CN105613582B - Anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles - Google Patents
Anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles Download PDFInfo
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- CN105613582B CN105613582B CN201410601663.9A CN201410601663A CN105613582B CN 105613582 B CN105613582 B CN 105613582B CN 201410601663 A CN201410601663 A CN 201410601663A CN 105613582 B CN105613582 B CN 105613582B
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- 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
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- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
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- 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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
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- 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
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- 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
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- 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
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
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- 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
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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- 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
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- 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
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Abstract
The present invention provides anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles.Anti-bacterial composition of the invention includes the mixture containing aluminium powder Yu phosphate glass powder, the above-mentioned content containing aluminium powder in said mixture is calculated as 5 mass % or more and 60 mass % hereinafter, the mass ratio i.e. A/P of the silver (A) and phosphate glass (P) that contain in said mixture is 0.05 or more and 1.5 or less with silver conversion.According to the anti-bacterial composition, antibiotic property can be improved, and can reduce the content of silver or silver compound.
Description
Technical field
The present invention relates to anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles, especially specifically,
It is related to suitable for building materials, vapour such as kitchen articles, the ceramic tiles such as health pottery tool, medical supplies, enamel articles, various containers, tableware
The various components of vehicle, electrical equipment the various components such as panel, anti-bacterial composition with excellent antibiotic property and contain
The anti-bacterial composition and the antibiotic property glaze compositions of glaze and resisting using antibiotic property glaze compositions formation overlay film
Bacterium property article.
Background technique
Currently, the metals such as silver, copper, zinc are widely used as antimicrobial component.Think that these metals pass through its ion pair bacterium
Deng cell in organized enzyme work and have the function of prevent bacterial multiplication.
The concentration of antimicrobial component needed for preventing the bacterial multiplication is indicated with minimum inhibitory concentration (MIC), it is however generally that, In
In the case where antimicrobial component containing silver, for example, being about 200ppm to the MIC of Escherichia coli.
In order to which what is to ware or enamelware endowing antibacterial, be currently known is using comprising silver, silver oxide, copper, oxygen
Change the method for the glaze of copper, zinc, the metals such as zinc oxide or metal oxide, and actual embodiment (referring for example to patent document 1
~3 etc.).
In order to assign good antibiotic property to these wares or enamelware, the metal for needing to make silver etc. that there is antibiotic property
Or metal oxide is evenly dispersed in the glaze layer for being formed in the surface of ware or enamelware, and make these metals or
Metal oxide dissolves out on the surface of ware or enamelware.
For example, proposing will make as method of the silver ion effectively in the dissolution of the surface of ware or enamelware is made
Material obtained from phosphate composition coexists with Ag-containing compound is used for the scheme of ware or enamel glaze etc. (referring for example to special
Sharp document 4).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-340513 bulletin
Patent document 2: Japanese Unexamined Patent Publication 7-196384 bulletin
Patent document 3: Japanese Unexamined Patent Publication 7-268652 bulletin
Patent document 4: Japanese Unexamined Patent Publication 11-001380 bulletin
Summary of the invention
Problems to be solved by the invention
Use contain silver or silver compound and form glaze layer as the glaze of antibacterial agent in the case where, in order to make by silver-colored or
Silver compound bring antibiotic property displays, for example, needing to make the silver in the surface of glaze layer dense for Escherichia coli
Degree is about 50ppm~about 200ppm (minimum inhibitory concentration (MIC)).The silver concentration in surface in order to make glaze layer is in the range
It is interior, it is said by reason, as long as addition is calculated as the silver of the mass % of about 0.01 mass %~about 0.02 relative to glaze total amount with silver conversion
Or silver compound.But in fact, lead to glaze because the evaporation of silver-colored ingredient or silver-colored ingredient are spread etc. to the substrate of ware
Silver content contained in the bed of material is greatly decreased than the amount of cooperation.Therefore, in order to make glaze layer show scheduled antibiotic property, phase is needed
Silver is been considerably cooperated for glaze, the problem of accordingly, there exist increased costs.
The present invention has been made in view of the above-described circumstances, even if it is intended that providing using compared with the past a small amount of
Silver or silver compound also can be improved the anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles of antibiotic property.
The method for solving problem
The present inventor is concentrated on studies to solve the above-mentioned problems, as a result, it has been found that, if be made containing aluminium powder with
The content containing aluminium powder in the mixture of phosphate glass powder with silver conversion be calculated as 5 mass % or more and 60 mass % with
Under, and the mass ratio i.e. A/P of the silver (A) contained in said mixture and phosphate glass (P) are 0.05 or more and 1.5 or less
Anti-bacterial composition, then in the antibiotic property glaze compositions for being added to the anti-bacterial composition, using compared with the past few
The silver or silver compound of amount can be shown than previous better antibiotic property, so as to complete the present invention.
That is, anti-bacterial composition of the invention, which is characterized in that contain aluminium powder and phosphate glass powder, it is above-mentioned
The above-mentioned content containing aluminium powder in mixture is calculated as 5 mass % or more and 60 mass % hereinafter, said mixture with silver conversion
In the mass ratio i.e. A/P of the silver (A) that contains and phosphate glass (P) be 0.05 or more and 1.5 or less.
Antibiotic property glaze compositions of the invention, which is characterized in that containing anti-bacterial composition and glaze of the invention, on
The content for stating anti-bacterial composition is calculated as 0.01 mass % or more and 3 mass % or less relative to above-mentioned glaze with silver conversion.
Antibacterial articles of the invention, which is characterized in that form overlay film using antibiotic property glaze compositions of the invention.
Invention effect
Anti-bacterial composition according to the present invention, due to the argentiferous in the mixture containing aluminium powder and phosphate glass powder
The content of powder 5 mass % or more are calculated as and 60 mass % with silver conversion hereinafter, and the silver (A) that contains in said mixture with
Mass ratio, that is, A/P of phosphate glass (P) is 0.05 or more and 1.5 hereinafter, therefore, can be improved antibiotic property, and can subtract
The content of few silver or silver compound.
