WO2008050625A1 - Produit céramique antibactérien, agent de traitement d'une surface céramique et procédé de fabrication d'un produit céramique antibactérien - Google Patents

Produit céramique antibactérien, agent de traitement d'une surface céramique et procédé de fabrication d'un produit céramique antibactérien Download PDF

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Publication number
WO2008050625A1
WO2008050625A1 PCT/JP2007/070076 JP2007070076W WO2008050625A1 WO 2008050625 A1 WO2008050625 A1 WO 2008050625A1 JP 2007070076 W JP2007070076 W JP 2007070076W WO 2008050625 A1 WO2008050625 A1 WO 2008050625A1
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Prior art keywords
antibacterial
ceramic
metal
surface treatment
treatment agent
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PCT/JP2007/070076
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English (en)
Japanese (ja)
Inventor
Kohei Shimoda
Issei Okada
Kenji Miyazaki
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Sumitomo Electric Industries, Ltd.
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Publication of WO2008050625A1 publication Critical patent/WO2008050625A1/fr

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    • 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
    • C04B41/88—Metals
    • 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
    • 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
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • 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

  • Antibacterial ceramic products are antibacterial ceramic products, ceramic surface treatment agents, and methods of manufacturing antibacterial ceramic products
  • the present invention relates to an antibacterial ceramic product provided with antibacterial properties on the surface of ceramic products represented by ceramic products such as sanitary ware and Japanese and Western tableware, and a ceramic industry used for manufacturing the antibacterial ceramic products.
  • the present invention relates to a surface treatment agent and a method for producing an antibacterial ceramic product using the ceramic surface treatment agent.
  • Antibacterial agents for imparting antibacterial properties to the surface of ceramic products include metals such as silver, copper, tin and zinc (hereinafter, these metals may be collectively referred to as "antibacterial metals") Is used. These antibacterial metals function as a catalyst, change oxygen dissolved in water to active oxygen, and suppress the growth of fungi and fungi by the action of the changed active oxygen. It is known that antibacterial properties are exhibited by the so-called oligodynamic effect. When antibacterial properties are imparted to the surface of ceramic products using the antibacterial metal, the substrate of ceramic products is considered in consideration of maintaining good antibacterial properties for as long as possible. In general, an antibacterial metal is contained in the glaze layer formed on the surface of the unglazed product or the like, or in the substrate itself.
  • Patent Document 1 in order to prevent the antibacterial metal from being eroded by the melt of the glaze component during firing, the antibacterial metal is supported on hydroxyapatite to form composite particles. After forming and adding the composite particles to the glaze, the glaze is applied to the surface of the substrate and baked to form a glaze layer containing an antibacterial metal. Further, in Patent Document 2, for the same purpose, an antibacterial metal ion is contained in a calcium phosphate compound to form composite particles, and after adding the composite particles to the glaze, the glaze is added to the surface of the substrate. It is described that a glaze layer containing an antibacterial metal is formed by applying and baking.
  • Patent Document 3 an inorganic pigment as composite particles retaining an antibacterial metal is added to a glaze, and the glaze is applied to the surface of the substrate and then baked to obtain an antibacterial agent. Contains metallic A glaze layer is formed, or the inorganic pigment is added to the clay or magnetic earth that is the basis of the ceramic product base. After the ceramic clay is molded into the shape of the ceramic product, it is baked and applied to the base itself. It describes that an antibacterial metal is contained. Further, in Patent Document 4, silver oxide, metallic silver, or an arbitrary silver compound is added to the lower paint, and the surface of the ceramic product base or the glaze layer formed on the surface is added using the lower paint. Antibacterial by drawing a sketch on the surface, adding silver oxide or the like to the glaze, and applying the glaze to the surface of the substrate or the glaze layer formed on the surface and baking. It describes the formation of a rough sketch or glaze layer containing a functional metal!
  • Patent Document 1 JP-A-5-201747 (Claim 1, Paragraph [0007], Paragraph [0010])
  • Patent Document 2 JP-A-6-127975 (Claim 1, Paragraphs [0008] to [0009]
  • Patent Document 3 Japanese Patent Laid-Open No. 7-233334 (Claims 1, 2, Paragraph [0009], Paragraph [0025])
  • Patent Document 4 Japanese Patent Laid-Open No. 7-196384 (Claims;! To 8, Paragraph [ 0014])
  • An object of the present invention is to provide a novel antibacterial ceramic industry that can obtain sufficient antibacterial properties even when the amount of the antibacterial metal used is less than the current amount because the use efficiency of the antibacterial metal is high.
