CN101298364A - Antimicrobial glass and method for producing the same - Google Patents

Antimicrobial glass and method for producing the same Download PDF

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Publication number
CN101298364A
CN101298364A CNA2007101954591A CN200710195459A CN101298364A CN 101298364 A CN101298364 A CN 101298364A CN A2007101954591 A CNA2007101954591 A CN A2007101954591A CN 200710195459 A CN200710195459 A CN 200710195459A CN 101298364 A CN101298364 A CN 101298364A
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Prior art keywords
antibacterial glass
glass
antibacterial
addition
weight
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CN101298364B (en
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神谷义明
金丸忍
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Koa Glass Co Ltd
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Koa Glass Co Ltd
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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
    • C03C4/00—Compositions for glass with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron

Abstract

An antibacterial glass which contacts with water directly, releases a silver ion, and thus exhibits an antibacterial effect, and a method for production thereof are provided. An antibacterial glass suitable as an antibacterial glass for a washing machine for subjecting an article to acquire antibacterial property to an antibacterial treatment with a silver ion during or after washing, or the like, wherein the antibacterial glass for a washing machine has a maximum diameter (t1) in the range of 1 to 50 mm and the amount of a silver ion to be eluted is a value in the range of 0.5 to 100 mg/(g 24Hrs); and a method for producing the antibacterial glass.

Description

The manufacture method of antibacterial glass and antibacterial glass
The application is that Chinese patent application number is the dividing an application of patent application of 2005800002398 (applying date is on March 11st, 2005, and denomination of invention is the manufacture method of antibacterial glass and antibacterial glass).
Technical field
The present invention relates to suit (to comprise use in washing machine antibacterial glass with mildew resistance as the use in washing machine antibacterial glass.Below identical.) antibacterial glass that waits and the manufacture method of this antibacterial glass, this antibacterial glass can directly contact and the stripping silver ions with water in by the washing of antibiont or after the washing.
Relate in more detail, suitable conduct is used at the antibacterial glass of being implemented the used use in washing machine antibiotic glass of antimicrobial treatment etc. by the washing of antibiont or washing back by silver ions, when this antibacterial glass directly contacts with water, can be rapidly and emit the silver ions of specified amount for a long time, also relate to the manufacture method of such antibacterial glass.
Background technology
In recent years, in order to give antibacterial effects such as building materials, tame electrical article (comprising TV, computer, mobile phone, pick up camera etc.), groceries, packing material, the common antibacterial resin composition that uses the antibacterial glass of the regulation particle diameter of in resin, sneaking into specified amount and get.
As such antibacterial resin composition, the someone discloses the forming synthetic resin thing (for example, with reference to patent documentation 1) of the borosilicic acid antibacterial glass that contains the stripping silver ions in resin.
More specifically, described forming synthetic resin thing contains the borosilicic acid antibacterial glass and constitutes in synthetic resins, and this borosilicic acid antibacterial glass is by SiO 2, B 2O 3, P 2O 5In the mesh of one or more kinds form oxide compound and Na 2O, K 2The Ag that contains 0.1～20 weight part in glass solid matter 100 weight parts that the mesh modification oxide compound of one or more kinds among O, CaO, the ZnO constitutes 2O is as univalent Ag.And, in the embodiment of this special permission communique, to put down in writing and in synthetic resins, containing the antibacterial resin composition that median size is 20 μ m or littler antibacterial glass, this antibacterial glass is by SiO 2: 40 moles of %, B 2O 3: 50 moles of %, Na 2Be added with the Ag of 2 weight parts in mixture 100 weight parts that O:10 mole % constitutes 2O.
In addition, as antibacterial resin composition, the someone discloses the resin combination that contains flaky-glass, and this flaky-glass has germ resistance, and particle diameter is that 10～1000 μ m, thickness are 0.1～20 μ m (for example, with reference to patent documentation 2).
More specifically, with regard to the composition of this flaky-glass, when containing B 2O 3The time, by SiO 2: 20～60 weight %, B 2O 3: 30～70 weight %, Na 2O:5～35 weight %, Ag 2O:0.5～3 weight % constitute, when not containing B 2O 3The time, by SiO 2: 55～80 weight %, Al 2O 3: 0.5～30 weight %, Na 2O:19.5～42 weight %, Ag 2O:0.5～3 weight % constitute.