Antibiotic property glaze compositions according to the present invention, due to containing anti-bacterial composition and glaze of the invention, and
The content of anti-bacterial composition is set to be calculated as 0.01 mass % or more and 3 mass % hereinafter, therefore with silver conversion relative to glaze, energy
The antibiotic property of antibiotic property glaze compositions is enough improved, and the content of silver or silver compound can be reduced.
Antibacterial articles according to the present invention, due to forming overlay film using antibiotic property glaze compositions of the invention,
It can be improved the antibiotic property on the surface of antibacterial articles, and the content of silver or silver compound can be reduced.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) image for indicating the anti-bacterial composition of the embodiment of the present invention 1.
Fig. 2 is reflective electron composition (COMPO) image for indicating the anti-bacterial composition of the embodiment of the present invention 1.
Specific embodiment
The embodiment of anti-bacterial composition of the invention and antibiotic property glaze compositions and antibacterial articles is carried out
Explanation.
It should be noted which is the purport invented in order to better understand and is specifically described, as long as not having
It specifies, is not intended to limit the present invention.
[anti-bacterial composition]
The anti-bacterial composition of present embodiment includes the mixture containing aluminium powder Yu phosphate glass powder, above-mentioned mixing
The content containing aluminium powder in object with silver conversion is calculated as 5 mass % or more and 60 mass % hereinafter, containing in said mixture
Mass ratio, that is, A/P of silver-colored (A) and phosphate glass (P) are 0.05 or more and 1.5 or less.
In the anti-bacterial composition of present embodiment, contain silver powder in the mixture containing aluminium powder and phosphate glass powder
The content of body 5 mass % or more are calculated as and 60 mass % with silver conversion hereinafter, preferably 10 mass % or more and 40 mass % with
Under.
The content containing aluminium powder in mixture containing aluminium powder and phosphate glass powder is in terms of silver conversion less than 5 matter
It is good in order to show the overlay film (glaze layer) formed using the antibiotic property glaze compositions comprising anti-bacterial composition when measuring %
Good antibiotic property, additive amount of the anti-bacterial composition in antibiotic property glaze compositions increase, it is possible to intensity, gloss, face
The original film quality of color etc overlay film has an impact.On the other hand, containing aluminium powder and containing in the mixture of phosphate glass powder
The content of aluminium powder in terms of silver conversion more than 60 mass % when, the content of the phosphate glass powder in anti-bacterial composition subtracts
It is few, therefore, according to the relationship of aftermentioned silver and the mass ratio of phosphate glass, by the antibiotic property glaze comprising anti-bacterial composition
Composition is coated in the roasting process behind the surface of ware or enamelware, is unable to get for inhibiting by evaporation/diffusion
The good effect of the loss of caused silver.
In the anti-bacterial composition of present embodiment, containing the silver contained in aluminium powder and the mixture of phosphate glass powder
It (A) is 0.05 or more and 1.5 with the mass ratio, that is, A/P of phosphate glass (P) hereinafter, preferably 0.15 or more and 1 or less.
The quality of the silver (A) and phosphate glass (P) that contain in the mixture containing aluminium powder and phosphate glass powder
Than be A/P less than 0.05 when, the absolute magnitude of the silver contained in anti-bacterial composition is few, therefore, in order to make using comprising antibiotic property
The overlay film that the antibiotic property glaze compositions of composition are formed shows good antibiotic property, and anti-bacterial composition is in antibiotic property glaze
Additive amount in composition increases, and the amount of the phosphate glass contained in antibiotic property glaze compositions increases.It should be noted that
Phosphate glass has with silica (SiO2) as split-phase in the glaze of principal component, inclining to emersion on the surface
To therefore, when the amount of the phosphate glass contained in antibiotic property glaze compositions is excessive, it is possible to it is outer that glaze layer albefaction etc. occur
Unfavorable condition in sight, or adverse effect is brought to the flatness on the surface of glaze layer.On the other hand, contain aluminium powder and phosphoric acid
It, cannot be with phosphorus when the mass ratio i.e. A/P of the silver (A) and phosphate glass (P) that contain in the mixture of salt glass powder is more than 1.5
The silver ion (Ag+) of silicate glass bonding increases, and will include the antibiotic property glaze compositions coating of anti-bacterial composition therefore
In roasting process behind the surface of ware or enamelware, the effect of loss silver-colored as caused by evaporation/diffusion is inhibited to become
It obtains insufficient.
Then, to the ingredient of the anti-bacterial composition as present embodiment containing aluminium powder and phosphate glass powder into
Row explanation.
" containing aluminium powder "
Containing aluminium powder preferably include selected from silver, silver orthophosphate, silver oxide, silver carbonate, silver nitrate, silver chlorate, silver sulfide with
And the powder of at least one of group of silver acetate, more preferably comprising in the group selected from silver, silver orthophosphate and silver oxide extremely
A kind of few powder.
BET specific surface area containing aluminium powder is preferably 0.2m2/ g or more, more preferably 0.3m2/ g or more, further preferably
For 0.4m2/ g or more and 2.5m2/ g or less.
The anti-bacterial composition of present embodiment, by being 0.2m containing BET specific surface area2/ g's or more contains aluminium powder,
Secondary aggregate easy to form containing aluminium powder Yu phosphate glass powder, to anti-bacterial composition or the combination of antibiotic property glaze
During object is roasted, silver ion increases with the probability that interaction (being bonded/split-phase) occurs for phosphate glass.As it
As a result, the effect of the loss of the silver as caused by evaporating, spread and the silver ion as caused by the split-phase of phosphate glass is inhibited to exist
The effect of the localization on overlay film surface improves, and the overlay film comprising antibiotic property glaze compositions can show excellent antibiotic property.
On the other hand, the BET specific surface area containing aluminium powder is less than 0.2m2When/g, it is difficult to be formed and contain aluminium powder and phosphate
The secondary aggregate of glass powder is also easy to become fragile and destroy even if forming secondary aggregate.Therefore, in preparation antibiotic property glaze
When feed composition, it is separately present containing aluminium powder with phosphate glass powder in glaze, to anti-bacterial composition or antibiotic property
When glaze compositions are roasted, silver ion is difficult to be bonded with phosphate glass, and the effect of diffusion, the evaporation of silver is inhibited to become not
Sufficiently.
