CN105613582A

CN105613582A - Antibacterial composition, antibacterial glaze composition and antibacterial goods

Info

Publication number: CN105613582A
Application number: CN201410601663.9A
Authority: CN
Inventors: 堀越秀纪; 野边正纮; 魏斯毅
Original assignee: Sumitomo Osaka Cement Co Ltd
Current assignee: Sumitomo Osaka Cement Co Ltd
Priority date: 2014-10-31
Filing date: 2014-10-31
Publication date: 2016-06-01
Anticipated expiration: 2034-10-31
Also published as: WO2016067898A1; TW201619302A; JP6690542B2; JPWO2016067898A1; TWI571498B; CN105613582B; DE112015004973T5

Abstract

The invention provides an antibacterial composition, an antibacterial glaze composition and antibacterial goods. The antibacterial composition provided by the invention contains a mixture of silver-bearing powder and phosphate glass powder, wherein the content of the silver-bearing powder in the mixture is higher than 5mass% and lower than 60mass% by silver, and the mass ratio of silver (A) and phosphate glass (P) contained in the mixture, i.e., A/P is greater than 0.05 and smaller than 1.5. According to the antibacterial composition, the antibacterial property can be improved, and the content of silver or silver compounds can be lowered.

Description

Anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles

Technical field

The present invention relates to anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles, especially specifically, relate to being suitable for the building materials such as kitchen articles, ceramic tile such as health pottery tool, medical supplies, enamel articles for use, various container, tableware, the various components of automobile, electrical equipment the various components such as panel, the anti-bacterial composition with excellent antibiotic property and the antibiotic property glaze compositions containing this anti-bacterial composition and glaze and utilize the antibacterial articles of this antibiotic property glaze compositions formation overlay film.

Background technology

At present, as antimicrobial component, widely use the metals such as silver, copper, zinc. Think these metals to be worked by the organized enzyme in the cell of its ion pair antibacterial etc. and have stop bacterial multiplication effect.

The concentration minimum inhibitory concentration (MIC) stoping the antimicrobial component needed for this bacterial multiplication represents, it is however generally that, when containing the antimicrobial component of silver, for instance, it is about 200ppm to colibacillary MIC.

In order to ware or enamelware endowing antibacterial, what be currently known is use the method for glaze comprising the metals such as silver, silver oxide, copper, copper oxide, zinc, zinc oxide or metal-oxide, and actual embodiment (referring for example to patent documentation 1��3 etc.).

In order to give good antibiotic property to these wares or enamelware, need to make silver etc. have the metal of antibiotic property or metal-oxide is evenly dispersed in the glaze layer on the surface being formed at ware or enamelware, and make these metals or metal-oxide in the surface dissolution of ware or enamelware.

Such as, as making silver ion effectively in the method for the surface dissolution of ware or enamelware, it is proposed that the material obtained making phosphate composition and Ag-containing compound coexist is used for the scheme (referring for example to patent documentation 4) of ware or enamel glaze etc.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 6-340513 publication

Patent documentation 2: Japanese Unexamined Patent Publication 7-196384 publication

Patent documentation 3: Japanese Unexamined Patent Publication 7-268652 publication

Patent documentation 4: Japanese Unexamined Patent Publication 11-001380 publication

Summary of the invention

The problem that invention to solve

When use containing silver or silver compound as antibacterial glaze formed glaze layer, in order to make the antibiotic property brought by silver or silver compound display, such as, for escherichia coli, it is necessary to making the silver concentration in the surface of glaze layer is about 50ppm��about 200ppm (minimum inhibitory concentration (MIC)). In order to make the silver concentration in the surface of glaze layer within the scope of this, say by reason, as long as adding the silver or the silver compound that are calculated as about 0.01 mass %��about 0.02 mass % relative to glaze total amount with silver conversion. But, it practice, because to the substrate diffusion of ware etc., silver composition evaporation or silver composition cause that silver amount contained in glaze layer is greatly decreased than the amount coordinated. Therefore, in order to make glaze layer show predetermined antibiotic property, it is necessary to been considerably coordinate silver relative to glaze, accordingly, there exist the problem that cost increases.

The present invention completes in view of the foregoing, its object is to, it is provided that even if using a small amount of silver compared with the past or silver compound also to be able to improve the anti-bacterial composition of antibiotic property and antibiotic property glaze compositions and antibacterial articles.

For the method solving problem

The present inventor has concentrated on studies to solve the problems referred to above, found that, if the content containing aluminium powder in making the mixture containing aluminium powder and phosphate glass powder body is calculated as more than 5 mass % and below 60 mass % with silver conversion, and the mass ratio of the silver contained in said mixture (A) and phosphate glass (P) and the anti-bacterial composition that A/P is more than 0.05 and less than 1.5, then in the antibiotic property glaze compositions that with the addition of this anti-bacterial composition, use a small amount of silver compared with the past or silver compound, better antibiotic property than ever can be shown, thus completing the present invention.

Namely, the anti-bacterial composition of the present invention, it is characterized in that, containing containing aluminium powder and phosphate glass powder body, the above-mentioned content containing aluminium powder in said mixture converts with silver and is calculated as more than 5 mass % and below 60 mass %, and mass ratio and the A/P of the silver contained in said mixture (A) and phosphate glass (P) are more than 0.05 and less than 1.5.

The antibiotic property glaze compositions of the present invention, it is characterised in that anti-bacterial composition containing the present invention and glaze, the content of above-mentioned anti-bacterial composition is calculated as more than 0.01 mass % and below 3 mass % relative to above-mentioned glaze with silver conversion.