In addition, also the someone discloses the germ resistance water pref that contains silver ions mineral-type antiseptic-germicide and mineral-type weighting agent, this contains silver ions mineral-type antiseptic-germicide, after in 100 ℃ boiling water, flooding 500～1000 hours, under 24 hours the situation of dipping, the stripping quantity of silver ions is 0.5ng/cm in 20 ℃ water or acid 2/ day or more (for example, with reference to patent documentations 3).
More specifically, disclose in resin and to have added the germ resistance water pref that silver ions mineral-type antiseptic-germicide 0.5～5 weight % and mineral-type weighting agent 5～80 weight % constitute that contains that median size is 2～20 μ m, this contains silver ions mineral-type antiseptic-germicide, at the P that contains 56～59 moles of % 2O 5, 33～38 moles of % MgO+CaO+ZnO, the Al of 6～8 moles of % 2O 3Glass be furnished with the Ag of 0～5 weight % in forming 2O.
In addition, as the purposes of antibacterial glass, the someone proposes to be used for for example antibacterial resin composition (for example, with reference to patent documentation 4 and patent documentation 5) of electrical articles such as dish cleaning machine, tableware drying machine, refrigerator, washing machine, pot.
That is to say, its be in constituting the shaping resin of described electrical article, contain respectively specified amount, median size be 20 μ m or littler, by ZnO:40～80 mole %, SiO 2: antibacterial glass that 5～35 moles of %, CaO:5～30 mole % constitutes and specified amount, median size be similarly 20 μ m or littler, by ZnO:54～60 mole %, B 2O 3: 25～32 moles of %, SiO 2: 7～12 moles of %, alkalimetal oxide: the antibacterial resin composition of the antibacterial glass that 5～8 moles of % constitute.
Have, as the purposes of antibacterial glass, the someone proposes to use the bath of glass treatment agent (for example, with reference to patent documentation 6) in water treatment device such as catch basin and cleaning tower again.
That is to say that this bath of glass treatment agent is that major diameter is 10mm or bigger phosphoric acid class glass, its weight ratio of components is: (RO+R 2O)/P 2O 3=0.4～1.2, R 2O/ (RO+R 2O 3)=0～10 (R is Ca, Na etc.), and, when be A with its initial stage solvent temperature, when latter stage, solvent temperature was B, B/A 〉=1/3, and the content of metal ion is 0.005～5 weight %.
[patent documentation 1] spy opens flat 1-313531 communique (scopes of claims)
[patent documentation 2] spy opens flat 7-25635 communique (scopes of claims)
[patent documentation 3] spy opens flat 10-72530 communique (scopes of claims)
[patent documentation 4] spy opens 2000-3238 communique (scopes of claims)
[patent documentation 5] spy opens 2000-3239 communique (scopes of claims)
[patent documentation 6] special fair 7-63701 communique (scopes of claims)
Summary of the invention
But disclosed antibacterial resin composition all constitutes by mix to add antibacterial glass in resin in the patent documentation 1～5, antibacterial glass indirectly be soaked in resin in water contact, thereby can emit silver ions first.
Therefore, when using described antibacterial resin composition, although can give the germ resistance of regulation to parts of electrical article etc., but, in fact, in by the washing of antibiont or washing back directly contacts with water, emits silver ions rapidly, the silver ions that makes specified amount is very difficult attached to this on by antibiont.
In addition, in patent documentation 1,3～5, in order to be blended in equably in the resin, the median size of antibacterial glass is preferably 20 μ m or littler, in patent documentation 2, though antibacterial glass is made the flaky-glass with prescribed level,, the problem that sorting equipment etc. is used as manufacturing installation, their value is limited to specialized range has appearred being used in combination on making.
On the other hand, patent documentation 6 disclosed bath of glass treatment agents, though length-to-diameter ratio is bigger,, the stripping quantity problem substantially seldom of silver ions has appearred.Therefore, identical with disclosed antibacterial resin composition in the patent documentation 1～5, in fact, in by the washing of antibiont or washing back directly contacts with water, emits silver ions rapidly, the silver ions that makes specified amount is very difficult attached to this on by antibiont.
Therefore, present inventors are through discovering with keen determination, and by the size of antibacterial glass and the stripping quantity of silver ions are limited in specialized range, directly contacting with water can be rapidly and emit the silver ions of specified amount for a long time repeatedly, thereby has finished the present invention.
