C以上且 1500°C以下， 更 优选为 500 °C以上且 1300°C以下。 该含银玻璃质粉体也可以含有软化点为 300°C以上且 1500°C以下 的第二种玻璃质粉体。 在此， 将含银玻璃质粉体、 第二种玻璃质粉体各自的软化点限定 为 300°C以上且 1500°C以下的理由在于： 如果软化点低于 300°C， 则玻 璃自身的耐水性等差， 因此不优选， 另一方面， 如果软化点超过 1500 °C， 则会超过通常使用的陶瓷器等的焙烧温度， 玻璃质可能不熔化， 特别是， 使用该含银玻璃质粉体作为釉料的成分的情况下， 釉料中的 玻璃质不熔化而残留， 可能会对釉料的质量造成不良影响， 因此不优 选。 作为这样的玻璃质粉体及第二种玻璃质粉体， 可以使用仅由选自 磷酸玻璃 (软化点： 300〜500°C)、 硼硅酸玻璃 (软化点： 400〜1000°C)、 硼 硅酸锌玻璃 (软化点： 500〜800°C)、 钠钙玻璃 (软化点： 500〜700°C)、 铝 硅酸玻璃 (软化点： 800〜1000°C)等中的一种玻璃构成的粉体， 或者混合 使用由选自上述玻璃中的两种以上的玻璃构成的粉体。 这些玻璃质粉体或第二种玻璃质粉体中， 也可以包含将长石、 硅 砂、 硼砂、 硅酸盐矿物等玻璃原料与由金属银及银化合物中的任意一 种或两种构成的银成分混合并熔融而得到的玻璃材料。 该含银玻璃质粉体或第二种玻璃质粉体优选含有一种或两种以上 软化点为银的熔点 (961.93 °C )以下的玻璃质粉体。 作为这样的玻璃质粉体的组合， 例如， 可以举出软化点为银的熔 点以下的磷酸玻璃、 钠钙玻璃等低软化点玻璃与软化点超过银的熔点 的硼硅酸玻璃、 硼硅酸锌玻璃、 铝硅酸玻璃等高软化点玻璃的组合。 特别是使用金属银粉体作为含银粉体的情况下， 需要为如下的玻 璃质粉体： 软化点和成分不同的多种玻璃质粉体中， 至少一种玻璃质 粉体的软化点为金属银粉体的熔点 (961.93°C)以下。 例如， 可以举出软 化点为 350°C的磷酸玻璃与软化点为 1200 °C的硅酸盐矿物的组合。
[抗菌性组合物的制造方法]
本实施方式的抗菌性组合物的制造中， 可以应用通常进行的玻璃 粉体 (玻璃粉)的制造工序。 首先， 使用球磨等混合装置将玻璃质粉体或其原料与规定量的由 金属银及银化合物中的任意一种或两种构成的银成分进行混合， 接着， 使用电炉等加热装置， 在 700°C以上且 1200°C以下的温度下加热 10分 钟以上且 10小时以下使其熔融， 然后进行冷却， 将得到的块状物用球 磨等混合 /粉碎装置进行粉碎， 使平均粒径为 Ο.ΐμηι以上且 30μηι以下。 由此， 得到具有所需平均粒径的含银玻璃质粉体。 另一方面， 将作为含银粉体的原料的由金属银及银化合物中的任 意一种或两种构成的银成分用球磨等混合 /粉碎装置进行粉碎， 使平均 粒径为 Ο.ΐμηι以上且 30μηι以下。 由此， 得到具有所需平均粒径的含银 粉体。 接着，称量含银粉体和含银玻璃质粉体，使该含银粉体的质量 (MAg) 与含银玻璃质粉体的质量 (Me)之比 (ΜΑ§:Μ(Ϊ)在 1 :0.1〜1 : 100的范围内， 并使用球磨等混合装置进行混合。 通过以上操作， 可得到平均粒径为 Ο. ΐμηι以上且 30μηι以下的抗 菌性组合物。 [抗菌性釉料组合物]
本实施方式的抗菌性釉料组合物为含有抗菌性组合物和釉料的抗 菌性釉料组合物， 上述抗菌性组合物含有含银粉体和含银玻璃质粉体， 上述含银粉体含有由金属银及银化合物中的任意一种或两种构成的银 成分，上述含银玻璃质粉体的玻璃质粉体中含有以金属银换算计为 0.01 质量％以上且 50质量％以下的由金属银及银化合物中的任意一种或两 种构成的银成分， 该抗菌性组合物的含量相对于釉料以金属银换算计 优选为 0.01质量％以上且 5质量％以下，更优选为 0.05质量％以上且 3 质量％以下。 关于该抗菌性釉料组合物中使用的抗菌性组合物， 与上述的抗菌 性组合物相同， 因此省略说明。 