The antibacterial articles of the present invention, it is characterised in that utilize the antibiotic property glaze compositions of the present invention to form overlay film.

Invention effect

Anti-bacterial composition according to the present invention, owing to being calculated as more than 5 mass % and below 60 mass % containing the content containing aluminium powder in the mixture of aluminium powder and phosphate glass powder body with silver conversion, and the mass ratio of the silver contained in said mixture (A) and phosphate glass (P) and A/P are more than 0.05 and less than 1.5, therefore, antibiotic property can be improved, and the content of silver or silver compound can be reduced.

Antibiotic property glaze compositions according to the present invention, due to the anti-bacterial composition containing the present invention and glaze, and the content making anti-bacterial composition is calculated as more than 0.01 mass % and below 3 mass % relative to glaze with silver conversion, therefore, the antibiotic property of antibiotic property glaze compositions can be improved, and the content of silver or silver compound can be reduced.

Antibacterial articles according to the present invention, owing to utilizing the antibiotic property glaze compositions of the present invention to form overlay film, therefore, it is possible to improve the antibiotic property on the surface of antibacterial articles, and can reduce the content of silver or silver compound.

Accompanying drawing explanation

Fig. 1 indicates that scanning electron microscope (SEM) image of the anti-bacterial composition of embodiments of the invention 1.

Fig. 2 indicates that reflection electronic composition (COMPO) image of the anti-bacterial composition of embodiments of the invention 1.

Detailed description of the invention

The anti-bacterial composition of the present invention and the embodiment of antibiotic property glaze compositions and antibacterial articles are illustrated.

It should be noted which is to be specifically described to be more fully understood that the purport of invention, as long as no specifying, it is not intended to limit the present invention.

[anti-bacterial composition]

The anti-bacterial composition of present embodiment comprises the mixture containing aluminium powder Yu phosphate glass powder body, the content containing aluminium powder in said mixture converts with silver and is calculated as more than 5 mass % and below 60 mass %, and mass ratio and the A/P of the silver contained in said mixture (A) and phosphate glass (P) are more than 0.05 and less than 1.5.

In the anti-bacterial composition of present embodiment, the content containing aluminium powder in mixture containing aluminium powder and phosphate glass powder body is calculated as more than 5 mass % and below 60 mass % with silver conversion, it is preferred to more than 10 mass % and below 40 mass %.

When the content containing aluminium powder in mixture containing aluminium powder and phosphate glass powder body converts less than 5 mass % in silver, in order to make the overlay film (glaze layer) that the antibiotic property glaze compositions that utilization comprises anti-bacterial composition is formed show good antibiotic property, anti-bacterial composition addition in antibiotic property glaze compositions increases, it is possible to the film quality that intensity, gloss, color etc overlay film is original is produced impact. On the other hand, when the content containing aluminium powder in mixture containing aluminium powder and phosphate glass powder body converts more than 60 mass % in silver, the content of the phosphate glass powder body in anti-bacterial composition reduces, therefore, relation according to silver described later Yu the mass ratio of phosphate glass, the antibiotic property glaze compositions comprising anti-bacterial composition is coated in the roasting process behind the surface of ware or enamelware, it is impossible to obtain for suppressing by the good effect of the loss evaporating/spread the silver caused.

In the anti-bacterial composition of present embodiment, the silver (A) contained in mixture containing aluminium powder and phosphate glass powder body and the mass ratio of phosphate glass (P) and A/P are more than 0.05 and less than 1.5, it is preferred to more than 0.15 and less than 1.

When the silver (A) contained in the mixture containing aluminium powder and phosphate glass powder body and the mass ratio of phosphate glass (P) and A/P are less than 0.05, the absolute magnitude of the silver contained in anti-bacterial composition is few, therefore, in order to make the overlay film that the antibiotic property glaze compositions that utilization comprises anti-bacterial composition is formed show good antibiotic property, anti-bacterial composition addition in antibiotic property glaze compositions increases, and the amount of the phosphate glass contained in antibiotic property glaze compositions increases. It should be noted that phosphate glass has with silicon dioxide (SiO₂) as point phase in the glaze of main constituent thus the tendency of emersion from the teeth outwards, therefore, when the amount of the phosphate glass contained in antibiotic property glaze compositions is too much, it is possible to the apparent unfavorable conditions such as glaze layer albefaction occur, or brings harmful effect to the flatness on the surface of glaze layer. On the other hand, when the silver (A) contained in mixture containing aluminium powder and phosphate glass powder body and the mass ratio of phosphate glass (P) and A/P are more than 1.5, the silver ion (Ag+) can not being bonded with phosphate glass increases, therefore, in roasting process behind the surface that the antibiotic property comprising anti-bacterial composition glaze compositions is coated ware or enamelware, it is suppressed that the effect of the loss of the silver caused by evaporation/diffusion becomes insufficient.

Then, illustrating containing aluminium powder and phosphate glass powder body the composition of the anti-bacterial composition as present embodiment.

" containing aluminium powder "

At least one powder body comprising in the group of silver, silver phosphate, silver oxide, Disilver carbonate, silver nitrate, silver chloride, Argentous sulfide. and silver acetate it is preferably, more preferably comprise at least one powder body in the group of silver, silver phosphate and silver oxide containing aluminium powder.

BET specific surface area containing aluminium powder is preferably 0.2m²/ more than g, more preferably 0.3m²/ more than g, more preferably 0.4m²/ more than g and 2.5m²/ below g.