That is to say, the present invention, provide suitable as the antibacterial glass of use in washing machine antibacterial glass etc. and the manufacture method of this antibacterial glass, this antibacterial glass can be in by the washing of antibiont or the washing back directly contact with water and the silver ions of stripping specified amount rapidly and for a long time, can be to the antimicrobial treatment of being implemented repeatedly by antibiont to stipulate.
According to the present invention, by providing following antibacterial glass to address the above problem, it is to be used for directly contacting with water emitting the antibacterial glass that silver ions is brought into play antibacterial effect, and maximum diameter (t1) is 1～50mm, and the stripping quantity of silver ions is 0.5～100mg/ (g24Hrs).
That is to say,, for example, in by the washing of antibiont or after the washing, directly contact with water according to antibacterial glass of the present invention, can be rapidly and emit the silver ions of specified amount for a long time.Therefore, can be to the antimicrobial treatment of being implemented repeatedly by antibiont to stipulate.In addition, so long as like this antibacterial glass of size not merely is easy processing, and, even contact between the high adjacent glass of solvability, also can effectively prevent their aggegations or molten sticking.
In addition, when constituting antibacterial glass of the present invention, be preferred for utilizing in by the washing of antibiont or after the washing silver ions to implement the use in washing machine antibacterial glass of antimicrobial treatment.
That is to say, in washing machine purposes etc., can emit the silver ions of specified amount for a long time, washes etc. is continued to give the antibacterial effect of regulation.
In addition, when constituting antibacterial glass of the present invention, preferably, contain B 2O 3, SiO 2, Ag 2O, alkalimetal oxide be as starting material, and, for total amount, B 2O 3Addition be 30～60 weight %, SiO 2Addition be 30～60 weight %, Ag 2The addition of O is that the addition of 2～5 weight %, alkalimetal oxide is 5～10 weight %.
That is to say, with the starting material of the boric acid class antibiotic glass of regulation respectively in accordance with regulations amount cooperate and form, so, can continue to bring into play the antibacterial effect of regulation by directly contacting the silver ions that can emit specified amount for a long time with water.
In addition,, lack with the reactivity of washing composition according to such use in washing machine antibacterial glass, for use that washing composition washs by antibiont, can stably implement the antimicrobial treatment of stipulating.
The situation of described antibacterial glass, the B of use more amount are arranged again 2O 3So,, according to creating conditions different, sometimes painted easily with working conditions.But,, perhaps implement subsidiary painted coating material around it for example by antibacterial glass being used the place that water route in washing machine etc. can't be visual, thereby, as described later, form compound, can avoid coloring problem by the title complex that adds as the anti-coloring agent.
In addition, when constituting antibacterial glass of the present invention, preferably, contain P 2O 5, Ag 2O, alkalimetal oxide be as starting material, and, for total amount, P 2O 5Addition be 40～70 weight %, Ag 2The addition of O is that the addition of 2～5 weight %, alkalimetal oxide is 15～35 weight %.
That is to say, with the starting material of the phosphoric acid class antibiotic glass of regulation respectively in accordance with regulations amount cooperate and form, so by directly contacting, for example in the washing machine purposes with water, the silver ions of specified amount can be emitted for a long time, the antibacterial effect of regulation can be given constantly to washes.
Have, according to such phosphoric acid class antibiotic glass, the transparency is excellent again, and, no matter be tabular or granular, can emit the silver ions of specified amount.Have again, so long as such phosphoric acid class antibiotic glass, little, the gentle advantage of creating conditions of corrodibility of the fusion kiln when just having etc. to manufacturing.
Have, when constituting antibacterial glass of the present invention, preferably, antibacterial glass all is a tabular, constitutes by with the thin-walled portion of this antibacterial glass identical component a plurality of sheet glass being connected again.
That is to say, flat a plurality of sheet glass are coupled together by the thin-walled portion of stipulating, so, be cut into prescribed level, can easily adjust the absolute stripping quantity (dissolution rate) of silver ions.Therefore,, consider the time of employed envrionment conditions, the water yield or life-time service etc., antibacterial glass of the present invention can be cut into any size and use by making the chocolate chip shape.In addition,, as place of incision, be used in combination the size and the shape in place, can make the antibacterial glass of suitable size and shape with the there because have the thin-walled portion of regulation.
In addition, when constituting antibacterial glass of the present invention, preferably, possess coating material on every side, changed by boxlike (cartridge).