  • An object of the present invention is to provide a product, a ceramic surface treatment agent that can be used for producing the antibacterial ceramic product, and a method for producing an antibacterial ceramic product using the ceramic surface treatment agent. Means for solving the problem
  • the antibacterial property of the antibacterial metal based on the oligodynamic effect described above is the antibacterial exposed on the surface of the glaze layer in the case of a ceramic product to be manufactured, for example, a ceramic product having a glaze layer
  • the contact area between the conductive metal and water increases, and the contact area tends to increase as the particle size of the antibacterial metal decreases and the specific surface area increases.
  • all of the conventional ceramic products have a large particle size of the antibacterial metal exposed on the surface and a small specific surface area, so the utilization efficiency of the antibacterial metal is low. Not enough antibacterial properties to meet the amount of antibacterial metal used.
  • the invention according to claim 1 is an antibacterial ceramic product characterized in that metal nanoparticles containing at least silver and having an average particle diameter of 200 nm or less are present on the surface!
  • the inventor exposes as many metal nanoparticles having an average particle diameter of 200 nm or less as described above to the surface of ceramic products as much as possible, thereby improving the utilization efficiency of the antibacterial metal constituting the metal nanoparticles.
  • a ceramic surface treatment agent in which metal nanoparticles with a 90% cumulative diameter D force S l 50 nm or less of particle size distribution are colloidally dispersed in a dispersion medium,
  • the invention described in claim 2 is characterized in that a metal nanoparticle force colloidal dispersion having a 90% cumulative diameter D force S l of 50 nm or less of the particle size distribution is dispersed in the dispersion medium.
  • the antibacterial property due to the antibacterial metal is manifested only in the antibacterial metal exposed to the surface of the glaze layer and in contact with water if it is a ceramic product having a glaze layer, for example, Antibacterial metals present in the glaze layer and the like hardly contribute to imparting antibacterial properties. Therefore, in order to increase the utilization efficiency of antibacterial metals, the proportion of antibacterial metals that are not exposed on the surface of the glaze layer or the like is reduced as much as possible, and the proportion of antibacterial metals that are exposed on the surface is relatively increased. It is important.
  • the composite particles carrying antibacterial metals described in Patent Documents 1 to 3 described earlier, the silver oxide described in Patent Document 4, water-insoluble and poorly soluble silver compounds, and the like are glazes.
  • the composition of the glaze is constantly changing due to aggregation and sedimentation, the exposure amount and particle size of the antibacterial metal on the surface of the glaze layer formed using the glaze and the associated antibacterial performance There is also a problem that it varies easily for each ceramic product manufactured.
  • the water-soluble silver compound described in Patent Document 4 is uniformly dissolved in a glaze that is usually aqueous, and therefore does not cause aggregation or sedimentation.
  • a glaze that is usually aqueous, and therefore does not cause aggregation or sedimentation.
  • the silver atoms generated as a result of thermal decomposition of the silver compound are used as the nucleus of precipitation, and the silver atoms are successively deposited and the silver particles gradually grow. Therefore, particularly on the surface of the glaze layer, the silver particles are liable to be volatilized and lost by the heat of firing at a stage before growing to a sufficient size. Therefore, if the ratio of silver exposed on the surface of the glaze layer is reduced, the utilization efficiency of the silver as an antibacterial metal is greatly reduced.
  • the silver deposited in the glaze layer often causes the glaze layer to have a specific color.
  • the metal nanoparticles having a 90% cumulative diameter D force Sl of 50 nm or less of the particle size distribution are uniformly and stably present in the dispersion medium.
  • the ceramic surface treatment agent of the present invention When the ceramic surface treatment agent of the present invention is used in the manufacture of ceramic products as glazes or underpaints, it is difficult to agglomerate or settle. It is not necessary to frequently perform operations such as crushing aggregates and redispersing sediments, and even without performing the above operations, the exposure amount and particle size of the antibacterial metal and the antibacterial performance associated therewith It is possible to produce antibacterial ceramic products with a constant and.
  • the average particle diameter of the remaining metal nanoparticles The force is 3 ⁇ 400 nm or less, and as described above, the specific surface area and thus the contact area with water are Combined with the large size, the utilization efficiency of the antibacterial metal constituting the metal nanoparticles in the antibacterial ceramic product can be improved more than before. Therefore, according to the ceramic surface treatment agent of the invention described in claim 2, it is possible to obtain sufficient antibacterial properties even if the amount of the antibacterial metal used is smaller than the current amount. In addition, it is possible to reliably prevent the glaze layer and the background from becoming a predetermined color and increasing the cost of ceramic products.