The anti-bacterial composition of present embodiment, by being 0.2m containing BET specific surface area²/ more than g containing aluminium powder, easily form the secondary aggregate containing aluminium powder Yu phosphate glass powder body, in the process that anti-bacterial composition or antibiotic property glaze compositions carry out roasting, interact with the phosphate glass probability of (being bonded/point phase) of silver ion increases. As its result, suppressing the effect of the loss of the silver caused by evaporation, diffusion and improved in the effect of the localization on overlay film surface by point silver ion caused mutually of phosphate glass, 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 0.2m²During/g, it is difficult to form the secondary aggregate containing aluminium powder Yu phosphate glass powder body, even if forming secondary aggregate, also easily becoming fragile and destroying. Therefore, when preparing antibiotic property glaze compositions, it is separately present containing aluminium powder and phosphate glass powder body in glaze, when anti-bacterial composition or antibiotic property glaze compositions are carried out roasting, silver ion is difficult to be bonded with phosphate glass, it is suppressed that silver-colored diffusion, the effect of evaporation become insufficient.

At this, secondary aggregate refers to the particle (offspring) of following state, and described state is: the state that the primary particle of at least one primary particle containing aluminium powder and at least one phosphate glass powder body is joined by the interaction of the noncovalent such as electrostatic interaction, Van der Waals force; Or shock between particle during due to interparticle surface because of mixing and geometry ground is gluing so that interface is fixed, the gluing and state gathered between particle.

Index as the size of secondary aggregate, it is possible to enumerate the mean diameter of anti-bacterial composition. The mean diameter (median particle diameter) that the anti-bacterial composition of present embodiment is measured by laser diffraction/Opticolor method is preferably less than 50 ��m, more preferably more than 1 ��m and less than 20 ��m.

Directly observe it addition, the size of secondary aggregate can also pass through scanning electron microscope (SEM) etc. The most length and width degree of secondary aggregate is preferably less than 100 ��m, more preferably less than 50 ��m. It should be noted that the most length and width degree of secondary aggregate is the width that the length from one end of secondary aggregate (unsetting) to the other end reaches the direction grown most.

In anti-bacterial composition, the mean diameter (median particle diameter) of secondary aggregate is more than 50 ��m, or when the most length and width degree thick secondary aggregate such more than 100 ��m of secondary aggregate increases, when the film comprising antibiotic property glaze compositions being carried out roasting and forms the overlay film comprising antibiotic property glaze compositions, the size of point phase of the phosphate glass containing abundant silver ion increases, and the decreased number of point phase in antibiotic property glaze compositions, therefore, the distribution of the silver ion in the surface of the overlay film comprising antibiotic property glaze compositions becomes uneven, this overlay film likely cannot obtain stable antibiotic property.

" phosphate glass powder body "

In phosphate glass powder body, as the composition utilizing the oxide of fluorescent X-ray algoscopy to convert, it is preferable that containing phosphorus pentoxide (P₂O₅), aluminium oxide (Al₂O₃) and selected from sodium oxide (Na₂And potassium oxide (K O)₂O) at least any one.

In phosphate glass powder body, as the P of the composition utilizing the oxide of fluorescent X-ray algoscopy to convert₂O₅Content be more than 25 mass % and below 60 mass %, it is preferred to more than 30 mass % and below 50 mass %.

P₂O₅Content less than 25 mass % time, the amount of the silver ion being bonded with phosphate glass reduces, it is suppressed that the diffusion of silver, evaporation effect become insufficient. On the other hand, P₂O₅Content more than 60 mass % time, when using the antibiotic property glaze compositions comprising anti-bacterial composition to form overlay film on the surface of ware or enamelware and make antibacterial articles, overlay film easily separates from antibacterial articles, therefore, it is possible to bring harmful effect to the outward appearance of antibacterial articles and flatness.

In phosphate glass powder body, as the Al of the composition utilizing the oxide of fluorescent X-ray algoscopy to convert₂O₃Content be more than 10 mass % and below 35 mass %, it is preferred to more than 20 mass % and below 30 mass %.

Phosphate glass powder body passes through P₂O₅With Al₂O₃Bonding and form tridimensional network. Due to only P₂O₅Time form the condensed phosphate of straight-chain and water soluble. Therefore, in phosphate glass powder body, Al₂O₃Content less than 10 mass % time, the condensed phosphate of straight-chain increases, therefore, when using the antibiotic property glaze compositions comprising anti-bacterial composition to form overlay film on the surface of ware or enamelware and make antibacterial articles, the resistance to water of antibacterial articles is deteriorated, when the environment having water uses, silver dissolution from overlay film, it is possible to be difficult to show permanent antibiotic property. On the other hand, Al₂O₃Content more than 35 mass % time, the reduction of the meltability of phosphate glass during due to roasting and Al₂O₃Precipitation, bring impact to the flatness of the reduction of antibiotic property and glaze layer surface.

In phosphate glass powder body, as the composition utilizing the oxide of fluorescent X-ray algoscopy to convert selected from Na₂O and K₂In O at least any one content, by Na₂O and K₂The total content that O combines is more than 10 mass % and below 35 mass %, it is preferred to more than 18 mass % and below 28 mass %.