That is to say to possess the coating material of regulation, by boxlikeization, so, not only processing and replacing etc. easily, and, even under the situation of using strong current, can prevent effectively that also it from flowing to the outside with current.
In addition, another embodiment of the present invention is the manufacture method of antibacterial glass, and it is to be used for directly contacting the manufacture method of emitting silver ions and bringing into play the antibacterial glass of antibacterial effect with water, comprises following operation (A)～(B).
(A) fusion operation: with starting material B 2O 3, SiO 2, Ag 2O, alkalimetal oxide heating make it fusion, make melten glass;
(B) forming process:, be that 1～50mm, silver ions stripping quantity are antibacterial glass 0.5～100mg/ (g24Hrs), that have the regulation shape Yi Bian form maximum diameter (t1) Yi Bian cool off melten glass.
That is to say, because comprise above-mentioned manufacturing process, so, directly contact, can emit silver ions, promptly bring into play antibacterial effect with water, consequently, can obtain antibacterial glass effectively, this glass is emitted the silver ions of specified amount in by the washing of antibiont or after the washing, to the antimicrobial treatment of stably being implemented by antibiont to stipulate.
Have, another embodiment of the present invention is the manufacture method of antibacterial glass again, and it is to be used for directly contacting the manufacture method of emitting silver ions and bringing into play the antibacterial glass of antibacterial effect with water, comprises following operation (A ')～(B ').
(A ') the fusion operation: with starting material P 2O 5, Ag 2O, alkalimetal oxide heating make it fusion, make melten glass;
(B ') forming process: Yi Bian cool off melten glass, be that 1～50mm, silver ions stripping quantity are antibacterial glass 0.5～100mg/ (g24Hrs), that have the regulation shape Yi Bian form maximum diameter (t1).
That is to say, because comprise above-mentioned manufacturing process, so, even phosphoric acid class antibiotic glass directly contacts with water, also can emit silver ions, promptly bring into play antibacterial effect.Consequently, can obtain antibacterial glass effectively, this glass is emitted the silver ions of specified amount in by the washing of antibiont or after the washing, to the antimicrobial treatment of stably being implemented by antibiont to stipulate.
In addition, when implementing the manufacture method of antibacterial glass of the present invention, preferably, in operation (B) or operation (B '), use the surface to possess the turning unit of recess, be configured as flat antibacterial glass.
That is to say, in the operation (B),, can utilize the chocolate cutting of thin-walled portion, can be handled, adjust easily the antibacterial glass of area and shape etc. effectively easily by using the turning unit of regulation.
In addition, when implementing the manufacture method of antibacterial glass of the present invention, preferably, between operation (A) and the operation (B) or between operation (A ') and the operation (B '), further comprise antibacterial glass is being possessed refrigerative operation on the substrate of refrigerating unit.
That is to say, because contain the refrigerating work procedure of regulation, so, need not make the water just can be fully and cool off melten glass equably, in follow-up operation, can be configured as the regulation shape accurately.
Description of drawings
[Fig. 1] (a)～(f) is the figure of shape that is used to illustrate the antibacterial glass of the 1st embodiment.
[Fig. 2] is the maximum diameter (t1) that is used to illustrate antibacterial glass and the figure of the relation between the residual rate.
[Fig. 3] is the figure that is used to illustrate the relation between silver ions stripping quantity and the washing times.
[Fig. 4] is the figure of the washing machine of the expression antibacterial glass that uses the 1st embodiment.
[Fig. 5] is the figure that is used to illustrate the shape of antibacterial glass.
[Fig. 6] be the figure that is used to illustrate the coating material of antibacterial glass (one of).
[Fig. 7] (a)～(c) is the figure that is used to illustrate the coating material of antibacterial glass (two).
[Fig. 8] is used to illustrate the shape of antibacterial glass and the figure of coating material.
[Fig. 9] is the figure that is used to illustrate the using method of antibacterial glass.
[Figure 10] is the figure that is used to illustrate by the antibiotic method of antibiont.
[Figure 11] be used to illustrate the 2nd embodiment antibacterial glass manufacture method figure (one of).
[Figure 12] is the figure (two) of manufacture method that is used to illustrate the antibacterial glass of the 2nd embodiment.
[Figure 13] be used to illustrate the 3rd embodiment antibacterial glass manufacture method figure (one of).
[Figure 14] is the figure (two) of manufacture method that is used to illustrate the antibacterial glass of the 3rd embodiment.