Here, secondary aggregate refers to the particle (offspring) of following state, the state are as follows: at least one contains silver powder
The primary particle of body and the primary particle of at least one phosphate glass powder are non-total by electrostatic interaction, Van der Waals force etc.
The state that valence link interaction merges；Or geometry due to due to the shock when the mixing between particle of interparticle surface
Gluing is to making interface be fixed, gluing between particle and the state gathered.
The index of size as secondary aggregate can enumerate the average grain diameter of anti-bacterial composition.Present embodiment
Anti-bacterial composition by the average grain diameter (median particle diameter) of laser diffraction/Opticolor method measurement be preferably 50 μm hereinafter,
More preferably 1 μm or more and 20 μm or less.
In addition, the size of secondary aggregate can also directly be observed by scanning electron microscope (SEM) etc..Second Aggregation
The longest width of body is preferably 100 μm hereinafter, more preferably 50 μm or less.It should be noted that the most length and width of secondary aggregate
Degree is the width for reaching longest direction from the length of one end to the other end of secondary aggregate (unsetting).
In anti-bacterial composition, the average grain diameter (median particle diameter) of secondary aggregate is more than 50 μm or Second Aggregation
When the longest width of body is more than that coarse secondary aggregate as 100 μm increases, to the film comprising antibiotic property glaze compositions
When being roasted and forming the overlay film comprising antibiotic property glaze compositions, the split-phase of the phosphate glass of silver ion rich in
Size increase, and the split-phase in antibiotic property glaze compositions number reduce, therefore, including antibiotic property glaze compositions
Overlay film surface in the distribution of silver ion become unevenly, which is possible to be unable to get stable antibiotic property.
" phosphate glass powder "
In phosphate glass powder, as the ingredient that the oxide using fluorescent X-ray measuring method converts, five are preferably comprised
Aoxidize two phosphorus (P2O5), aluminium oxide (Al2O3) and selected from sodium oxide molybdena (Na2) and potassium oxide (K O2O in) at least any one.
P in phosphate glass powder, as the ingredient that the oxide using fluorescent X-ray measuring method converts2O5Content
For 25 mass % or more and 60 mass % hereinafter, preferably 30 mass % or more and 50 mass % or less.
P2O5Content less than 25 mass % when, the amount of the silver ion being bonded with phosphate glass is reduced, and inhibits the expansion of silver
It dissipates, the effect of evaporation becomes inadequate.On the other hand, P2O5Content when being more than 60 mass %, using including anti-bacterial composition
Antibiotic property glaze compositions overlay film is formed on the surface of ware or enamelware and in the case where make antibacterial articles,
Overlay film is easy to separate from antibacterial articles, therefore, it is possible to which the appearance and flatness to antibacterial articles bring adverse effect.
Al in phosphate glass powder, as the ingredient that the oxide using fluorescent X-ray measuring method converts2O3Contain
Amount is 10 mass % or more and 35 mass % are hereinafter, preferably 20 mass % or more and 30 mass % or less.
Phosphate glass powder passes through P2O5With Al2O3Bonding and form tridimensional network.Due to only P2O5When formed
The condensed phosphate of straight-chain and it is water-soluble.Therefore, in phosphate glass powder, Al2O3Content less than 10 mass % when,
The condensed phosphate of straight-chain increases, therefore, using the antibiotic property glaze compositions comprising anti-bacterial composition in ware or
Overlay film is formed on the surface of enamelware in the case where making antibacterial articles, the water resistance of antibacterial articles is deteriorated, and is having
In use, silver is dissolved out from overlay film in the environment of water, it is possible to be difficult to show permanent antibiotic property.On the other hand, Al2O3's
When content is more than 35 mass %, the reduction of the meltability of phosphate glass when due to roasting and Al2O3Precipitation, give antibiotic property
Reduction and the flatness of glaze layer surface affect.
In phosphate glass powder, Na is selected from as the ingredient for utilizing the oxide of fluorescent X-ray measuring method to convert2O
And K2At least content of any one in O, i.e. by Na2O and K2Total content that O is merged be 10 mass % or more and
35 mass % are hereinafter, preferably 18 mass % or more and 28 mass % or less.
Na2O and K2When the content of O is less than 10 mass %, sodium ion that silver ion is not contained in phosphate glass powder
(Na+) it is replaced with potassium ion (K+) with full amount, therefore, the amount for the silver ion being bonded with phosphate glass is reduced, and inhibits silver
Diffusion, evaporation effect become inadequate.On the other hand, Na2O and K2When the content of O is more than 35 mass %, in preparation antibacterial
In the case where property glaze compositions, the amount of dissolution of alkaline components increases, and has an impact to the viscosity of antibiotic property glaze compositions, has
Adverse effect may be brought to coating.
In the above-mentioned secondary aggregate containing aluminium powder and phosphate glass powder, being averaged for phosphate glass powder is primary
Partial size is preferably 20 μm hereinafter, more preferably 5 μm or less.
When the average primary particle diameter of phosphate glass powder is more than 20 μm, it is difficult to be formed and contain aluminium powder and phosphate glass powder
The secondary aggregate of body is also easy to become fragile and destroy even if forming secondary aggregate.Therefore, in preparation antibiotic property glaze combination
When object, it is separately present containing aluminium powder with phosphate glass powder in glaze, to anti-bacterial composition or antibiotic property glaze group
When conjunction object is roasted, silver ion is difficult to be bonded with phosphate glass, and the effect of diffusion, the evaporation of silver is inhibited to become inadequate.
In the anti-bacterial composition of present embodiment, the softening point of preferably phosphate glass powder is lower than molten containing aluminium powder
Point.In the case where the softening point of phosphate glass powder is higher than the fusing point containing aluminium powder, to anti-bacterial composition or antibiotic property
During glaze compositions are roasted, the silver melted first is until softening ability and phosphate glass occur for phosphate glass
Bonding, therefore, can due to evaporation, diffusion and lose.
The anti-bacterial composition of present embodiment, other than containing aluminium powder and phosphate glass powder, in order to adjust roasting
Meltability etc. when burning can also contain glass powder, mineral dust, metal oxide, metal salt compound, phosphorus as needed
Hydrochlorate etc..