Na₂O and K₂When the content of O is less than 10 mass %, sodium ion (Na+) and potassium ion (K+) that silver ion is not contained in phosphate glass powder body are replaced with sufficient amount, therefore, the amount of the silver ion being bonded with phosphate glass reduces, it is suppressed that silver-colored diffusion, the effect of evaporation become insufficient. On the other hand, Na₂O and K₂When the content of O is more than 35 mass %, when preparing antibiotic property glaze compositions, the stripping quantity of alkaline components increases, and the viscosity of antibiotic property glaze compositions is produced impact, it is possible to bring harmful effect to coating.

In the above-mentioned secondary aggregate containing aluminium powder with phosphate glass powder body, the average primary particle diameter of phosphate glass powder body is preferably less than 20 ��m, more preferably less than 5 ��m.

When the average primary particle diameter of phosphate glass powder body is more than 20 ��m, it is difficult to form the secondary aggregate containing aluminium powder Yu phosphate glass powder body, even if forming secondary aggregate, also easily becoming fragile and destroying. Therefore, when preparing antibiotic property glaze compositions, it is separately present containing aluminium powder and phosphate glass powder body in glaze, when anti-bacterial composition or antibiotic property glaze compositions are carried out roasting, silver ion is difficult to be bonded with phosphate glass, it is suppressed that silver-colored diffusion, the effect of evaporation become insufficient.

In the anti-bacterial composition of present embodiment, it is preferable that the softening point of phosphate glass powder body is lower than the fusing point containing aluminium powder. When the softening point of phosphate glass powder body is higher than fusing point containing aluminium powder, anti-bacterial composition or antibiotic property glaze compositions are carried out in the process of roasting, first the silver melted is until phosphate glass generation softening could be bonded with phosphate glass, therefore, can lose due to evaporation, diffusion.

The anti-bacterial composition of present embodiment, except containing aluminium powder and phosphate glass powder body, in order to regulate the meltability etc. during roasting, it is also possible to contain glass powder, mineral dust, metal-oxide, metal salt compound, phosphate etc. as required.

[manufacture method of anti-bacterial composition]

The manufacture method of the anti-bacterial composition of present embodiment is the method mixed with containing aluminium powder by phosphate glass powder body, and the manufacture method of phosphate glass powder body can apply the manufacture method etc. of the glass powder (sintered glass (frittedglass)) generally carried out.

Mixed method containing aluminium powder Yu phosphate glass powder body is not particularly limited, in order to generate the secondary aggregate containing aluminium powder Yu phosphate glass powder body in a large number, produce, between particle, the mixed method that the collision frequency between the Impact energy of appropriateness, particle is high, it is preferable that the mixed method of strong impact force and shearing force does not occur during preferably in mixing. When strong impact force and shearing force play a role, the secondary aggregate formed containing aluminium powder and phosphate glass powder body it is likely to occur destruction. It addition, in incorporation time length, occur in the mixed method of high frictional heat, secondary aggregate likely thicker greatly, therefore not preferred.

As such mixed method, it is possible to enumerate such as: mixing impeller type mixer, the fluidized bed type mixers such as container rotating type mixer, ribbon mixer such as cone-type mixers.

Using in the mixing containing aluminium powder and phosphate glass powder body of above-mentioned mixed method, incorporation time was preferably 1 hour less than 100 hours.

In short-term, admixture likely becomes uneven to incorporation time. On the other hand, when incorporation time is long, producing thick aggregation, the distribution of the silver ion on glaze layer surface becomes uneven, and antibiotic property likely becomes unstable.

The mass ratio of silver (A) and the phosphate glass (P) contained and anti-bacterial composition that A/P is more than 0.05 and less than 1.5, mean diameter is less than 50 ��m it is calculated as in more than 5 mass % and below 60 mass %, said mixture with silver conversion containing aluminium powder and the content containing aluminium powder in the mixture of phosphate glass powder body, said mixture by obtaining above comprising.

[antibiotic property glaze compositions]

The antibiotic property glaze compositions of present embodiment is the anti-bacterial composition containing above-mentioned present embodiment and glaze and the antibiotic property glaze compositions that obtains, the content of anti-bacterial composition is preferably more than 0.01 mass % and below 3 mass % relative to glaze in silver conversion, more preferably more than 0.05 mass % and below 1.5 mass %.

At this, the content of anti-bacterial composition is made to be calculated as reason for this is that of more than 0.01 mass % and below 3 mass % relative to glaze with silver conversion, when the content of anti-bacterial composition converts less than 0.01 mass % in silver, the amount of the silver contained in anti-bacterial composition is very few, antibiotic property reduces, as a result of which it is, desired antibiotic property cannot be shown, antibiotic property as anti-bacterial composition reduces, therefore not preferred. On the other hand, when the content of anti-bacterial composition converts more than 3 mass % in silver, containing silver to showing more than desired antibiotic property, most of silver are wasted, therefore not preferred.

The antibiotic property glaze compositions of present embodiment, except the anti-bacterial composition and glaze of above-mentioned present embodiment, it is also possible to containing auxiliary agents such as the inorganic powder such as glass powder, mineral dust, thickening agent, dispersants.

The antibiotic property glaze compositions of present embodiment is by the anti-bacterial composition containing the present embodiment being calculated as more than 0.01 mass % and below 3 mass % relative to glaze with silver conversion, to glaze endowing antibacterial, and can reduce the content of silver or silver compound.

Therefore, film is formed by being coated with the antibiotic property glaze compositions of present embodiment on ceramic product or enamelware, and this film is carried out heat treatment, it is consequently formed overlay film (glaze layer), it is possible to ceramic product or enamelware endowing antibacterial.