Embodiment
Below, based on the use in washing machine antibacterial glass, the embodiment of the using method of the manufacture method that relates to antibacterial glass of the present invention, antibacterial glass and antibacterial glass is specifically described.
[the 1st embodiment]
The 1st embodiment is an antibacterial glass, and it is to emit the antibacterial glass that silver ions is brought into play antibacterial effect by directly contacting with water, and maximum diameter (t1) is 1～50mm, and the stripping quantity of silver ions is 0.5～100mg/ (g24Hrs).
1. antibacterial glass
(1) shape 1
The shape of antibacterial glass has no particular limits, and preferably shown in Fig. 1 (a)～(f), is the tabular of rectangular-shaped, polygon, circle shape, ellipticity, different form, perforate shape etc.
Its reason is, the tabular of, perforate shape rectangular-shaped etc. by antibiotic shape glass is made, even being positioned over prescribed position with situation that water directly contacts under, also can prevent from effectively to be promoted by the hydraulic pressure extruding and flow out from prescribed position.In addition,, be difficult to aggegation during manufacturing or when using etc., so can more easily control antibacterial glass size and shape during fabrication or the envrionment conditions when using if antibacterial glass is rectangular-shaped etc.
But, as long as satisfy the stripping quantity scope of maximum diameter (t1) and silver ions, antibacterial glass can be made shape arbitrarily such as polyhedron, granular, spherical, spheroid, column, pulverizing body.
(2) shape 2
In addition, it is characterized in that the maximum diameter of antibacterial glass (t1) is 1～50mm.Here the maximum diameter of said antibacterial glass (t1) is meant, for example, shown in Fig. 1 (a)～(e), in the shape of antibacterial glass, the maximum length when drawing free-throw line.That is to say that when antibacterial glass for example is under the flat situation, the maximum diameter of described antibacterial glass (t1) is the maximum diameter of in-plane, when being under the granulous situation, the maximum diameter of described antibacterial glass (t1) is the maximum diameter of grain.
In addition, the reason of the maximum diameter (t1) of restriction antibacterial glass is, if the not enough 1mm of maximum diameter, being placed on prescribed position with situation that water directly contacts under, sometimes flow out by hydraulic pressure extruding promotion and from prescribed position easily, perhaps, be difficult to emit for a long time the silver ions of normality sometimes, have again, sometimes easy aggegation when keeping.
In addition, if maximum diameter surpasses 50mm, then be difficult to handle or be difficult to stable the manufacturing.
Therefore, being shaped as under the flat situation of antibacterial glass, its maximum diameter is 8～30mm more preferably, further is preferably 15～20mm.In addition, under the situation that is shaped as granular grade of antibacterial glass, consider that from the easiness of making its maximum diameter is 3～25mm more preferably, further is preferably 5～10mm.
In addition, antibacterial glass is under the flat situation, and the thickness of antibacterial glass is preferably 0.1～10mm.
Its reason is, if the not enough 0.1mm of the thickness of antibacterial glass is difficult to emit the silver ions of normality sometimes, perhaps is difficult to sometimes handle, and then, be difficult to sometimes stably make.On the other hand, if the thickness of antibacterial glass surpasses 10mm, be difficult to handle or be difficult to stable the manufacturing on the contrary.
Therefore, antibacterial glass is under the flat situation, and its thickness is 0.5～8mm more preferably, further preferred 1～5mm.
Have, the maximum diameter of above-mentioned antibacterial glass and thickness for example use optical microscope photograph, vernier callipers to measure at an easy rate again.
(3) shape 3
Then, for the shape of antibacterial glass, describe the maximum diameter (t1) of the in-plane of antibacterial glass and the relation between this antibacterial glass residual rate in use in detail with reference to Fig. 2.The transverse axis of Fig. 2 represents that with logarithm the maximum diameter (mm) of the in-plane of antibacterial glass, the longitudinal axis represent when using the antibacterial glass of various particle diameters, the residual rate of measuring according to the measuring method of antibacterial glass residual rate among the aftermentioned embodiment (%).
As shown in Figure 2, if the maximum diameter of the in-plane of antibacterial glass (t1) is 5mm or bigger, its residual rate is higher, that is to say, demonstrates 50% or bigger value, can be understood as and can use for a long time.