[manufacturing method of anti-bacterial composition]
The manufacturing method of the anti-bacterial composition of present embodiment is to mix phosphate glass powder with containing aluminium powder
The manufacturing method of method, phosphate glass powder can be using the glass powder (sintered glass (fritted usually carried out
Glass manufacturing method etc.)).
Mixed method containing aluminium powder and phosphate glass powder is not particularly limited, in order to largely generate containing aluminium powder with
The secondary aggregate of phosphate glass powder preferably generates between appropriate Impact energy, particle between particle in mixing
The mixed method of strong impact force and shearing force does not preferably occur for the high mixed method of collision frequency.Strong impact force and
When shearing force plays a role, destruction is likely to occur by the secondary aggregate formed containing aluminium powder and phosphate glass powder body.Separately
Outside, in incorporation time length, the mixed method that high frictional heat occurs, secondary aggregate is possible to thicker big, therefore not preferably.
It as such mixed method, can enumerate for example: the container rotating types such as cone-type mixer mixing machine, ribbon mixing
The mixing impellers type such as device mixing machine, fluidized bed type mixing machine.
Using in the mixing containing aluminium powder and phosphate glass powder of above-mentioned mixed method, incorporation time is preferably 1 small
When more than and less than 100 hours.
In short-term, admixture is possible to become uneven incorporation time.On the other hand, it when incorporation time is long, generates coarse
Aggregation, the distribution of the silver ion of glaze layer surface becomes unevenly, and antibiotic property is possible to become unstable.
By that can be obtained above comprising the mixture containing aluminium powder and phosphate glass powder, the argentiferous in said mixture
The silver (A) and phosphoric acid that the content of powder is calculated as 5 mass % or more and 60 mass % or less, is contained in said mixture with silver conversion
Mass ratio, that is, A/P of salt glass (P) be it is 0.05 or more and 1.5 below, average grain diameter is 50 μm of anti-bacterial compositions below.
[antibiotic property glaze compositions]
The antibiotic property glaze compositions of present embodiment are anti-bacterial composition and glaze containing above-mentioned present embodiment
Antibiotic property glaze compositions obtained from material, the content of anti-bacterial composition preferably 0.01 matter in terms of silver conversion relative to glaze
% or more and 3 mass % are measured hereinafter, more preferably 0.05 mass % or more and 1.5 mass % or less.
Here, the content of anti-bacterial composition is made to be calculated as 0.01 mass % or more and 3 matter relative to glaze with silver conversion
Measure % it is below reason for this is that, the content of anti-bacterial composition in terms of silver conversion less than 0.01 mass % when, anti-bacterial composition
In the amount of silver that contains it is very few, antibiotic property reduces, as a result, desired antibiotic property can not be shown, combines as antibiotic property
The antibiotic property of object reduces, therefore not preferably.On the other hand, the content of anti-bacterial composition by silver conversion in terms of more than 3 mass % when,
Containing silver to desired antibiotic property or more is shown, most of silver are wasted, therefore not preferably.
The antibiotic property glaze compositions of present embodiment, in addition to the anti-bacterial composition and glaze of above-mentioned present embodiment
In addition, the auxiliary agents such as inorganic powders, thickener, the dispersing agents such as glass powder, mineral dust can also be contained.
The antibiotic property glaze compositions of present embodiment, which pass through, is calculated as 0.01 mass % containing converting relative to glaze with silver
Above and the anti-bacterial composition of 3 mass % present embodiments below, can be to glaze endowing antibacterial, and can reduce
The content of silver or silver compound.
Therefore, it is formed by being coated with the antibiotic property glaze compositions of present embodiment on ceramic product or enamelware
Film, and the film is heat-treated, overlay film (glaze layer) is consequently formed, ceramic product or enamelware can be assigned
Antibiotic property.
The antibiotic property glaze compositions of present embodiment are relative to pottery chinaware product or the coating film thickness (film of enamelware
Thickness) be preferably 10 μm more than and less than 1000 μm.When the coating film thickness of antibiotic property glaze compositions is less than 10 μm, it is difficult to
The formation uniformly over the surface of pottery chinaware product or enamelware includes the overlay film of antibiotic property glaze compositions, it is possible in antibacterial
Property show aspect generate it is uneven.On the other hand, when the coating film thickness of antibiotic property glaze compositions is 1000 μm or more, antibiotic property
The usage amount of glaze compositions increases, and therefore, cost increases, economically not preferably.
[antibacterial articles]
The antibacterial articles of present embodiment are to form overlay film (glaze using the antibiotic property glaze compositions of present embodiment
Layer) article, as these articles, can enumerate be should guard against as caused by bacterium in washroom, lavatory, kitchen, bathroom etc.
Used in the field that the place of pollution or hospital, food processing facilities, communal facility etc. need that life is protected to threaten from bacterium
Article, such as: ceramic products, the container such as health pottery tool, container, tableware, ceramic tile, pottery, cooker, electric product, are built panel
The enamelwares such as material component.
By the antibiotic property glaze compositions using present embodiment on these ceramic products or enamelware surface
At least necessary position forms overlay film, can be improved the antibiotic property of the article surface, and can reduce silver-colored or silver compound
Content.
The overlay film formed on the surface of pottery chinaware product or enamelware can be single layer, or two layers or more,
But it is preferred that making the overlay film formed using the antibiotic property glaze compositions of present embodiment as outermost layer.Do not make to utilize this reality
The overlay film of antibiotic property glaze compositions formation of mode is applied as in outermost situation, silver ion is difficult to be present in the table of overlay film
Face, it is possible to be difficult to show by silver-colored bring antibiotic property.
As described above, anti-bacterial composition according to the present embodiment, due to comprising containing aluminium powder and phosphate
The mixture of glass powder, the content containing aluminium powder in said mixture are calculated as 5 mass % or more and 60 matter with silver conversion
Amount % hereinafter, and the mass ratio i.e. A/P of the silver (A) that contains in said mixture and phosphate glass (P) be 0.05 or more and
Therefore 1.5 hereinafter, can be improved antibiotic property, and can reduce the content of silver or silver compound.