在此， 将抗菌性组合物的含量设定为相对于釉料以金属银换算计 为 0.01质量％以上且 5质量％以下的理由在于：抗菌性组合物的含量以 金属银换算计低于 0.01 质量％时， 抗菌性组合物所含的银量过少而使 抗菌性降低， 结果无法表现所需的抗菌性， 作为抗菌性组合物的抗菌 性降低， 因此不优选。 另一方面， 抗菌性组合物的含量以金属银换算 计超过 5质量％时，银含量超出表现所需抗菌性的含量，会浪费很多银， 因此不优选。 关于该抗菌性釉料组合物， 通过相对于釉料含有以金属银换算计 为 0.01质量％以上且 5质量％以下的该抗菌性组合物，能够对釉料赋予 抗菌性， 而且， 能够减少所含的金属银或银化合物的量。 因而， 通过在陶瓷器制品或搪瓷制品上涂布该抗菌性釉料组合物 并进行热处理， 能够对陶瓷器制品或搪瓷制品赋予抗菌性。 [抗菌性物品] 本实施方式的抗菌性物品为利用本实施方式的抗菌性釉料组合物 形成了覆膜的物品， 作为这些物品， 可以举出在盥洗室、 厕所、 厨房、 浴室等应当防止由细菌造成的污染的场所或医院、 食品加工设施、 公 共设施等需要保护生命免受细菌威胁的场所使用的物品， 例如： 卫生 陶具、 容器、 餐具、 瓷砖、 陶器等陶瓷器制品， 容器、 面板、 炊具、 电气制品、 建材构件等搪瓷制品。 通过利用本实施方式的抗菌性釉料组合物在这些陶瓷器制品或搪 瓷制品表面的至少必要的部位形成覆膜， 能够提高该物品表面的抗菌 性， 而且， 能够减少所含的金属银或银化合物的量。 如以上说明所述， 根据本实施方式的抗菌性组合物， 由于其含有 含银粉体和含银玻璃质粉体， 所述含银粉体含有由金属银及银化合物 中的任意一种或两种构成的银成分， 所述含银玻璃质粉体在玻璃质粉 体中含有以金属银换算计为 0.01质量％以上且 50质量％以下的由金属 银及银化合物中的任意一种或两种构成的银成分， 因此能够提高抗菌 性， 而且， 与现有的抗菌性组合物相比， 能够减少所含的金属银或银 化合物的量。 根据本实施方式的抗菌性釉料组合物， 由于其含有本实施方式的 抗菌性组合物和釉料， 且设定该抗菌性组合物的含量相对于釉料以金 属银换算计为 0.01质量％以上且 5质量％以下， 因此， 能够提高釉料的 抗菌性， 而且， 与现有的抗菌性釉料组合物相比， 能够减少所含的金 属银或银化合物的量。 根据本实施方式的抗菌性物品， 由于其利用本实施方式的抗菌性 釉料组合物形成了覆膜， 因此， 能够提高该抗菌性物品表面的抗菌性， 而且， 与现有的抗菌性物品相比， 能够减少所含的金属银或银化合物 的量。 实施例
下面， 利用实施例及比较例具体地说明本发明， 但是本发明并不 受这些实施例的限定。
A. 抗菌性组合物、 抗菌性釉料组合物、 抗菌性陶瓷器板的制作及 评价
[实施例 1]
"抗菌性组合物的制作"
使用磷酸银作为银化合物，使用以软化点为 650°C的硼硅酸玻璃成 分为主要成分的玻璃质粉体作为玻璃质粉体， 将 45g 磷酸银和 1455g 玻璃质粉体投入球磨中混合 3小时， 然后， 使用电炉在 1000°C下加热 4小时使其熔融后， 进行冷却， 将得到的块状物投入球磨中粉碎 25小 时， 得到软化点为 650°C、 平均粒径为 8μηι， 银含量以金属银换算计为 2.3质量％的含银玻璃质粉体。 另一方面， 将磷酸银投入球磨中粉碎 15 小时， 得到平均粒径为 ΙΟμηι的磷酸银粉体。 然后， 以 1 :2 的质量比称量磷酸银粉体和含银玻璃质粉体， 投入 球磨中混合 5小时， 得到实施例 1 的抗菌性组合物。 该抗菌性组合物 的平均粒径为 8μηι， 银含量以金属银换算计为 27质量％。
"抗菌性釉料组合物的制作"
作为釉料原料， 使用具有下述组成的釉料原料。
SiO2 55质 1%
Α12Ο3 lo质 1%
ZrO2 lo质 1%
CaO lo质 1%
ZnO lo质 1% K2O 4质量％