The antibiotic property glaze compositions of present embodiment is preferably 10 ��m less than 1000 ��m relative to the coating film thickness (thickness of film) of pottery chinaware goods or enamelware. When the coating film thickness of antibiotic property glaze compositions is less than 10 ��m, it is difficult to comprise the overlay film of antibiotic property glaze compositions at pottery chinaware goods or being formed uniformly over the surface of enamelware, it is possible to produce inequality in the manifesting of antibiotic property. On the other hand, when the coating film thickness of antibiotic property glaze compositions is more than 1000 ��m, the consumption that makes of antibiotic property glaze compositions increases, therefore, cost up, economically not preferred.

[antibacterial articles]

The antibacterial articles of present embodiment is the article utilizing the antibiotic property glaze compositions of present embodiment to form overlay film (glaze layer); as these article; can enumerate in washroom, the article of lavatory, kitchen, bathroom etc. should guard against the place of the pollution caused by antibacterial or hospital, food processing facilities, communal facility etc. need protection life to threaten from antibacterial place use; such as: the health pottery ceramic product such as tool, container, tableware, ceramic tile, pottery, the enamelware such as container, panel, cooker, electric product, building materials component.

By utilizing the antibiotic property glaze compositions of present embodiment to form overlay film at least necessary position on these ceramic products or enamelware surface, it is possible to increase the antibiotic property of this article surface, and the content of silver or silver compound can be reduced.

The overlay film formed on the surface of pottery chinaware goods or enamelware can be monolayer, it is also possible to more than two-layer, but preferably make the overlay film that the antibiotic property glaze compositions utilizing present embodiment is formed as outermost layer. At the overlay film not making the antibiotic property glaze compositions utilizing present embodiment be formed as in outermost situation, silver ion is difficult to be present in the surface of overlay film, it is possible to be difficult to show the antibiotic property brought by silver.

As described above, anti-bacterial composition according to present embodiment, owing to comprising the mixture containing aluminium powder Yu phosphate glass powder body, the content containing aluminium powder in said mixture is calculated as more than 5 mass % and below 60 mass % with silver conversion, and the mass ratio of the silver contained in said mixture (A) and phosphate glass (P) and A/P are more than 0.05 and less than 1.5, therefore, it is possible to raising antibiotic property, and the content of silver or silver compound can be reduced.

By comprise the above-mentioned anti-bacterial composition containing aluminium powder Yu the mixture of above-mentioned phosphate glass powder body add to glaze carries out roasting time, in roasting process, silver ion is with the monovalent cation in phosphate glass (such as, Na+, K+) replace, silver ion is bonded with phosphate glass, therefore, it is possible to suppress the silver-colored loss owing to evaporation or the silver composition of silver composition cause to the diffusion in the substrate (biscuit) of ware. That is, silver ion is in order to be bonded with phosphate glass, it is necessary to replace with the monovalent cation in phosphate glass. Cation (such as, Ca2+) more than bivalence combines due to strong with phosphate glass, thus is difficult to and silver ion displacement. Therefore, in the anti-bacterial composition of present embodiment, it is preferable that phosphate glass powder body contains the monovalent cations such as a certain amount of above Na+, K+.

The anti-bacterial composition of present embodiment, except can suppressing the silver-colored loss that the evaporation by silver composition as above or diffusion cause, and, due to phosphate glass in using silicon dioxide as the glaze of main constituent contracted payment and there is a point phase, and the thermal coefficient of expansion of phosphate glass is big, light specific gravity during roasting, therefore, utilize the phenomenon that the near surface at the overlay film comprising antibiotic property glaze compositions easily localizes, it is possible to make the amount of the silver on the surface of this overlay film increase. Thus, even if reducing silver or silver compound to the addition in anti-bacterial composition, anti-bacterial composition also is able to show antibiotic property.

In order to play above-mentioned effect fully, the mixing ratio containing aluminium powder Yu phosphate glass powder body is critically important. In anti-bacterial composition, when the content containing aluminium powder is more than phosphate glass powder body, the effect of the loss of the silver that silver ion is that bring with being bonded of phosphate glass, suppression is caused by evaporation or the diffusion of silver composition becomes insufficient. On the other hand, in anti-bacterial composition, when the content containing aluminium powder is fewer than phosphate glass powder body, the content of the silver in anti-bacterial composition 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 adding antibacterial in this antibiotic property glaze compositions in a large number, the phosphate glass concentration in antibiotic property glaze compositions increases. As mentioned above, a point phase is being there is in phosphate glass using silicon dioxide as the glaze of main constituent, there is the tendency of surface colocalization at the overlay film comprising antibiotic property glaze compositions, therefore, when the content of the phosphate glass in antibiotic property glaze compositions is many, it is likely to occur the apparent unfavorable conditions such as the overlay film albefaction that comprises antibiotic property glaze compositions, or brings harmful effect to the flatness on the surface of overlay film.

It addition, phosphate glass has in the tendency that point phase occurs using silicon dioxide as the glaze of main constituent, in a point middle mutually silver ion concentration. Further, since the thermal coefficient of expansion of phosphate glass is big, at high temperature proportion lightens, and therefore, the phosphate glass after point middle mutually silver ion concentration has the tendency of emersion on glaze layer surface. As a result of which it is, the amount at the silver ion on glaze layer surface increases.

Due to above effect, the anti-bacterial composition of present embodiment can show excellent antibiotic property with the use level of lesser amount of silver or silver compound than ever.