  • the antibacterial metal forming the metal nanoparticles among the antibacterial metals exemplified above, silver excellent in antibacterial property based on the oligodynamic effect is preferable. Therefore, the invention described in claim 3 is the ceramic surface treatment agent according to claim 2, wherein the metal nanoparticles contain at least silver. Further, when the dispersion medium is water, in order to maintain the colloidal dispersion of the metal nanoparticles in the dispersion medium more stably, the metal nanoparticles are coated with a dispersant having a hydrophilic group. In this state, it is preferably dispersed in a colloid.
  • the invention according to claim 4 is characterized in that the metal nanoparticles are colloidally dispersed in water as a dispersion medium in a state where they are coated with a dispersant having a hydrophilic group.
  • the degree of stabilization of the colloidal dispersion of the metal nanoparticles is the total amount of the metal nanoparticles settled after 24 hours from the preparation of the dispersion containing the metal nanoparticles. It is preferably 0.1% by weight or less. Therefore, the invention according to claim 5 uses a dispersion liquid in which the amount of sedimentation of the metal nanoparticles after the lapse of 24 hours after preparation is 0.1% by weight or less of the total amount of the metal nanoparticles. 5.
  • the invention according to claim 6 includes a step of baking at 800 to 1600 ° C. after coating the ceramic surface treatment agent according to any of claims 2 to 5 on the surface of the ceramic product.
  • the metal nanoparticle having an average particle diameter of 200 nm or less is formed on the surface simply by applying the ceramic surface treatment agent of the present invention to the surface of the ceramic product and firing in the temperature range. It is the ability to produce the antibacterial ceramic products of the present invention that are present with high productivity.
  • the invention's effect since the utilization efficiency of the antibacterial metal is high, a novel antibacterial ceramic industry that can obtain sufficient antibacterial properties even if the amount of the antibacterial metal used is less than the current amount. It is possible to provide a product, a ceramic surface treatment agent that can be used to produce the antibacterial ceramic product, and a method for producing an antibacterial ceramic product using the ceramic surface treatment agent.
  • FIG. 1 is a scanning electron micrograph showing the surface on which silver nanoparticles are formed of the antibacterial ceramic product produced in Sample No. 2-3 of Example 2.
  • the ceramic surface treatment agent of the present invention used for producing the antibacterial ceramic product of the present invention is a gold having 90% cumulative particle size distribution D force of 50 nm or less in a dispersion medium.
  • the genus nanoparticles are colloidally dispersed.
  • the 90% cumulative diameter of metal nanoparticles, D force is limited to 50 nm or less.
  • the colloidal dispersion cannot be stably performed in the ceramic surface treatment agent, the ratio of metal nanoparticles exposed on the surface of the manufactured antibacterial ceramic product is reduced because it aggregates or settles.
  • the ceramic surface treatment agent containing metal nanoparticles having a large particle diameter it is difficult to make the average particle diameter of the metal nanoparticles formed on the surface of the antibacterial ceramic product 200 nm or less.
  • the antibacterial ceramic product has a small proportion of metal nanoparticles exposed on the surface of the antibacterial ceramic product, and the average particle diameter of the exposed metal nanoparticles exceeds 200 nm and the specific surface area is small. In this case, the utilization efficiency of the antibacterial metal constituting the metal nanoparticles is reduced.
  • the 90% cumulative diameter D is preferably 40 nm or more even within the above range. Also, metal nanoparticles, grains
  • the median diameter D of the degree distribution is preferably lOOnm or less.
  • Particle size of metal nanoparticles in the present invention are the laser Doppler method.
  • the metal nanoparticles are one kind of antibacterial metal such as silver, copper, tin, zinc, etc. that can exhibit antibacterial properties by an oligodynamic effect, or two or more kinds.
  • antibacterial metal such as silver, copper, tin, zinc, etc.
  • it can also be formed from an alloy of one or more of the antibacterial metals with other metals.
  • the metal nanoparticles are made of silver and other antibacterial metals or alloys with other metals, considering the more effective expression of antibacterial properties due to silver, the silver content is It is preferably 50% by weight or more, particularly 80% by weight or more of the total amount of the alloy.