Na2O 1质量％ 在该釉料原料中， 添加相对于釉料原料以金属银换算计为 0.30质 量％的上述抗菌性组合物， 并使水相对于这些物质的总量 60质量份为 40质量份， 然后投入球磨中分散 15小时， 得到实施例 1的抗菌性釉料 组合物。
"抗菌性陶瓷器板的制作"
准备长 50mm X宽 50mmX厚 5mm的陶瓷器板， 在该陶瓷器板上 以 30g/m2的涂布量喷涂上述抗菌性釉料组合物， 干燥后， 在 1200°C的 温度下焙烧 1小时， 得到实施例 1的抗菌性陶瓷器板。
"抗菌性陶瓷器板的评价"
根据 ISO22196 "塑料-塑料表面抗菌活性的测量"评价上述抗菌性 陶瓷器板的抗菌性， 由下面的计算公式求出抗菌活性值。 抗菌活性值 (R) = (Ut-Uo)-(At-U0) = Ut-At
Uo: 未加工试验片刚接种后的活菌数的平均值 (个）
Ut: 未加工试验片 24小时后的活菌数的平均值 (个）
At: 抗菌加工试验片 24小时后的活菌数的平均值 (个） 在此， 就大肠杆菌和金黄色葡萄球菌进行了试验， 评价了对两种 细菌有无抗菌性能。 评价根据日本工业标准 JIS Z 2800 "抗菌加工制品 -抗菌性试验方法及抗菌效果" 进行， 对大肠杆菌及金黄色葡萄球菌两 者的抗菌活性值均为 2.0以上时评价为合格，对大肠杆菌及金黄色葡萄 球菌中的任意一者或两者的抗菌活性值低于 2.0时评价为不合格。 评价结果示于表 1。 "外观评价"
通过目视检查对所得抗菌性陶瓷器板的外观与不含抗菌性组合物 的陶瓷器板进行比较， 确认有无变色、 凹凸、 异物析出、 气泡等， 将 确认到显著外观不良的陶瓷器板评价为不合格。 评价结果示于表 1。 [实施例 2]
"抗菌性组合物的制作"
使用金属银和作为玻璃质粉体的以软化点为 950°C的铝硅酸玻璃 成分为主要成分的玻璃质粉体， 将 lg银和 1499g玻璃质粉体投入球磨 中混合 3小时， 然后， 使用电炉在 1100°C下加热 1小时使其熔融后， 进行冷却，将得到的块状物投入球磨中粉碎 25小时，得到软化点为 950 V、 平均粒径为 10μηι、 银含量以金属银换算计为 0.05质量％的含银玻 璃质粉体。 另一方面，将金属银投入球磨中粉碎 15小时，得到平均粒径为 6μηι 的银粉体。 然后， 以 1 :2 的质量比称量银粉体和含银玻璃质粉体， 投入球磨 中混合 5小时， 得到实施例 2 的抗菌性组合物。 该抗菌性组合物的平 均粒径为 7μηι， 银含量以金属银换算计为 33质量％。 使用该抗菌性组合物， 按照实施例 1， 制作实施例 2的抗菌性釉料 组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。
[实施例 3]
"抗菌性组合物的制作" 使用金属银和作为玻璃质粉体的以软化点为 650°C的硼硅酸玻璃 成分为主要成分的玻璃质粉体， 将 22g银和 1478g玻璃质粉体投入球 磨中混合 3小时， 然后， 使用电炉在 1000°C下加热 4小时使其熔融后， 进行冷却，将得到的块状物投入球磨中粉碎 25小时，得到软化点为 650 V、 平均粒径为 6μηι、 银含量以金属银换算计为 1.0质量％的含银玻璃 质粉体。 另一方面， 将磷酸银投入球磨中粉碎 15 小时， 得到平均粒径为 ΙΟμηι的磷酸银粉体。 另外，使用以软化点为 950°C的铝硅酸玻璃成分为主要成分的玻璃 质粉体作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量磷酸银粉体、含银玻璃质粉体和第二 种玻璃质粉体， 投入球磨中混合 5小时， 得到实施例 3 的抗菌性组合 物。 该抗菌性组合物的平均粒径为 7μηι， 银含量以金属银换算计为 25 质量％。 使用该抗菌性组合物， 按照实施例 1， 制作实施例 3的抗菌性釉料 组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。
[实施例 4]
"抗菌性组合物的制作"