Then, shape for antibacterial glass, describe with reference to Fig. 3 that to use antibacterial glass of the present invention (the maximum diameter 15mm of in-plane) and median size respectively be under the situation of antibacterial glass of 20 μ m in detail, the variation of the stripping quantity of washing times and silver ions.That is to say that the number of times that the transverse axis of Fig. 3 is represented to use washing machine shown in Figure 4 50 and used antibacterial glass separately to wash, the longitudinal axis of Fig. 3 are represented the middle stripping quantity (mg/ (g24Hrs)) of silver ions in water of each time.In addition, among the figure, represent the data of antibacterial glass of the present invention with solid line A, with dashed lines B represents that median size is the data of the antibacterial glass of 20 μ m.
As shown in Figure 3, antibacterial glass of the present invention (use in washing machine antibacterial glass), the maximum diameter of in-plane is a prescribed level, is not promoted by extruding such as hydraulic pressure, so residual quantity does not significantly reduce.Therefore, also can keep desirable stripping quantity even be considered to use repeatedly.So antibacterial glass of the present invention is considered to and can uses for a long time.
On the other hand, median size is the antibacterial glass of 20 μ m, as shown in Figure 2, the residual quantity of antibacterial glass will reduce during each the use, so the stripping quantity of the silver ions when just bringing into use is compared, be accompanied by the increase of washing times, stripping quantity significantly reduces.Therefore, be considered to just must frequently replenish antibacterial glass if guarantee desirable silver ions stripping quantity.
(4) shape 4
In addition, about the shape of antibacterial glass, preferably, shown in Fig. 5 (a)～(b), antibacterial glass all is a tabular, constitutes by with the thin-walled portion 12 of this antibacterial glass identical component a plurality of sheet glass 10a being connected.
Its reason is, for large-area antibacterial glass, considers the time of employed envrionment conditions, the water yield or life-time service etc., by so-called chocolate patterning method, antibacterial glass can be cut into any size and use.That is to say, utilize the thin-walled portion of regulation, large-area antibacterial glass is cut into prescribed level, can easily adjust the stripping quantity (dissolution rate) of silver ions.
In addition,, as place of incision, be used in combination the size and the shape in place, can make suitable antibacterial glass size and shape with the there because have the thin-walled portion of regulation.
(5) kind 1
In addition, about the kind of antibacterial glass, the preferred boric acid class antibacterial glass that uses with following composition.That is to say and contain B 2O 3, SiO 2, Ag 2O, alkalimetal oxide be as starting material, and, for total amount, B 2O 3Addition be 30～60 weight %, SiO 2Addition 30～60 weight %, Ag 2Addition 2～5 weight % of O, the addition of alkalimetal oxide are 5～10 weight %.
Its reason is, if such glass is formed formed antibacterial glass, directly contacts the silver ions that can emit specified amount rapidly with water.In addition,, lack with the reactivity of washing composition if such glass is formed formed antibacterial glass, for use that washing composition washs by antibiont, can stably implement the antimicrobial treatment of stipulating.
Here, B 2O 3Basically bringing into play the function that mesh forms oxide compound, in addition, in the present invention, also to improve the even release performance of function and silver ions relevant with the transparency of antibacterial glass.
In addition, SiO 2In antibacterial glass, bringing into play mesh and modifying the function of oxide compound, also bringing into play preventing xanthochromic function simultaneously.
In addition, Ag 2O is a constituent essential in the antibacterial glass, makes the silver ions stripping by the dissolving glass ingredient, can show excellent germ resistance for a long time.
In addition, such as Na 2O and K 2The alkalimetal oxide of O is being brought into play the effect that mesh is modified oxide compound basically, in addition, also can the controlled function that the transparency of antibacterial glass is improved function and melt temperature be played a role.
Have again, by the alkaline-earth metals oxide of further interpolation such as MgO and CaO, can bring into play the function that mesh is modified oxide compound, and, identical with alkalimetal oxide, also can the controlled function that the transparency of antibacterial glass is improved function and melt temperature be played a role.
Have again, by other interpolation CeO 2And Al 2O 3Deng, can improve discolouration and the transparency or physical strength for electron beam.
(6) kind 2
Have again, about the kind of antibacterial glass, the preferred phosphoric acid class antibiotic glass that uses with following composition.That is to say, contain P 2O 5, Ag 2O, alkalimetal oxide be as starting material, and, for total amount, P 2O 5Addition be 40～70 weight %, Ag 2Addition 2～5 weight % of O, the addition of alkalimetal oxide are 15～35 weight %.