  • Examples of metals other than the antibacterial metal that form an alloy with silver include platinum, palladium, rhodium, iridium, nickel, and iron. Since these metals all have a higher melting point than silver, the melting point of the alloy is increased, and the metal nanoparticles are prevented from growing due to, for example, fusing due to heat during firing, and thus the antibacterial ceramic industry. It works to prevent the average particle size of the metal nanoparticles exposed on the surface of the product from becoming too large. In addition, the metal forms an alloy with silver, thereby preventing oxidation or so-called migration and maintaining the antibacterial property of silver for a long period of time.
  • the metal nanoparticles may have a composite structure in which the surface of core particles made of any metal is covered with a skin layer made of silver, an alloy containing silver, or the like.
  • the metal nanoparticles can be produced by various conventionally known methods such as a high temperature treatment method called an impregnation method, a liquid phase reduction method, and a gas phase method.
  • a high temperature treatment method called an impregnation method
  • a liquid phase reduction method for example, a water-soluble metal compound that is a source of metal ions forming the metal nanoparticles and a dispersant are dissolved in water.
  • a reducing agent may be added, and the metal ions may be preferably subjected to a reduction reaction with stirring for a certain period of time.
  • metal nanoparticles made of an alloy by a liquid phase reduction method two or more water-soluble metal compounds that form the alloy and are sources of at least two kinds of metal ions. May be used in combination.
  • the deposition of the core material particles and the deposition of the coating layer on the surface of the core material particles may be sequentially performed by a liquid phase reduction method.
  • the metal nanoparticles produced by the liquid phase reduction method are characterized by having a spherical or granular shape, a sharp particle size distribution, and a small particle size.
  • Examples of the water-soluble metal compound that is a source of metal ions include silver nitrate (I) [AgNO] and silver methanesulfonate [CH 2 SO Ag] in the case of silver.
  • silver nitrate (I) [AgNO] and silver methanesulfonate [CH 2 SO Ag] in the case of silver.
  • copper copper nitrate (II) [Cu (NO)]
  • tin chloride (IV) pentahydrate [SnCl ⁇ 5 ⁇ ] can be mentioned.
  • rhodium rhodium (III) chloride trihydrate [RhCl ⁇ 3 ⁇ 0], rhodium nitrate (III) solution [Rh (NO)] and the like can be mentioned.
  • iridium iridium chloride ( IIlKlrCl] etc.
  • nickel nickel chloride ( ⁇ ) hexahydrate [NiCl ⁇ 6 ⁇ 0], nickel nitrate ( ⁇ ) hexahydrate [Ni (NO) ⁇ 6 ⁇ 0], etc.
  • iron iron nitrate (III) hexahydrate, nonahydrate (Fe (NO) ⁇ 6 ⁇ 0, 9H O), iron chloride ( ⁇ ) tetrahydrate (FeCl ⁇ 4 ⁇ ⁇ ) , Iron sulfate ( ⁇ ) heptahydrate (FeSO ⁇ 7 ⁇ ⁇ ), acetylacetone iron (III) (Fe [CH (COCH)]) and the like.
  • any of various reducing agents capable of reducing metal ions and precipitating them as metal nanoparticles in a liquid phase reaction system can be used.
  • the reducing agent include sodium borohydride, sodium hypophosphite, hydrazine, and transition metal ions (trivalent titanium ions, divalent cobalt ions, etc.).
  • transition metal ions trivalent titanium ions, divalent cobalt ions, etc.
  • the reduction of metal ions and the deposition rate should be slowed.
  • a reducing agent having a reducing power as weak as possible.
  • the reducing agent having a weak reducing power include alcohols such as methanol, ethanol, 2-propanol, and ascorbic acid, as well as ethylene glycol, glutathione, organic acids (taenoic acid, malic acid, Tartaric acid, etc.), reducing saccharides (glucose, galactose, mannose, funolectus, sucrose, manoletose, raffinose, starchy etc.), sugar alcohols (sorbitol, etc.), among others, reducing saccharides, Sugar alcohols as derivatives thereof are preferred.
  • the dispersant various dispersants are used that have a hydrophilic group, have good solubility in water, and can disperse precipitated metal nanoparticles in water. it can .
  • the dispersing agent coats the surface of the deposited metal nanoparticles to prevent aggregation of the metal nanoparticles and maintain the dispersion.
  • the liquid phase reaction system in which the metal nanoparticles are deposited is a starting point for preparing a ceramic surface treatment agent in a liquid phase state in which only impurities are removed without separating the metal nanoparticles from the reaction system. It can be used as a raw material.