使用金属银和作为玻璃质粉体的以软化点为 650°C的硼硅酸玻璃 成分为主要成分的玻璃质粉体， 将 22g银和 1478g玻璃质粉体投入球 磨中混合 3小时， 然后， 使用电炉在 1000°C下加热 4小时使其熔融后， 进行冷却，将得到的块状物投入球磨中粉碎 25小时，得到软化点为 650 °C、 平均粒径为 6μηι、 银含量以金属银换算计为 1.0质量％的含银玻璃 质粉体。 另一方面，将金属银投入球磨中粉碎 15小时，得到平均粒径为 6μηι 的银粉体。 另外，使用以软化点为 350°C的磷酸玻璃成分为主要成分的玻璃质 粉体作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量银粉体、含银玻璃质粉体和第二种玻 璃质粉体， 投入球磨中混合 5小时， 得到实施例 4 的抗菌性组合物。 该抗菌性组合物的平均粒径为 8μηι， 银含量以金属银换算计为 25质量 %。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.10质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 4的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照 实施例 1进行评价。 评价结果示于表 1。
[实施例 5]
"抗菌性组合物的制作"
按照实施例 2， 得到含银玻璃质粉体及银粉体。 另外，使用以软化点为 500°C的钠钙玻璃成分为主要成分的玻璃质 粉体作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量银粉体、 含银玻璃质粉体和第二种玻 璃质粉体， 投入球磨中混合 5小时， 得到实施例 5 的抗菌性组合物。 该抗菌性组合物的平均粒径为 7μηι， 银含量以金属银换算计为 25质量 %。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.05 质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 5的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照 实施例 1进行评价。 评价结果示于表 1。
[实施例 6]
"抗菌性组合物的制作"
按照实施例 3， 得到含银玻璃质粉体。 另一方面， 将硝酸银投入球磨中粉碎 15 小时， 得到平均粒径为 15μηι的硝酸银粉体。 然后， 以 1 :2 的质量比称量硝酸银粉体和含银玻璃质粉体， 投入 球磨中混合 5小时， 得到实施例 6 的抗菌性组合物。 该抗菌性组合物 的平均粒径为 ΙΟμηι, 银含量以金属银换算计为 21质量％。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.10质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 6的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照 实施例 1进行评价。 评价结果示于表 1。 [实施例 7]
"抗菌性组合物的制作"
按照实施例 4， 得到实施例 6的含银玻璃质粉体及银粉体。 另外， 使用以软化点为 1200°C的硅酸盐矿物为主要成分的玻璃质 粉体作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量银粉体、含银玻璃质粉体和第二种玻 璃质粉体， 投入球磨中混合 5小时， 得到实施例 7 的抗菌性组合物。 该抗菌性组合物的平均粒径为 15μηι， 银含量以金属银换算计为 25质 量0 /0。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.30质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 7的抗菌性釉料组合物以及抗菌性陶瓷器板， 并按 照实施例 1进行评价。 评价结果示于表 1。