Glaze will be added to comprising the above-mentioned anti-bacterial composition containing aluminium powder and the mixture of above-mentioned phosphate glass powder
When being roasted in material, in roasting process, the monovalent cation (for example, Na+, K+) in silver ion and phosphate glass is carried out
Displacement, silver ion is bonded with phosphate glass, therefore, is able to suppress evaporation due to silver-colored ingredient or silver ingredient to ware
Silver-colored loss caused by diffusion in substrate (biscuit).That is, silver ion in order to be bonded with phosphate glass, needs and phosphate
Monovalent cation in glass is replaced.More than divalent cation (for example, Ca2+) is due to strong with phosphate glass
In conjunction with, thus be difficult to replace with silver ion.Therefore, in the anti-bacterial composition of present embodiment, preferably phosphate glass powder
Contain the monovalent cations such as a certain amount of above Na+, K+.
The anti-bacterial composition of present embodiment is led by evaporating or diffusing for silver-colored ingredient as described above in addition to being able to suppress
Cause silver loss except, moreover, because phosphate glass in the glaze using silica as principal component interior contracted payment and send out
Phase estranged, and the thermal expansion coefficient of phosphate glass is big, light specific gravity when roasting, therefore, using including antibiotic property glaze
The surface of the overlay film of composition is nearby easy the phenomenon that localization, and the amount of the silver on the surface of the overlay film can be made to increase.It is as a result,
Make to reduce the additive amount of silver or silver compound into anti-bacterial composition, anti-bacterial composition can also show antibiotic property.
In order to fully play above-mentioned effect, the mixing ratio containing aluminium powder and phosphate glass powder is critically important.Antibacterial
In property composition, in the case where the content containing aluminium powder is more than phosphate glass powder, the key of silver ion and phosphate glass
Brought by closing, inhibit to be become inadequate by the effect of the loss for evaporating or diffusing caused silver of silver-colored ingredient.On the other hand, resist
In bacterium property composition, in the case where the content containing aluminium powder is fewer than phosphate glass powder, in anti-bacterial composition silver
Content is few, therefore, in order to make the antibiotic property glaze compositions containing anti-bacterial composition and glaze show antibiotic property, it is necessary to
Antibacterial agent is largely added in the antibiotic property glaze compositions, the phosphate glass concentration in antibiotic property glaze compositions increases.Such as
Upper described, in the glaze using silica as principal component split-phase occurs for phosphate glass, has and is including antibiotic property glaze
The tendency of the surface colocalization of the overlay film of composition, therefore, the content of the phosphate glass in antibiotic property glaze compositions is more
When, it is possible to the apparent unfavorable conditions such as the overlay film albefaction comprising antibiotic property glaze compositions, or the table to overlay film occurs
The flatness in face brings adverse effect.
In addition, phosphate glass has the tendency that split-phase occurs in the glaze using silica as principal component, dividing
Silver ion is concentrated in phase.In addition, the thermal expansion coefficient due to phosphate glass is big, specific gravity lightens at high temperature, therefore, in split-phase
Phosphate glass after the concentration of middle silver ion has to float tendency out in glaze layer surface.As a result, in glaze layer surface
The amount of silver ion increase.
Due to above effect, the anti-bacterial composition of present embodiment can be to close than previous lesser amount of silver or patina
The use level of object shows excellent antibiotic property.
Since coordination bonding occurs for condensed phosphate (polymer of phosphoric acid) and metal ion, it can be used as water process
The agent for capturing of the metal ion of agent etc. utilizes.Condensed phosphate does not have water resistance, but contains the phosphate of aluminium oxide in structure
Glass forms tridimensional network.In addition, aluminium enters in the reticular structure of phosphate glass, phosphate glass is by charge as a result,
Neutrality is remained, therefore, the double bond of phosphate glass is opened, and the structure of phosphate glass becomes close, and therefore, present embodiment resists
The water resistance of bacterium property composition improves.
The anti-bacterial composition of present embodiment is suitable for health pottery tool or enamelware, and therefore, water resistance is emphasis.Cause
This, the phosphate glass in the anti-bacterial composition of present embodiment needs to contain aluminium in the structure.
In addition, forming Second Aggregation containing aluminium powder and phosphate glass powder body in the anti-bacterial composition of present embodiment
Body adjoins each other presence containing aluminium powder and phosphate glass powder, as a result, in the roasting process of antibiotic property glaze compositions,
The probability that silver ion is bonded with phosphate glass improves.
Antibiotic property glaze compositions according to the present embodiment, due to anti-bacterial composition and glaze containing present embodiment
Material, and make the content of the anti-bacterial composition relative to glaze with silver conversion be calculated as 0.01 mass % or more and 3 mass % with
Under, therefore, it can be improved the antibiotic property of antibiotic property glaze compositions, and the content of silver or silver compound can be reduced.
Antibacterial articles according to the present embodiment, since the antibiotic property glaze compositions formation using present embodiment is covered
Therefore film can be improved the antibiotic property on the surface of the antibacterial articles, and can reduce the content of silver or silver compound.
Embodiment
Hereinafter, being more specifically illustrated by embodiment and comparative example to the present invention, but the present invention is not limited to following
Embodiment.
[embodiment 1]
" production of anti-bacterial composition "
It will be 0.6m as the BET specific surface area containing aluminium powder2The silver of/g: the phosphorus of ingredient is shown in 35 mass parts and table 1
Silicate glass powder A:65 mass parts are put into container rotating type mixing machine, are mixed 3 hours, are obtained by containing aluminium powder and phosphate
The anti-bacterial composition for the embodiment 1 that the mixture of glass powder A is constituted.
" measurement of average grain diameter "
Anti-bacterial composition is suspended in water, using laser diffraction/scattering formula particle diameter distribution meter (trade name: LA-920,
Ku Chang manufacturing company system), measure the average grain diameter (median particle diameter) of anti-bacterial composition.
Show the results of the evaluation table 2.
" confirmation of secondary aggregate "
The presence or absence of anti-bacterial composition, confirmation secondary aggregate are observed by scanning electron microscope (SEM).
In addition, measuring the longest width (μm) of secondary aggregate by scanning electron microscope (SEM).