  • the dispersant remains almost removed in the impurity removal step, and covers the surface of the metal nanoparticles in the prepared ceramic surface treatment agent as described above, thereby agglomerating. And can continue to function as a dispersant to maintain dispersion
  • Dispersion homogeneous IJi number average molecular weight ⁇ force 1000 to 800,000, particularly 2000 to 300,000 force S is preferable.
  • the number average molecular weight ⁇ is less than the above range, there is a possibility that the effect of maintaining the dispersion by preventing the aggregation of the metal nanoparticles by the dispersing agent may not be obtained.
  • the said range is exceeded, there exists a possibility that the handling at the time of the application
  • Hydrophilic groups introduced into the dispersant include oxygen-containing functional groups such as oxy group (— ⁇ —), hydroxy group (- ⁇ ), carboxy group (—COOH), amino group ( ⁇ ), imino group (> ⁇ ), Ammonium group (- ⁇ + )
  • Examples include nitrogen-containing functional groups such as 2 4, sulfur-containing yellow functional groups such as sulfanyl group (one SH), sulfandyl group (one S), and the like.
  • the dispersant may have one kind of the hydrophilic group, or two or more kinds.
  • Suitable dispersants include, for example, poval (polybulal alcohol), polyethylene oxide, polypropylene oxide, polyethyleneimine, polybulylpyrrolidone, polyalkane. Examples include thiol and maleic acid-based copolymers.
  • the dispersant can be added to the reaction system in the form of a solution dissolved in water or a water-soluble organic solvent.
  • the amount of the dispersing agent added is such that when the dispersing agent is subsequently used as a dispersing agent that coats the surface of the metal nanoparticles and prevents its aggregation in the ceramic surface treatment agent, the ceramic surface treatment
  • the content of the dispersant expressed as a percentage of the amount of metal nanoparticles, is preferably !!-20% by weight, in particular 8-8%, preferably 15% by weight. If the content of the dispersant is less than the above range, the effect of preventing the aggregation by covering the surface of the metal nanoparticles in the reaction system and in the ceramic surface treatment agent by the dispersant cannot be sufficiently obtained. ! / There is a risk.
  • the ceramic surface treatment agent is a glaze
  • an excessive dispersant is sintered in the glaze component contained in the glaze during firing. May be hindered to reduce the denseness of the formed glaze layer.
  • a base paint there is a risk that the density of the base picture formed, the adhesion to the glaze layer, and the like may be reduced.
  • the stirring speed, temperature, time, pH, etc. may be adjusted when the metal compound is reduced.
  • the pH of the reaction system is 7 to 13 considering the formation of metal nanoparticles with a 90% cumulative diameter D as small as possible.
  • a pH adjuster In order to adjust the pH of the reaction system to the above range, a pH adjuster is used.
  • the pH adjuster include various acids such as nitric acid and various alkalis such as ammonia depending on the pH value to be adjusted.
  • a ceramic surface treatment agent may be prepared by blending with a water-soluble organic solvent at a predetermined ratio, but as described above, a liquid-phase reaction system in which metal nanoparticles are precipitated is used. It is preferable to prepare a ceramic surface treatment agent using as a starting material. That is, gold
  • Ceramic table A ceramic surface treatment agent is prepared by blending other components constituting the surface treatment agent in a predetermined ratio. This method can prevent the generation of coarse and irregular particles due to the aggregation of metal nanoparticles.
  • Other components constituting the ceramic surface treatment agent include water-soluble organic solvents for adjusting the viscosity and vapor pressure of the ceramic surface treatment agent.
  • water-soluble organic solvent various organic solvents that are water-soluble can be used. Specific examples thereof include alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl ethyl ketone, ethylene glycol monomethino ethenore, ethylene glycol monomethino reetor and the like.
  • Daricol ethers and the like can be mentioned.
  • the addition amount of the water-soluble organic solvent is preferably 30 to 900 parts by weight per 100 parts by weight of the metal nanoparticles.
  • the addition amount is less than the above range, the effect of adjusting the viscosity or vapor pressure of the dispersion by adding the organic solvent may not be sufficiently obtained.
  • the above range is exceeded, it is possible to sufficiently swell the dispersant with water so that the metal nanoparticles coated with the dispersant do not cause aggregation in the ceramic surface treatment agent. Dispersing effect may be hindered.
  • the amount of sedimentation of the metal nanoparticles when the dispersion has been prepared for 24 hours after preparation is 0.1% by weight or less of the total amount of the metal nanoparticles.