[实施例 8]
"抗菌性组合物的制作"
使用金属银和作为玻璃质粉体的以软化点为 1200°C的硅酸盐矿物 为主要成分的玻璃质粉体， 将 450g银和 1050g玻璃质粉体投入球磨中 混合 5小时， 然后， 使用电炉在 1500°C下加热 1小时使其熔融后， 进 行冷却， 将得到的块状物投入球磨中粉碎 25小时， 得到软化点为 1200 V、平均粒径为 15μηι、银含量以金属银换算计为 30质量％的含银玻璃 质粉体。 另一方面，将金属银投入球磨中粉碎 15小时，得到平均粒径为 6μηι 的银粉体。 另外，使用以软化点为 650°C的硼硅酸玻璃为主要成分的玻璃质粉 体作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量银粉体、含银玻璃质粉体和第二种玻 璃质粉体， 投入球磨中混合 5小时， 得到实施例 8 的抗菌性组合物。 该抗菌性组合物的平均粒径为 15μηι， 银含量以金属银换算计为 40质 量0 /0。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.30质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 8的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照 实施例 1进行评价。 评价结果示于表 1。
[实施例 9]
"抗菌性组合物的制作"
按照实施例 3， 得到含银玻璃质粉体及磷酸银粉体。 然后， 以 1 :2 的质量比称量磷酸银粉体和含银玻璃质粉体， 投入 球磨中混合 5小时， 得到实施例 9 的抗菌性组合物。 该抗菌性组合物 的平均粒径为 8μηι， 银含量以金属银换算计为 26质量％。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.10质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 9的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照 实施例 1进行评价。 评价结果示于表 1。 [实施例 10]
按照实施例 9， 得到实施例 10的抗菌性组合物。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 3.0质量％的上述抗菌性组合物， 除此以外， 按 照实施例 1， 制作实施例 10的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。 [实施例 1 1]
按照实施例 9， 得到实施例 1 1的抗菌性组合物。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 5.0质量％的上述抗菌性组合物， 除此以外， 按 照实施例 1， 制作实施例 1 1 的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。 [实施例 12]
"抗菌性组合物的制作"