Due to condensed phosphate (polymer of phosphoric acid) and metal ion generation coordination bonding, therefore, can utilize as the agent for capturing of the metal ion of water treatment agent etc. Condensed phosphate does not have resistance to water, but the phosphate glass containing aluminium oxide in structure forms tridimensional network. It addition, aluminum enters in the network structure of phosphate glass, thus, electric charge is remained neutrality by phosphate glass, and therefore, the double bond of phosphate glass is opened, and the structure of phosphate glass becomes close, and therefore, the resistance to water of the anti-bacterial composition of present embodiment improves.

The anti-bacterial composition of present embodiment is applicable to health pottery tool or enamelware, and therefore, resistance to water is emphasis. Therefore, the phosphate glass in the anti-bacterial composition of present embodiment needs to contain in the structure aluminum.

It addition, in the anti-bacterial composition of present embodiment, form secondary aggregate containing aluminium powder with phosphate glass powder body, adjoin each other existence containing aluminium powder and phosphate glass powder body, thus, 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 present embodiment, due to the anti-bacterial composition containing present embodiment and glaze, and the content making this anti-bacterial composition is calculated as more than 0.01 mass % and below 3 mass % relative to glaze with silver conversion, therefore, the antibiotic property of antibiotic property glaze compositions can be improved, and the content of silver or silver compound can be reduced.

Antibacterial articles according to present embodiment, owing to utilizing the antibiotic property glaze compositions of present embodiment to form overlay film, therefore, it is possible to improve the antibiotic property on the surface of this antibacterial articles, and can reduce the content of silver or silver compound.

Embodiment

Hereinafter, by embodiment and comparative example, the present invention is more specifically illustrated, but the invention is not restricted to below example.

[embodiment 1]

" making of anti-bacterial composition "

Using as the BET specific surface area containing aluminium powder be 0.6m²The silver of/g: the phosphate glass powder body A:65 mass parts of 35 mass parts and composition shown in table 1 puts in container rotating type mixer, mix 3 hours, obtain the anti-bacterial composition of the embodiment 1 being made up of the mixture containing aluminium powder and phosphate glass powder body A.

" mensuration of mean diameter "

By anti-bacterial composition suspendible in water, use laser diffraction/scattering formula particle size distribution meter (trade name: LA-920, Ku Chang manufacturing company system), measure the mean diameter (median particle diameter) of anti-bacterial composition.

Evaluation result is shown in table 2.

" confirmation of secondary aggregate "

Observe anti-bacterial composition by scanning electron microscope (SEM), confirm the presence or absence of secondary aggregate.

It addition, measured most length and width degree (��m) of secondary aggregate by scanning electron microscope (SEM).

Evaluation result is shown in table 2. It addition, scanning electron microscope (SEM) image of anti-bacterial composition is shown in Fig. 1. The reflection electronic of anti-bacterial composition is formed (COMPO) image and is shown in Fig. 2. It should be noted that the shape that scanning electron microscope image makes measuring object is clear and definite. It addition, reflection electronic composition diagram seems reflection electronic picture is carried out image procossing and obtains, the composition according to measuring object, the brightness of image is different, and atom sequence number is more big more bright.

In Fig. 1, particle diameter is little and the glomerate particle of shape is containing aluminium powder, and particle diameter is big and to be formed without spherical particle be phosphate glass powder body A. In Fig. 2, the particle of bright (partially white) is that the particle of dark (partially black) is phosphate glass powder body A containing aluminium powder.

" making of antibiotic property glaze compositions "

As glaze raw material, use the glaze raw material with following composition.

SiO₂: 60 mass %

Al₂O₃: 13 mass %

CO₂: 10 mass %

CaO:11 mass %

ZnO:1 mass %

K₂O:3 mass %

Na₂O:2 mass %

This glaze raw material 60 mass parts and water 40 mass parts are put in ball mill, after pulverizing 15 hours, adding above-mentioned anti-bacterial composition makes it reach 0.30 mass % in silver conversion relative to glaze raw material, and mixing 1 hour, obtains the antibiotic property glaze compositions of embodiment 1 further.

" making of antibiotic property pottery chinaware plate "

Prepare the ware plate of long 50mm �� wide 50mm �� thickness 5mm, with 1000g/m on this ware plate²Coating weight spray above-mentioned antibiotic property glaze compositions, after drying, at the roasting temperature 1 hour of 1200 DEG C, obtain the antibiotic property ware plate of embodiment 1.

" the antibiotic property evaluation of antibiotic property pottery chinaware plate "

In order to confirm resistance to water, chinaware plate of above-mentioned antibiotic property being made pottery impregnates 16 hours in the water of 50 DEG C. Then, by Japanese Industrial Standards JISZ2801 " antibacterial fabricated product-antibiotic property test method and the antibacterial effect " antibiotic property evaluating antibiotic property pottery chinaware plate, following calculating formula antibacterial activity value is obtained.

Antibacterial activity value (R)=(Ut-U0)-(At-U0)=Ut-At

U0: the meansigma methods (individual) of the firm postvaccinal viable count of undressed test film

Ut: the meansigma methods (individual) of the viable count behind 24 hours of undressed test film

At: the meansigma methods (individual) of the viable count behind 24 hours of antibacterial processing experiment sheet

At this, escherichia coli and staphylococcus aureus are tested, have rated two kinds of antibacterials with or without anti-microbial property. Evaluate and carry out according to Japanese Industrial Standards JISZ2801 " antibacterial fabricated product-antibiotic property test method and antibacterial effect ", it is qualified to be evaluated as when the antibacterial activity value of both escherichia coli and staphylococcus aureus is more than 2.0, is evaluated as defective during to any one in escherichia coli and staphylococcus aureus or both antibacterial activity values lower than 2.0.