Its reason is, if such glass is formed formed phosphoric acid class antibiotic glass, directly contacts the silver ions that can emit specified amount rapidly with water.In addition, if such glass is formed formed antibacterial glass, the transparency is excellent, and, no matter be the granular of tabular or regulation particle diameter, can emit the silver ions of specified amount at the appointed time, the ease of use excellence.Have again, if such phosphoric acid class antibiotic glass, the corrodibility with fusion kiln when making etc. is little, the gentleness of creating conditions, manufacturing cost reduce, the so-called manufacturing go up and advantage economically.
Here, P 2O 5Basically bringing into play the function that mesh forms oxide compound, in addition, in the present invention, also to improve the even release performance of function and silver ions relevant with the transparency of antibacterial glass.
In addition, Ag 2O is a constituent essential in the antibacterial glass, makes the silver ions stripping by the dissolving glass ingredient, can show excellent germ resistance for a long time.
In addition, such as Na 2O and K 2The alkalimetal oxide of O is being brought into play the effect that mesh is modified oxide compound basically, in addition, also can the controlled function that the transparency of antibacterial glass is improved function and melt temperature be played a role.
Have again, by the alkaline-earth metals oxide of further interpolation such as MgO and CaO, can bring into play the function that mesh is modified oxide compound, and, identical with alkalimetal oxide, also can the controlled function that the transparency of antibacterial glass is improved function and melt temperature be played a role.
Have again, by other interpolation CeO 2And Al 2O 3Deng, can improve discolouration and the transparency or physical strength for electron beam.
(7) silver ions stripping quantity
It is characterized in that the stripping quantity of silver ions is 0.5～100mg/ (g24Hrs) in the antibacterial glass.
Its reason is, if the not enough 0.5mg/ (g24Hrs) of the stripping quantity of described silver ions under situation that water directly contacts, is difficult to emit rapidly the silver ions of normality sometimes.
On the other hand,, be difficult to emit for a long time the silver ions of normality sometimes, perhaps be difficult to handle, perhaps be difficult to stable the manufacturing if the stripping quantity of described silver ions surpasses 100mg/ (g24Hrs).
Therefore, the stripping quantity of silver ions 1～90mg/ (g24Hrs) more preferably further is preferably 10～70mg/ (g24Hrs) in the antibacterial glass.
Have, the stripping quantity of silver ions can be measured according to the measuring method of record among the aftermentioned embodiment 1 in the antibacterial glass again.
2. coating material or additive
(1) title complex forms compound
Preferred interpolation can form the title complex formation compound of title complex with silver ions, for example, add independent a kind of in ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium thiosulfate, ammonium sulfide, EDTA (EDTA), ammonium acetate, ammoniumper chlorate and the ammonium phosphate or the combination of two or more.
Its reason is, forms compound by adding such title complex, can significantly prevent the variable color of antibacterial glass and painted.
Have again, even from environment strong basicity, for example pH value is 10 or more, also easy and silver ions forms title complex, can prevent painted angle consideration, form compound as title complex, more preferably use at least a compound that is selected from ammonium sulfate, ammonium nitrate, ammonium chloride and the ammonium thiosulfate.
In addition, title complex forms the addition of compound, for total amount, is preferably 0.01～30 weight %.
Its reason is if title complex forms the addition less than 0.01 weight % of compound, to be difficult to effectively prevent variable color sometimes.On the other hand, surpass 30 weight % if title complex forms the addition of compound, sometimes, the germ resistance in the antibacterial glass reduces, and perhaps is difficult to uniform mixing.
Therefore, be more preferably equilibriums such as the discoloration-resistant of antibacterial glass and germ resistance, from this point of view, title complex forms the addition of compound, for total amount, more preferably 0.1～20 weight %, further be preferably 0.5～10 weight %.
(2) coating material
In addition, as shown in Figure 6, as coating material, preferred form is at the particle 14 that covers inorganics and organism or any one party around the antibacterial glass 10.
By such formation, control the dissolution rate of silver ions easily, in addition, can make the anti-compendency of germ resistance good.
In addition, as the particle that covers antibacterial glass, preferably titanium dioxide, silicon-dioxide, colloid silica, zinc oxide, stannic oxide, plumbous oxide, white carbon black, acrylic acid or the like particle, vinylbenzene particle, polycarbonate particle etc. independent a kind of or the combination of two or more.