Show the results of the evaluation table 2.In addition, scanning electron microscope (SEM) image of anti-bacterial composition is shown in figure
1.Reflective electron composition (COMPO) image of anti-bacterial composition is shown in Fig. 2.It should be noted that scanning electron microscope
Image keeps the shape of measuring object clear.In addition, reflective electron composition image be to reflective electron picture carry out image procossing and
It obtains, according to the ingredient of measuring object, the brightness of image is different, and the bigger atom serial number the brighter.
In Fig. 1, partial size is small and the glomerate particle of shape is containing aluminium powder, and partial size is big and is phosphorus without the glomerate particle of shape
Silicate glass powder A.In Fig. 2, bright (partially white) particle is containing aluminium powder, and the particle of dark (partially black) is phosphate glass powder A.
" production of antibiotic property glaze compositions "
As glaze raw material, the glaze raw material with following compositions is used.
SiO2: 60 mass %
Al2O3: 13 mass %
CO2: 10 mass %
CaO:11 mass %
ZnO:1 mass %
K2O:3 mass %
Na2O:2 mass %
By in 60 mass parts of glaze raw material and 40 mass parts of water investment ball mill, after crushing 15 hours, add above-mentioned anti-
Bacterium property composition makes it reach 0.30 mass % relative to glaze raw material in terms of silver conversion, and further mixing 1 hour, is implemented
The antibiotic property glaze compositions of example 1.
" production of antibiotic property pottery chinaware plate "
Prepare long 50mm × wide 50mm × thickness 5mm ware plate, with 1000g/m on the ware plate2Coating weight
It sprays above-mentioned antibiotic property glaze compositions and, roasting temperature 1 hour of 1200 DEG C, obtains the antibiotic property of embodiment 1 after dry
Ware plate.
" the antibiotic property evaluation of antibiotic property pottery chinaware plate "
In order to confirm water resistance, above-mentioned antibiotic property pottery chinaware plate is impregnated 16 hours in 50 DEG C of water.Then, with Japan
Industrial standard JIS Z 2801 " antibacterial fabricated product-antibiotic property test method and antibacterial effect " evaluates antibiotic property pottery chinaware plate
Antibiotic property finds out antibacterial activity value by calculating formula below.
Antibacterial activity value (R)=(Ut-U0)-(At-U0)=Ut-At
U0: the average value of the logarithm of the viable count after the rigid inoculation of undressed test film
Ut: the average value of the logarithm of the viable count behind 24 hours of undressed test film
At: the average value of the logarithm of the viable count behind 24 hours of antibacterial processing experiment piece
Here, tested with regard to Escherichia coli and staphylococcus aureus, have rated that whether there is or not antibiotic properties to two kinds of bacteriums
Energy.Evaluation is carried out according to Japanese Industrial Standards JIS Z 2801 " antibacterial fabricated product-antibiotic property test method and antibacterial effect ",
Antibacterial activity value to both Escherichia coli and staphylococcus aureus is evaluated as qualification when being 2.0 or more, to Escherichia coli
And the antibacterial activity value of any one in staphylococcus aureus or both be lower than 2.0 when be evaluated as it is unqualified.
Show the results of the evaluation table 2.
" ocular estimate of antibiotic property pottery chinaware plate "
About obtained antibiotic property pottery chinaware plate appearance, by with coating do not contain anti-bacterial composition glaze
The visual inspection Check of the pottery chinaware plate roasted afterwards, the presence or absence of confirmation discoloration, bumps, foreign matter precipitation, bubble etc., it will be observed that aobvious
The case where bad order of work, is set as unqualified.
Show the results of the evaluation table 2.
[embodiment 2]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 25 mass parts, phosphate glass powder A:75 mass
Other than part, other are operated similarly to Example 1, make the anti-bacterial composition of embodiment 2.
It for the anti-bacterial composition of embodiment 2, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 2 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 2, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 3]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 15 mass parts, phosphate glass powder A:85 mass
Other than part, other are operated similarly to Example 1, make the anti-bacterial composition of embodiment 3.
It for the anti-bacterial composition of embodiment 3, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 3 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 3, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 4]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 45 mass parts, phosphate glass powder A:55 mass
Other than part, other are operated similarly to Example 1, make the anti-bacterial composition of embodiment 4.
It for the anti-bacterial composition of embodiment 4, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 4 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 4, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 5]
It is 0.3m in addition to using BET specific surface area2As containing other than aluminium powder, other are grasped the silver of/g similarly to Example 1
Make, makes the anti-bacterial composition of embodiment 5.
It for the anti-bacterial composition of embodiment 5, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 5 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 5, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 6]
It is 2.0m in addition to using BET specific surface area2The silver orthophosphate of/g is used as containing other than aluminium powder, other are same with embodiment 1
Sample operation, makes the anti-bacterial composition of embodiment 6.
It for the anti-bacterial composition of embodiment 6, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 6 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 6, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 7]
It is 1.5m in addition to using BET specific surface area2The silver oxide of/g is used as containing other than aluminium powder, other are same with embodiment 1
Sample operation, makes the anti-bacterial composition of embodiment 7.
It for the anti-bacterial composition of embodiment 7, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 7 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 7, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 8]
In addition to use shown in table 1 ingredient phosphate glass powder B replace phosphate glass powder A other than, other with
Embodiment 1 equally operates, and makes the anti-bacterial composition of embodiment 8.
It for the anti-bacterial composition of embodiment 8, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 8 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 8, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 9]
In addition to use shown in table 1 ingredient phosphate glass powder C replace phosphate glass powder A other than, other with
Embodiment 1 equally operates, and makes the anti-bacterial composition of embodiment 9.
It for the anti-bacterial composition of embodiment 9, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, operating similarly to Example 1, the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 9 are made
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 9, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 10]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 60 mass parts, phosphate glass powder A:40 mass
Other than part, other are operated similarly to Example 1, make the anti-bacterial composition of embodiment 10.
It for the anti-bacterial composition of embodiment 10, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, making it reach 2.5 matter relative to glaze raw material in terms of silver conversion in addition to adding above-mentioned anti-bacterial composition
It measures other than %, other are operated similarly to Example 1, make the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 10
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 10, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[embodiment 11]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 5 mass parts, phosphate glass powder A:95 mass
Other than part, other are operated similarly to Example 1, make the anti-bacterial composition of embodiment 11.