  • the amount of sedimentation exceeds the above range, the metal nanoparticles tend to settle. Therefore, when a ceramic surface treatment agent is prepared using the dispersion, the proportion of metal nanoparticles exposed on the surface formed by firing the ceramic surface treatment agent is reduced, and the use efficiency of the antibacterial metal is reduced. There is a risk of lowering or poor appearance.
  • the amount of sedimentation of the metal nanoparticles is within the above range, the stability of the colloidal dispersion of the metal nanoparticles can be improved, and the colloidal dispersion can be more uniformly dispersed in the ceramic surface treatment agent. In addition, sedimentation can be prevented. Therefore, by increasing the proportion of metal nanoparticles exposed on the surface formed by firing the ceramic surface treatment agent, the utilization efficiency of the antibacterial metal constituting the metal nanoparticles can be further improved. It becomes possible to make the appearance good.
  • the particle diameter of the metal nanoparticles and the coating amount of the dispersant may be adjusted. In general, the smaller the particle size of the metal nanoparticles, the greater the coating amount of the dispersant. The more you decrease, the more you can reduce the amount of sediment.
  • the method for producing an antibacterial ceramic product of the present invention is as follows. After applying the ceramic surface treatment agent of the present invention to the surface of the ceramic product, 800 ⁇ ; 1600 ° It includes a step of firing with C. Specifically, for example, using the ceramic surface treatment agent of the present invention as a glaze, it is applied to the surface of a ceramic product substrate or the surface of the glaze layer formed on the surface, or the ceramic surface treatment agent. Is used as a base paint to draw a rough sketch on the surface of the glaze layer formed on the surface of the ceramic product substrate, and then fired in the above temperature range to give metal nano particles with an average particle diameter of 200 nm or less to the surface. The antibacterial ceramic product of the present invention in which particles are present is produced.
  • the reason why the firing temperature is limited to 800 to 1600 ° C is as follows. That is, when the firing temperature is less than the above range, for example, when the ceramic surface treatment agent is a glaze, the glaze component cannot be sufficiently sintered, so that the density of the formed glaze layer may be reduced. There is. Further, in the case of a base paint, there is a risk that the density of the formed base sketch, the adhesion to the glaze layer, and the like may be reduced. On the other hand, when the firing temperature exceeds the above range, the metal nanoparticles exposed on the surface of the glaze layer and the lower paint are volatilized by the heat of firing and are easily lost.
  • the firing temperature depends on the type of glaze component, pigment, etc., but is 1000 to 1600 even within the above range. C, especially from 1150; It's about C.
  • the firing may be performed in an air atmosphere, or depending on the type of glaze or lower paint, it may be performed in an appropriate firing atmosphere such as a reducing atmosphere.
  • the firing time is set so that the average particle diameter of the metal nanoparticles formed on the surface of the ceramic product to be produced is 200 nm or less and imparts good antibacterial properties. , 20 minutes to 30 hours is preferred!
  • the antibacterial ceramic product of the present invention that can be manufactured by the above-described manufacturing method or the like has metal nanoparticles having an average particle diameter of 200 nm or less and containing at least silver on the surface. It is characterized by that.
  • the reason why the average particle diameter of the metal nanoparticles present on the surface is limited to 200 nm or less is as follows. That is, the average particle Within the above range, the utilization efficiency of the antibacterial metal forming the metal nanoparticles can be improved, and sufficient antibacterial properties commensurate with the amount of the antibacterial metal used can be obtained. For this reason, the amount of antibacterial metal used can be reduced, and for example, it is possible to reliably prevent the glaze layer and the background from becoming a predetermined color or increasing the cost of ceramic products. .
  • the average particle size is preferably 0.5 to 100 nm, and more preferably 0.5 to 50 nm, even within the above range.
  • the average particle size can be determined from the particle size by direct observation. Specifically, for example, particles of at least 10 metal nanoparticles obtained by observing the surface of an antibacterial ceramic product using a high-resolution SEM (scanning electron microscope) having an observation magnification of 10,000 times or more. The average value can be obtained from the diameter to obtain the average particle diameter.
  • Silver nitrate (I) as a metal compound is dissolved in pure water, ammonia water is added to adjust the pH of the solution to 10, and then maleic acid as a dispersant.
  • a copolymer (Crobacs (registered trademark) 400-21S manufactured by Nippon Kasei Co., Ltd., molecular weight: 9000, acid value: 10 OmgKOH / g) was added and dissolved, and then ethylene glycol as a reducing agent was purified.