Evaluation result is shown in table 2.

" ocular estimate of antibiotic property pottery chinaware plate "

Outward appearance about obtained antibiotic property pottery chinaware plate, by the visual inspection with the pottery chinaware plate carrying out roasting after being coated with the glaze not containing anti-bacterial composition, confirm the presence or absence of variable color, concavo-convex, foreign body precipitations, bubble etc., it will be observed that the situation of bad order is set to defective significantly.

Evaluation result is shown in table 2.

[embodiment 2]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 25 mass parts, phosphate glass powder body A:75 mass parts, other operate similarly to Example 1, make the anti-bacterial composition of embodiment 2.

For the anti-bacterial composition of embodiment 2, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 2.

For the antibiotic property pottery chinaware plate of embodiment 2, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 3]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 15 mass parts, phosphate glass powder body A:85 mass parts, other operate similarly to Example 1, make the anti-bacterial composition of embodiment 3.

For the anti-bacterial composition of embodiment 3, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 3.

For the antibiotic property pottery chinaware plate of embodiment 3, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 4]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 45 mass parts, phosphate glass powder body A:55 mass parts, other operate similarly to Example 1, make the anti-bacterial composition of embodiment 4.

For the anti-bacterial composition of embodiment 4, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 4.

For the antibiotic property pottery chinaware plate of embodiment 4, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 5]

It is 0.3m except with BET specific surface area²The silver of/g is as containing beyond aluminium powder, and other operate similarly to Example 1, makes the anti-bacterial composition of embodiment 5.

For the anti-bacterial composition of embodiment 5, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 5.

For the antibiotic property pottery chinaware plate of embodiment 5, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 6]

It is 2.0m except with BET specific surface area²The silver phosphate of/g is as containing beyond aluminium powder, and other operate similarly to Example 1, makes the anti-bacterial composition of embodiment 6.

For the anti-bacterial composition of embodiment 6, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 6.

For the antibiotic property pottery chinaware plate of embodiment 6, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 7]

It is 1.5m except with BET specific surface area²The silver oxide of/g is as containing beyond aluminium powder, and other operate similarly to Example 1, makes the anti-bacterial composition of embodiment 7.

For the anti-bacterial composition of embodiment 7, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 7.

For the antibiotic property pottery chinaware plate of embodiment 7, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 8]

Phosphate glass powder body B except with composition shown in table 1 replaces beyond phosphate glass powder body A, and other operate similarly to Example 1, makes the anti-bacterial composition of embodiment 8.

For the anti-bacterial composition of embodiment 8, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 8.

For the antibiotic property pottery chinaware plate of embodiment 8, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 9]

Phosphate glass powder body C except with composition shown in table 1 replaces beyond phosphate glass powder body A, and other operate similarly to Example 1, makes the anti-bacterial composition of embodiment 9.

For the anti-bacterial composition of embodiment 9, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 9.

For the antibiotic property pottery chinaware plate of embodiment 9, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 10]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 60 mass parts, phosphate glass powder body A:40 mass parts, other operate similarly to Example 1, make the anti-bacterial composition of embodiment 10.

For the anti-bacterial composition of embodiment 10, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, except adding above-mentioned anti-bacterial composition and making it reach 2.5 mass % in silver conversion relative to glaze raw material, other operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 10.

For the antibiotic property pottery chinaware plate of embodiment 10, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[embodiment 11]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 5 mass parts, phosphate glass powder body A:95 mass parts, other operate similarly to Example 1, make the anti-bacterial composition of embodiment 11.

For the anti-bacterial composition of embodiment 11, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 2.

It addition, except adding above-mentioned anti-bacterial composition and making it reach 0.05 mass % in silver conversion relative to glaze raw material, other operate similarly to Example 1, make antibiotic property glaze compositions and the antibiotic property pottery chinaware plate of embodiment 11.

For the antibiotic property pottery chinaware plate of embodiment 11, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 2.

[comparative example 1]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 3 mass parts, phosphate glass powder body A:97 mass parts, other operate similarly to Example 1, the anti-bacterial composition of comparison example 1.

For the anti-bacterial composition of comparative example 1, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 1 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 1, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 2]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 70 mass parts, phosphate glass powder body A:30 mass parts, other operate similarly to Example 1, the anti-bacterial composition of comparison example 2.

For the anti-bacterial composition of comparative example 2, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 2 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 2, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 3]

Phosphate glass powder body D except with composition shown in table 1 replaces beyond phosphate glass powder body A, and other operate similarly to Example 1, the anti-bacterial composition of comparison example 3.

For the anti-bacterial composition of comparative example 3, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 3 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 3, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 4]

Phosphate glass powder body E except with composition shown in table 1 replaces beyond phosphate glass powder body A, and other operate similarly to Example 1, the anti-bacterial composition of comparison example 4.

For the anti-bacterial composition of comparative example 4, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 4 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 4, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 5]

Phosphate glass powder body F except with composition shown in table 1 replaces beyond phosphate glass powder body A, and other operate similarly to Example 1, the anti-bacterial composition of comparison example 4.

For the anti-bacterial composition of comparative example 5, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 5 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 5, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 6]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 5 mass parts, phosphate glass powder body A:95 mass parts, other operate similarly to Example 1, the anti-bacterial composition of comparison example 6.