It for the anti-bacterial composition of embodiment 11, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 2.
In addition, making it reach 0.05 matter relative to glaze raw material in terms of silver conversion in addition to adding above-mentioned anti-bacterial composition
It measures other than %, other are operated similarly to Example 1, make the antibiotic property glaze compositions and antibiotic property pottery chinaware of embodiment 11
Plate.
It for the antibiotic property pottery chinaware plate of embodiment 11, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 2.
[comparative example 1]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 3 mass parts, phosphate glass powder A:97 mass
Other than part, other are operated similarly to Example 1, the anti-bacterial composition of comparison example 1.
It for the anti-bacterial composition of comparative example 1, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 1
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 1, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 2]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 70 mass parts, phosphate glass powder A:30 mass
Other than part, other are operated similarly to Example 1, the anti-bacterial composition of comparison example 2.
It for the anti-bacterial composition of comparative example 2, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 2
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 2, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 3]
In addition to use shown in table 1 ingredient phosphate glass powder D replace phosphate glass powder A other than, other with
Embodiment 1 equally operates, the anti-bacterial composition of comparison example 3.
It for the anti-bacterial composition of comparative example 3, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 3
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 3, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 4]
In addition to use shown in table 1 ingredient phosphate glass powder E replace phosphate glass powder A other than, other with
Embodiment 1 equally operates, the anti-bacterial composition of comparison example 4.
It for the anti-bacterial composition of comparative example 4, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 4
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 4, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 5]
In addition to use shown in table 1 ingredient phosphate glass powder F replace phosphate glass powder A other than, other with
Embodiment 1 equally operates, the anti-bacterial composition of comparison example 4.
It for the anti-bacterial composition of comparative example 5, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 5
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 5, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 6]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 5 mass parts, phosphate glass powder A:95 mass
Other than part, other are operated similarly to Example 1, the anti-bacterial composition of comparison example 6.
It for the anti-bacterial composition of comparative example 6, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, making it reach 0.005 matter relative to glaze raw material in terms of silver conversion in addition to adding above-mentioned anti-bacterial composition
It measures other than %, other are operated similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 6
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 6, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 7]
In addition to making mixing ratio silver of the silver with phosphate glass powder A: 60 mass parts, phosphate glass powder A:40 mass
Other than part, other are operated similarly to Example 1, the anti-bacterial composition of comparison example 7.
It for the anti-bacterial composition of comparative example 7, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, making it reach 6 mass % relative to glaze raw material in terms of silver conversion in addition to adding above-mentioned anti-bacterial composition
In addition, other are operated similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware plate of comparison example 7.
It for the antibiotic property pottery chinaware plate of comparative example 7, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 8]
It is 0.1m in addition to using BET specific surface area2As containing other than aluminium powder, other are grasped the silver of/g similarly to Example 1
Make, the anti-bacterial composition of comparison example 8.
It for the anti-bacterial composition of comparative example 8, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 8
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 8, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
[comparative example 9]
Incorporation time 100 containing aluminium powder and phosphate glass powder A in production in addition to making anti-bacterial composition is small
When other than, other are operated similarly to Example 1, the anti-bacterial composition of comparison example 9.
It for the anti-bacterial composition of comparative example 9, operates similarly to Example 1, carries out the measurement of average grain diameter and secondary
The confirmation of aggregation.Show the results of the evaluation table 3.
In addition, operating similarly to Example 1, antibiotic property glaze compositions and antibiotic property the pottery chinaware of comparison example 9
Plate.
It for the antibiotic property pottery chinaware plate of comparative example 9, operates similarly to Example 1, carries out antibiotic property evaluation and appearance is commented
Valence.Show the results of the evaluation table 3.
As shown in Table 2, the antibiotic property pottery chinaware plate of 1~embodiment of embodiment 11 does not have bad order.In addition may be used
Know, the excellent antibacterial performance of the antibiotic property pottery chinaware plate of 1~embodiment of embodiment 11.
On the other hand, in comparative example 1, the silver content in anti-bacterial composition is 3 mass %, the matter of silver and phosphate glass
Amount is 0.031 than (A/P), and therefore, albefaction occurs for antibiotic property pottery chinaware plate, observes bad order.In addition we know, comparative example 1
Antibiotic property pottery chinaware plate do not have anti-microbial property.
In comparative example 2, the silver content in anti-bacterial composition is 70 mass %, the mass ratio (A/ of silver and phosphate glass
It P) is 2.33, thus, it can be known that antibiotic property pottery chinaware plate does not have anti-microbial property.
In comparative example 3, the P that contains in phosphate glass powder D2O5Amount it is few, therefore, in antibiotic property glaze compositions
In roasting process, inhibit the effect by the loss for evaporating or diffusing caused silver of silver-colored ingredient insufficient, thus, it can be known that antibiotic property
Chinaware plate of making pottery does not have anti-microbial property.
In comparative example 4, the Al that contains in phosphate glass powder E2O3Amount it is few, therefore, water resistance is low, in 50 DEG C of water
At middle dipping 16 hours, silver and P2O5It dissolves out together, thus, it can be known that antibiotic property pottery chinaware plate does not have anti-microbial property.
In comparative example 5, the Na that contains in phosphate glass powder F2O and K2The amount of O is few, and therefore, silver cannot be with phosphate glass
Glass bonding inhibits the loss for evaporating or diffusing caused silver by silver-colored ingredient in the roasting process of antibiotic property glaze compositions
Effect it is insufficient, thus, it can be known that antibiotic property pottery chinaware plate do not have anti-microbial property.
In comparative example 6, silver is 0.005 mass % relative to the content of glaze, thus, it can be known that antibiotic property pottery chinaware plate does not have
There is anti-microbial property.
In comparative example 7, silver is 6 mass % relative to the content of glaze, and therefore, antibiotic property pottery chinaware plate colours, and is seen
Observe bad order.
In comparative example 8, the BET specific surface area containing aluminium powder is 0.1m2/ g, thus, it can be known that antibiotic property pottery chinaware plate does not have
There is antibiotic property,.