使用硝酸银作为银化合物，使用以软化点为 650°C的硼硅酸玻璃成 分为主要成分的玻璃质粉体作为玻璃质粉体， 将 35g 硝酸银和 1465g 玻璃质粉体投入球磨中混合 3小时， 然后， 使用电炉在 1000°C下加热 4小时使其熔融后， 进行冷却， 将得到的块状物投入球磨中粉碎 25小 时， 得到软化点为 650°C、 平均粒径为 6μηι、 银含量以金属银换算计为 1.5质量％的含银玻璃质粉体。 另一方面，将金属银投入球磨中粉碎 15小时，得到平均粒径为 6μηι 的银粉体。 然后， 以 1 :2 的质量比称量银粉体和含银玻璃质粉体， 投入球磨 中混合 5小时， 得到实施例 12的抗菌性组合物。 该抗菌性组合物的平 均粒径为 6μηι， 银含量以金属银换算计为 25质量％。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 0.3质量％的上述抗菌性组合物， 除此以外， 按 照实施例 1， 制作实施例 12的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。 [实施例 13]
"抗菌性组合物的制作"
使用金属银、 作为银化合物的磷酸银和作为玻璃质粉体的以软化 点为 650°C的硼硅酸玻璃成分为主要成分的玻璃质粉体，将 22g银、 20g 磷酸银和 1458g玻璃质粉体投入球磨中混合 3小时， 然后， 使用电炉 在 1000°C下加热 4小时使其熔融后， 进行冷却， 将得到的块状物投入 球磨中粉碎 25小时， 得到软化点为 650°C、 平均粒径为 6μηι、 银含量 以金属银换算计为 2.0质量％的含银玻璃质粉体。 另一方面，将金属银投入球磨中粉碎 15小时，得到平均粒径为 6μηι 的银粉体。 另外，使用以软化点为 350°C的磷酸玻璃为主要成分的玻璃质粉体 作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量银粉体、含银玻璃质粉体和第二种玻 璃质粉体， 投入球磨中混合 5小时， 得到实施例 13的抗菌性组合物。 该抗菌性组合物的平均粒径为 8μηι， 银含量以金属银换算计为 26质量
%。
"抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.30质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 13的抗菌性釉料组合物及抗菌性陶瓷器板， 并按 照实施例 1进行评价。 评价结果示于表 1。
[实施例 14]
"抗菌性组合物的制作"
按照实施例 3， 得到含银玻璃质粉体。 另一方面， 以 1 : 1 的质量比称量金属银和磷酸银， 将这些物质投 入球磨中粉碎 15小时， 得到平均粒径为 8μηι的含银粉体。 另外，使用以软化点为 650°C的硼硅酸玻璃为主要成分的玻璃质粉 体作为第二种玻璃质粉体。 然后， 以 1 :2: 1的质量比称量含银粉体、 含银玻璃质粉体和第二种 玻璃质粉体，投入球磨中混合 5小时，得到实施例 14的抗菌性组合物。 该抗菌性组合物的平均粒径为 6μηι， 银含量以金属银换算计为 25质量 %。 "抗菌性釉料组合物及抗菌性陶瓷器板的制作、 评价"
使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料原料以 金属银换算计为 0.30质量％的上述抗菌性组合物， 除此以外， 按照实 施例 1， 制作实施例 14的抗菌性釉料组合物及抗菌性陶瓷器板， 并按 照实施例 1进行评价。 评价结果示于表 1。
[比较例 1]
使用实施例 1 的釉料原料作为釉料原料， 添加相对于上述釉料原 料以金属银换算计为 0.30质量％的磷酸银粉体， 制作抗菌性釉料组合 物。 使用该抗菌性釉料组合物， 按照实施例 1，制作比较例 1的抗菌性 陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。 [比较例 2]
使用金属银作为银粉体， 使用以软化点为 1200°C的硅酸盐矿物为 主要成分的玻璃质粉体作为第二种玻璃质粉体， 以 1 :2的质量比称量银 粉体和第二种玻璃质粉体， 投入球磨中混合 5小时， 得到比较例 2 的 抗菌性组合物。 该抗菌性组合物的平均粒径为 15μηι， 银含量以金属银 换算计为 25质量％。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 0.30质量％的上述抗菌性组合物， 除此以外， 按照实施例 1， 制作比较例 2的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。 [比较例 3]