For the anti-bacterial composition of comparative example 6, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, except add above-mentioned anti-bacterial composition make its in silver conversion reach 0.005 mass % relative to glaze raw material except, other operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 6 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 6, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 7]

Except making silver and the mixing ratio of phosphate glass powder body A for silver-colored: except 60 mass parts, phosphate glass powder body A:40 mass parts, other operate similarly to Example 1, the anti-bacterial composition of comparison example 7.

For the anti-bacterial composition of comparative example 7, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, except add above-mentioned anti-bacterial composition make its in silver conversion reach 6 mass % relative to glaze raw material except, other operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 7 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 7, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 8]

It is 0.1m except with BET specific surface area²The silver of/g is as containing beyond aluminium powder, and other operate similarly to Example 1, the anti-bacterial composition of comparison example 8.

For the anti-bacterial composition of comparative example 8, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 8 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 8, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

[comparative example 9]

Except in the making making anti-bacterial composition, incorporation time containing aluminium powder Yu phosphate glass powder body A is except 100 hours, other operate similarly to Example 1, the anti-bacterial composition of comparison example 9.

For the anti-bacterial composition of comparative example 9, operate similarly to Example 1, the mensuration of the particle diameter that is averaged and the confirmation of secondary aggregate. Evaluation result is shown in table 3.

It addition, operate similarly to Example 1, the antibiotic property glaze compositions of comparison example 9 and antibiotic property pottery chinaware plate.

For the antibiotic property pottery chinaware plate of comparative example 9, operate similarly to Example 1, carry out antibiotic property evaluation and ocular estimate. Evaluation result is shown in table 3.

As shown in Table 2, the antibiotic property pottery chinaware plate of embodiment 1��embodiment 11 does not have bad order. In addition we know, the excellent antibacterial performance of the antibiotic property pottery chinaware plate of embodiment 1��embodiment 11.

On the other hand, in comparative example 1, the silver content in anti-bacterial composition is 3 mass %, and the mass ratio (A/P) of silver and phosphate glass is 0.031, therefore, and antibiotic property pottery chinaware plate generation albefaction, it was observed that bad order. In addition we know, the antibiotic property pottery chinaware plate of comparative example 1 does not have anti-microbial property.

In comparative example 2, the silver content in anti-bacterial composition is 70 mass %, and the mass ratio (A/P) of silver and phosphate glass 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 contained in phosphate glass powder body D₂O₅Amount few, therefore, in the roasting process of antibiotic property glaze compositions, it is suppressed that the effect of the loss of the silver caused by the silver evaporation of composition or diffusion is insufficient, thus, it can be known that antibiotic property pottery chinaware plate does not have anti-microbial property.

In comparative example 4, the Al contained in phosphate glass powder body E₂O₃Amount few, therefore, resistance to water is low, in the water of 50 DEG C impregnate 16 little constantly, silver and P₂O₅Dissolution together, thus, it can be known that antibiotic property pottery chinaware plate does not have anti-microbial property.

In comparative example 5, the Na contained in phosphate glass powder body F₂O and K₂The amount of O is few, and therefore, silver can not be bonded with phosphate glass, in the roasting process of antibiotic property glaze compositions, it is suppressed that the effect of the loss of the silver caused by the evaporation of silver composition or diffusion is insufficient, thus, it can be known that antibiotic property pottery chinaware plate does 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 anti-microbial property.

In comparative example 7, silver is 6 mass % relative to the content of glaze, and therefore, antibiotic property pottery chinaware plate occurs painted, it was observed that 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 antibiotic property.

In comparative example 9, the mean diameter of anti-bacterial composition is 65 ��m, thus, it can be known that show the region of anti-microbial property and do not show that the region of anti-microbial property is mixed in antibiotic property pottery chinaware plate, it is impossible to practical application.

Claims

1. an anti-bacterial composition, it is characterised in that

Comprise the mixture containing aluminium powder Yu phosphate glass powder body,

The described content containing aluminium powder in described mixture is calculated as more than 5 mass % and below 60 mass % with silver conversion,

Mass ratio and the A/P of the silver-colored A contained in described mixture and phosphate glass P are more than 0.05 and less than 1.5.

2. anti-bacterial composition as claimed in claim 1, it is characterised in that in described phosphate glass powder body, as the composition utilizing the oxide of fluorescent X-ray algoscopy to convert, containing the P of more than 25 mass % and below 60 mass %₂O₅, more than 10 mass % and below 35 mass % Al₂O₃, add up to more than 10 mass % and below 35 mass % selected from Na₂O and K₂In O at least any one.

3. anti-bacterial composition as claimed in claim 1 or 2, it is characterised in that comprise by the described secondary aggregate formed containing aluminium powder and described phosphate glass powder body, and to utilize the mean diameter of laser diffraction/Opticolor method mensuration be less than 50 ��m.

4. the anti-bacterial composition as according to any one of claims 1 to 3, it is characterised in that the described BET specific surface area containing aluminium powder is 0.2m²/ more than g.

5. the anti-bacterial composition as according to any one of Claims 1 to 4, it is characterised in that described is by least one powder body constituted in the group being selected from silver, silver phosphate and silver oxide containing aluminium powder.

6. an antibiotic property glaze compositions, it is characterised in that

Containing the anti-bacterial composition according to any one of Claims 1 to 5 and glaze,

The content of described anti-bacterial composition is calculated as more than 0.01 mass % and below 3 mass % relative to described glaze with silver conversion.

7. an antibacterial articles, it is characterised in that utilize the antibiotic property glaze compositions described in claim 6 to form overlay film.