In comparative example 9, the average grain diameter of anti-bacterial composition is 65 μm, thus, it can be known that showing in antibiotic property pottery chinaware plate
The region of anti-microbial property is mixed with the region without display anti-microbial property, can not practical application.
Claims (4)
1. a kind of anti-bacterial composition, which is characterized in that
Comprising the mixture containing aluminium powder Yu phosphate glass powder,
The content containing aluminium powder in the mixture 5 mass % or more are calculated as and 60 mass % with silver conversion hereinafter,
The mass ratio i.e. A/P of the silver-colored A that contains in the mixture and phosphate glass P be 0.05 or more and 1.5 hereinafter,
In the phosphate glass powder, as the ingredient that the oxide using fluorescent X-ray measuring method converts, contain 25 matter
Measure % or more and 60 mass % P below2O5, 10 mass % or more and 35 mass % Al below2O3, add up to 10 mass %
Above and 35 mass % are below selected from Na2O and K2In O at least any one,
The anti-bacterial composition include by the secondary aggregate formed containing aluminium powder and the phosphate glass powder body, and
And using the average grain diameter of laser diffraction/Opticolor method measurement be 50 μm hereinafter,
The BET specific surface area containing aluminium powder is 0.2m2/ g or more.
2. anti-bacterial composition as described in claim 1, which is characterized in that the aluminium powder that contains is by selected from silver, silver orthophosphate
The powder constituted at least one of the group of silver oxide.
3. a kind of antibiotic property glaze compositions, which is characterized in that
Containing anti-bacterial composition of any of claims 1 or 2 and glaze,
The content of the anti-bacterial composition relative to the glaze with silver conversion be calculated as 0.01 mass % or more and 3 mass % with
Under.
4. a kind of antibacterial articles, which is characterized in that form overlay film using antibiotic property glaze compositions as claimed in claim 3.
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| CN201410601663.9A CN105613582B (en) | 2014-10-31 | 2014-10-31 | Anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles |
| DE112015004973.8T DE112015004973T5 (en) | 2014-10-31 | 2015-10-09 | Antibacterial composition, antibacterial glaze composition, and antibacterial article |
| PCT/JP2015/078768 WO2016067898A1 (en) | 2014-10-31 | 2015-10-09 | Antibacterial composition, antibacterial glaze composition, and antibacterial article |
| JP2016556483A JP6690542B2 (en) | 2014-10-31 | 2015-10-09 | Antibacterial composition, antibacterial glaze composition, and antibacterial article |
| TW104135356A TWI571498B (en) | 2014-10-31 | 2015-10-28 | Antibacterial composition, antibacterial glaze composition, and antibacterial article |
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| CN201410601663.9A CN105613582B (en) | 2014-10-31 | 2014-10-31 | Anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles |
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| CN105613582A CN105613582A (en) | 2016-06-01 |
| CN105613582B true CN105613582B (en) | 2019-11-22 |
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| JP (1) | JP6690542B2 (en) |
| CN (1) | CN105613582B (en) |
| DE (1) | DE112015004973T5 (en) |
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| CN112830678A (en) * | 2021-01-22 | 2021-05-25 | 深圳市尤佳环境科技有限公司 | Ceramic antibacterial additive, preparation method thereof and ceramic glaze |
| CN113415995B (en) * | 2021-07-14 | 2022-08-05 | 佛山东鹏洁具股份有限公司 | FFC ceramic, antibacterial easy-cleaning glaze thereof, preparation method and application |
| CN114671711B (en) * | 2022-04-19 | 2023-05-23 | 新明珠集团股份有限公司 | Antibacterial rock plate and manufacturing method thereof |
| CN118109013A (en) * | 2023-11-10 | 2024-05-31 | 海信容声(广东)冰箱有限公司 | Modified antibacterial LLDPE material, preparation method thereof and refrigerator |
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| JP3051019B2 (en) * | 1994-04-18 | 2000-06-12 | 住友大阪セメント株式会社 | Antibacterial and antifungal glaze composition and antibacterial and antifungal composition for adding glaze |
| CN1179702A (en) * | 1995-02-02 | 1998-04-22 | 东陶机器株式会社 | Method for preparing antibacterial glaze, antibacterial part and method for preparing part |
| WO1996023412A1 (en) * | 1995-02-02 | 1996-08-08 | Toto Ltd. | Process for producing antibacterial glaze, antibacterial member, and process for producing the member |
| CN1373998A (en) * | 2002-03-28 | 2002-10-16 | 上海维安新材料研究中心有限公司 | Antiseptic glass pellet with slowly released component and its prepn |
| JP2004115422A (en) * | 2002-09-26 | 2004-04-15 | Tadashi Inoue | Inorganic antimicrobial agent, method for producing the same and product containing the same |
| EP1597211A2 (en) * | 2003-02-25 | 2005-11-23 | Schott AG | Antimicrobial phosphate glass |
| JP4293806B2 (en) * | 2003-02-28 | 2009-07-08 | 石塚硝子株式会社 | Antibacterial imparting glass composition and antibacterial polymer composite material using the same |
| JP2004300086A (en) * | 2003-03-31 | 2004-10-28 | Inax Corp | Antimicrobial agent for glaze and method for producing antimicrobial ceramic product |
| JP2005126348A (en) * | 2003-10-22 | 2005-05-19 | National Institute Of Advanced Industrial & Technology | Metal-based inorganic antibacterial and antifungal agent, method for producing the same and use |
| JP5358877B2 (en) * | 2006-10-27 | 2013-12-04 | 住友電気工業株式会社 | Antibacterial ceramic product, ceramic surface treatment agent, and method for manufacturing antibacterial ceramic product |
| CN103145334A (en) * | 2011-12-06 | 2013-06-12 | 住友大阪水泥股份有限公司 | Antibacterial compositions, antibacterial glaze compositions and antimicrobial articles |
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| JP6690542B2 (en) | 2020-04-28 |
| TW201619302A (en) | 2016-06-01 |
| JPWO2016067898A1 (en) | 2017-08-10 |
| WO2016067898A1 (en) | 2016-05-06 |
| TWI571498B (en) | 2017-02-21 |
| DE112015004973T5 (en) | 2017-07-13 |
| CN105613582A (en) | 2016-06-01 |
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