使用金属银作为银粉体，使用以软化点为 350°C的磷酸玻璃为主要 成分的玻璃质粉体作为第二种玻璃质粉体， 以 1 :4的质量比称量银粉体 和第二种玻璃质粉体， 投入球磨中混合 5小时， 得到比较例 3 的抗菌 性组合物。 该抗菌性组合物的平均粒径为 8μηι， 银含量以金属银换算 计为 25质量％。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 0.50质量％的上述抗菌性组合物， 除此以外， 按照实施例 1， 制作比较例 3的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。
[比较例 4]
使用实施例 1 的釉料原料作为釉料原料， 添加相对于上述釉料原 料以金属银换算计为 0.30质量％的金属银作为银粉体， 制作抗菌性釉 料组合物。 使用该抗菌性釉料组合物， 按照实施例 1，制作比较例 1的抗菌性 陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。
[比较例 5]
使用金属银作为银粉体， 使用以软化点为 1600°C的石英玻璃为主 要成分的玻璃质粉体作为第二种玻璃质粉体，以 1 :2的质量比称量银粉 体和第二种玻璃质粉体， 投入球磨中混合 5小时， 得到比较例 5 的抗 菌性组合物。 该抗菌性组合物的平均粒径为 ΙΟμηι, 银含量以金属银换 算计为 25质量％。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 0.30质量％的上述抗菌性组合物， 除此以外， 按照实施例 1， 制作比较例 5的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 1。
[比较例 6]
使用金属银和作为玻璃质粉体的以软化点为 1600°C的石英玻璃为 主要成分的玻璃质粉体， 将 22g银和 1478g玻璃质粉体投入球磨中混 合 3小时， 然后， 使用电炉在 1650°C下加热 4小时使其熔融后， 进行 冷却， 将得到的块状物投入球磨中粉碎 25 小时， 得到软化点为 1600
°C的含银玻璃质粉体。 目视观察该含银玻璃质粉体， 结果发现银通过蒸发而消失， 不存 在于石英玻璃中。
[比较例 7]
使用金属银和作为玻璃质粉体的以软化点为 1200°C的硅酸盐矿物 为主要成分的玻璃质粉体， 将 825g银和 675g玻璃质粉体投入球磨中 混合 3小时， 然后， 使用电炉在 1500°C下加热 4小时使其熔融后， 进 行冷却， 将得到的块状物投入球磨中粉碎 25小时， 得到软化点为 1200
°C的含银玻璃质粉体。 目视观察该含银玻璃质粉体， 结果发现银和玻璃质粉体分离， 无 法得到均匀的玻璃质粉体。 表 1
Figure imgf000029_0001
根据表 1可知： 实施例 1〜14的抗菌性陶瓷器板， 从对大肠杆菌的 抗菌活性值及对金黄色葡萄球菌的抗菌活性值中的任意一者来看， 均 具有良好的抗菌性。 另一方面， 可知： 比较例 1〜4 的抗菌性陶瓷器板， 对大肠杆菌的 抗菌活性值及对金黄色葡萄球菌的抗菌活性值中的任意一者在合格范 围之外， 或者两者均在合格范围之外， 与实施例 1〜14的抗菌性陶瓷器 板相比抗菌性差。 比较例 5的抗菌性陶瓷器板， 表面析出异物， 外观明显受损。 比较例 6的含银玻璃质粉体， 银通过蒸发而消失， 比较例 7的含 银玻璃质粉体， 银和玻璃质粉体分离， 两者均无法得到具有抗菌性的 均匀的玻璃质粉体。 B. 本发明范围外的抗菌性釉料组合物的制作、抗菌性陶瓷器板的 制作及评价