  • a solution dissolved in water was added to prepare a liquid phase reaction system. The concentration of each component in the reaction system was silver nitrate (I): 25 g / liter, maleic acid copolymer: 20 g / liter, reducing agent: 120 g / liter.
  • the reaction system was reacted at 85 ° C for 180 minutes with vigorous stirring at a force and stirring speed of lOOrpm to precipitate silver nanoparticles, and then diluted with pure water by ultrafiltration treatment.
  • the impurities were removed by repeating the above to obtain a dispersion liquid in which the silver nanoparticles were colloidally dispersed.
  • the 90% cumulative diameter D of the particle size distribution of the silver nanoparticles in the above dispersion is determined using the laser Doppler method.
  • the solid content concentration in the dispersion is 10% by weight, and the dispersion per 100 parts by weight of silver nanoparticles is The amount of the agent was 9 parts by weight.
  • the dispersion lOOOOg was collected in a glass container, and the glass container was allowed to stand for 24 hours in a thermostatic bath maintained at 25 ° C. in a state where the glass container was sealed with a polypropylene resin cap. The supernatant was removed with a dropper, and the sediment settled on the bottom of the glass container was collected, dried at 105 ° C for 3 hours, and weighed with a precision balance. The sedimentation amount was 0% of the total amount of silver nanoparticles. It was confirmed to be 03% by weight.
  • ⁇ Preparation of ceramic surface treatment agent 35.58 parts by weight of feldspar, 13.5 parts by weight of lime, 9.7 parts by weight of clay, and 40.2 parts by weight of silica sand as glaze components
  • feldspar 13.5 parts by weight of lime
  • silica sand 40.2 parts by weight of silica sand as glaze components
  • the previously prepared dispersion of silver nanoparticles is added to the slurry so that the ratio of silver nanoparticles in the total amount of solids is 0.02 wt%, and mixed to obtain a ceramic surface treatment agent.
  • a glaze was prepared.
  • the glaze it is expressed as a percentage of the amount of the dispersing agent relative to the amount of metal nanoparticles from the content of the dispersant obtained by performing TG-MASS analysis and the content of silver obtained by performing ICP analysis.
  • the content was determined to be 3.3% by weight.
  • Example 2 In accordance with the method described in Example 1, as shown in Table 1, five types of silver nanoparticle dispersions having different 90% cumulative diameter D of the particle size distribution of silver nanoparticles were prepared, and the silver nanoparticles were Dispersion
  • the glaze was prepared under the same conditions as in Example 1 to produce an antibacterial ceramic product, and then the sterilization rate was determined to evaluate the antibacterial property. The results are shown in Table 1.
  • the 90% cumulative diameter D of the particle size distribution of silver nanoparticles in the glaze was set to 150 nm or less.
  • a silver nanoparticle dispersion having 90 nm and a sedimentation amount of 0.06% by weight of the total amount of silver nanoparticles was prepared. Using the silver nanoparticle dispersion, the content of the dispersant was 1.2% by weight. After the preparation of the glaze, an antibacterial ceramic product was manufactured in the same manner as in Example 1 except that the firing conditions shown in Table 2 were used, and the antibacterial properties were evaluated by obtaining the sterilization rate. did. The results are shown in Table 2.
  • the 90% cumulative diameter D of the particle size distribution of the silver nanoparticles was 33.
  • Example 1 contains metal nanoparticles made of silver or a combination of silver and palladium, and 90% cumulative diameter of the particle size distribution of the metal nanoparticles D
  • a glaze having a dispersant content of 12.5 to 15.0 wt% is prepared, Using glaze, antibacterial ceramic products were produced under the same conditions as in Example 1, the sterilization rate was determined, and antibacterial properties were evaluated.
  • the dispersant polyacrylic acid (molecular weight 5000) was used. The results are shown in Table 4.
  • the silver content is preferably 50% by weight or more, particularly 80% by weight or more in the total amount of the alloy!