在此， 制作本发明范围外的抗菌性釉料组合物， 使用该抗菌性釉 料组合物， 按照实施例 1制作抗菌性陶瓷器板并进行评价。 [比较例 8]
使用金属银和作为玻璃质粉体的以软化点为 650°C的硼硅酸玻璃 成分为主要成分的玻璃质粉体， 将 22g银和 1478g玻璃质粉体投入球 磨中混合 3小时， 然后， 使用电炉在 1000°C下加热 4小时使其熔融后， 进行冷却，将得到的块状物投入球磨中粉碎 25小时，得到软化点为 650 V、 平均粒径为 6μηι、 银含量以金属银换算计为 1.0质量％的含银玻璃 质粉体。 另一方面，将金属银投入球磨中粉碎 15小时，得到平均粒径为 6μηι 的银粉体。 然后， 以 1 :2 的质量比称量银粉体和含银玻璃质粉体， 投入球磨 中混合 5小时， 得到比较例 8 的抗菌性组合物。 该抗菌性组合物的平 均粒径为 6μηι， 银含量以金属银换算计为 25质量％。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 0.005质量％的上述抗菌性组合物， 除此以外， 按照实施例 1， 制作比较例 8的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 2。 [比较例 9]
使用按照比较例 8制作的含银玻璃质粉体和银粉体， 以 1 :2 的质 量比称量银粉体和含银玻璃质粉体， 投入球磨中混合 5 小时， 得到比 较例 9 的抗菌性组合物。 该抗菌性组合物的平均粒径为 6μηι， 银含量 以金属银换算计为 25质量％。 然后， 使用实施例 1 的釉料原料作为釉料原料， 添加相对于釉料 原料以金属银换算计为 10.0质量％的上述抗菌性组合物， 除此以外， 按照实施例 1， 制作比较例 9的抗菌性釉料组合物及抗菌性陶瓷器板， 并按照实施例 1进行评价。 评价结果示于表 2。 表 2
Figure imgf000031_0001
根据表 2可知， 比较例 8的抗菌性陶瓷器板， 对大肠杆菌的抗菌 活性值及对金黄色葡萄球菌的抗菌活性值均没有表现出抗菌性。 比较例 9的抗菌性陶瓷器板， 涂膜着色， 透明性降低。

Claims

1. 一种抗菌性组合物， 其特征在于， 含有含银粉体和含银玻璃质 粉体， 所述含银粉体含有由金属银及银化合物中的任意一种或两种构 成的银成分， 所述含银玻璃质粉体的玻璃质粉体中含有以金属银换算 计为 0.01质量％以上且 50质量％以下的由金属银及银化合物中的任意 一种或两种构成的银成分。
2. 根据权利要求 1所述的抗菌性组合物， 其特征在于， 所述含银 玻璃质粉体的软化点为 300°C以上且 1500°C以下。
3. 根据权利要求 1或 2所述的抗菌性组合物， 其特征在于， 还含 有软化点为 300°C以上且 1500°C以下的第二种玻璃质粉体。
4. 根据权利要求 1〜3中任一项所述的抗菌性组合物，其特征在于， 所述含银玻璃质粉体或所述第二种玻璃质粉体含有一种或两种以上软 化点为银的熔点以下的玻璃质粉体。
5. 根据权利要求 1〜4中任一项所述的抗菌性组合物，其特征在于， 所述银化合物为选自磷酸银、 氧化银、 碳酸银、 硝酸银、 氯化银、 硫 化银、 醋酸银中的一种或两种以上。
6. 一种抗菌性釉料组合物， 含有抗菌性组合物和釉料， 所述抗菌 性组合物含有含银粉体和含银玻璃质粉体， 所述含银粉体含有由金属 银及银化合物中的任意一种或两种构成的银成分， 所述含银玻璃质粉 体的玻璃质粉体中含有以金属银换算计为 0.01质量％以上且 50质量％ 以下的由金属银及银化合物中的任意一种或两种构成的银成分， 所述 抗菌性釉料组合物的特征在于， 所述抗菌性组合物的含量相对于所述 釉料以金属银换算计为 0.01质量％以上且 5质量％以下。
7. 一种抗菌性物品， 其特征在于， 利用权利要求 6所述的抗菌性 釉料组合物形成覆膜。
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