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Abstract

L'invention concerne un nouveau produit céramique antibactérien qui présente une grande efficacité d'utilisation d'un métal antibactérien et peut donc fournir des propriétés antibactériennes satisfaisantes même lorsque le métal antibactérien est utilisé en une quantité réduite en comparaison d'un produit classique. L'invention concerne également un agent de traitement d'une surface céramique qui peut être utilisé pour la fabrication du produit céramique antibactérien. L'invention concerne également un procédé de fabrication d'un produit céramique antibactérien utilisant l'agent de traitement d'une surface céramique. Le produit céramique antibactérien comporte, à sa surface, une nanoparticule métallique qui comprend au moins de l'argent et a un diamètre de particule moyen inférieur ou égal à 200 nm. L'agent de traitement d'une surface céramique comprend une nanoparticule métallique dispersée dans un milieu de dispersion sous forme colloïdale, ladite nanoparticule métallique ayant un diamètre accumulé à 90 % (D90) dans la distribution de taille de particule inférieur ou égal à 150 nm. Le procédé de fabrication du produit céramique antibactérien comprend les étapes consistant à appliquer l'agent de traitement d'une surface céramique sur la surface d'un produit céramique et à traiter thermiquement le produit céramique à une température de 800 à 1 600 °C.
PCT/JP2007/070076 2006-10-27 2007-10-15 Produit céramique antibactérien, agent de traitement d'une surface céramique et procédé de fabrication d'un produit céramique antibactérien WO2008050625A1 (fr)

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JP5599060B2 (ja) * 2010-10-14 2014-10-01 三菱製紙株式会社 銀超微粒子分散液を含有する抗菌性窯業用表面処理剤
CN105613582B (zh) * 2014-10-31 2019-11-22 住友大阪水泥股份有限公司 抗菌性组合物及抗菌性釉料组合物以及抗菌性物品
WO2017082117A1 (fr) * 2015-11-12 2017-05-18 三菱電機株式会社 Agent et objet antimicrobiens à libération prolongée
JP6930343B2 (ja) 2017-09-29 2021-09-01 信越化学工業株式会社 消臭・抗菌・抗カビ剤含有分散液、その製造方法、及び消臭・抗菌・抗カビ剤を表面に有する部材
CN109384452A (zh) * 2018-10-31 2019-02-26 福建省德化县合和陶瓷技术开发有限公司 一种自洁型抗菌日用陶瓷制品及其制备工艺
KR101975955B1 (ko) * 2018-12-20 2019-05-08 맥섬석 지.엠. 주식회사 맥섬석 과립 항균 플라스틱 마스터배치 제조 방법
CN111559926B (zh) * 2020-07-15 2020-10-27 广东蒲公英新型材料有限公司 一种基于硅酸盐基体表面的抗菌材料及其制备方法
CN113248143B (zh) * 2021-07-14 2021-09-24 广东欧文莱陶瓷有限公司 一种抗菌数码保护釉料
CN114853340A (zh) * 2022-04-20 2022-08-05 德化县宏顺陶瓷有限公司 抗菌陶瓷的釉浆配方、抗菌陶瓷及抗菌陶瓷的烧制工艺
CN116283244B (zh) * 2023-05-17 2023-07-21 湖南大学 一种采用流延成型制备氧化铝陶瓷薄片的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873256A (ja) * 1994-09-01 1996-03-19 Inax Corp 抗菌性陶磁器の製造方法
JP2000143405A (ja) * 1998-11-05 2000-05-23 Mitsubishi Materials Corp 表面処理材及び抗菌性窯業製品並びにその製造方法
JP2004033901A (ja) * 2002-07-03 2004-02-05 Nippon Paint Co Ltd 金属コロイド溶液の製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08290985A (ja) * 1995-04-20 1996-11-05 Narumi China Corp 抗菌性窯業製品及びその製造方法
JP3454640B2 (ja) * 1996-07-04 2003-10-06 住友大阪セメント株式会社 抗菌・防黴・防藻性物品およびその製造方法
JPH11189509A (ja) * 1997-12-25 1999-07-13 Sumitomo Osaka Cement Co Ltd 抗菌性塗布液
JP4148078B2 (ja) * 2003-09-12 2008-09-10 住友電気工業株式会社 金属粉末の製造方法
JP3952027B2 (ja) * 2004-03-01 2007-08-01 住友電気工業株式会社 金属コロイド溶液
JP4735939B2 (ja) * 2004-12-27 2011-07-27 住友電気工業株式会社 合金微粒子の製造方法とそれによって製造される合金微粒子および金属コロイド溶液

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873256A (ja) * 1994-09-01 1996-03-19 Inax Corp 抗菌性陶磁器の製造方法
JP2000143405A (ja) * 1998-11-05 2000-05-23 Mitsubishi Materials Corp 表面処理材及び抗菌性窯業製品並びにその製造方法
JP2004033901A (ja) * 2002-07-03 2004-02-05 Nippon Paint Co Ltd 金属コロイド溶液の製造方法

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