Have, there is no particular limitation to cover the method for antibacterial glass with particle, for example preferably with behind antibacterial glass and the particle uniform mixing, heats under 600～1200 ℃ temperature, makes glass melting, perhaps is fixed by tackiness agent again.
In addition, preferably make antibacterial glass around possess as the wrapping material of coating material or possess framework, carry out boxlikeization.
Its reason is by being provided with such coating material, to handle or can prevent the aggegationization of antibacterial glass during preservation easily.In addition, can improve usability during use, and, even under the situation of using strong current, can prevent that also it from flowing out from prescribed position.Have again, because by boxlikeization, so handle easily and exchange etc.
For example, preferably, shown in Fig. 7 (a), use the moisture proof material of aluminium lamination press mold 16 grades to encase a plurality of antibacterial glass 10a; Shown in Fig. 7 (b), it is encased being divided under the state of aliquot; In addition, shown in Fig. 7 (c), use open-cell material (mesh material) 18 to cover on every side.
In addition, when using granular or spherical shape as antibacterial glass, preferably, shown in Fig. 8 (a), antibacterial glass 10 is sealing into both ends of the surface by in the round shape framework 18 ' that covers than the little mesh material of its particle diameter, shown in Fig. 8 (b), they is coupled together carry out boxlikeization.By such formation, be difficult to the granular or spherical of the shape that covers with coating material even belong to, also the aggegation between the antibacterial glass can be controlled at inferior limit.In addition, by such formation, can extremely easily adjust the Ag stripping quantity.
Have again, granular antibacterial glass, particularly by being that starting material constitute with phosphoric acid class glass, thus can to remedy dissolution rate slow by enlarging glass surface area, the Ag stripping quantity that can obtain wishing.
(3) surface treatment
In addition, for antibacterial glass, for anti-oxidation or paintedization etc., preferred tensio-active agent, stearic acid, tetradecanoic acid, sodium stearate or the silane coupling agent etc. that add as dispersion agent; As the hindered phenol compound of oxidation inhibitor, hindered amine compound etc.; As the pigment of tinting material, dyestuff etc.
Have, the addition of these additives is preferably considered additive effect etc. and is formulated, for example, more preferably, for total amount, is respectively 0.01～30 weight % again.
3. make use-case
When using antibacterial glass of the present invention, preferably comprise following operation (C)～(D):
(C) antibacterial glass is directly contacted with water, make the operation (being called the contact operation sometimes) that contains silver ionized water
(D) handle by antibiont with containing silver ionized water, implement the operation (being called antibiotic operation sometimes) of antimicrobial treatment.
Have, below imagination is used the situation of washing machine 50 as shown in Figure 4, specifies the using method of described antibacterial glass (use in washing machine antibacterial glass) again.
(1) contact operation
Antibacterial glass has no particular limits with the method that water directly contacts, and preferably, for example antibacterial glass is immersed in the water, perhaps antibacterial glass is dropped in the current, and antibacterial glass is directly contacted with water, makes to contain silver ionized water.
At this moment, for example antibacterial glass is being used under the situation of washing machine, preferably, as shown in Figure 9, bypass pipe 26 is set, places use in washing machine antibacterial glass 10 there, open and close the valve 28 that is communicated with bypass pipe 26 in case of necessity, move the water to flow into, directly contact, obtain containing silver ionized water with use in washing machine antibacterial glass 10.
Its reason is that for example, only the final stage use in washing contains silver ionized water, thereby silver ions is run off in vain, that is to say, when washings is implemented antimicrobial treatment, can limit the usage quantity of use in washing machine antibacterial glass effectively.
(2) antibiotic operation
In addition, as shown in figure 10, preferably, contain silver ionized water 30 or direct impregnation is handled by antibiont 32, implement antimicrobial treatment by spray.
Have again,, can enumerate cloth, fibre object, non-woven fabrics, seat pad, clothes, towel class, footwear etc. as by the typical example of antibiont.
[the 2nd embodiment]
The 2nd embodiment is the manufacture method of antibacterial glass, and it is to be used for it is characterized in that being implemented the manufacture method of the antibacterial glass of antimicrobial treatment by the washing of antibiont or washing back by silver ions, comprises following operation (A)～(B):
(A) fusion operation: with starting material B 2O 3, SiO 2, Ag 2The heating of O, alkalimetal oxide makes it fusion, makes melten glass (below be sometimes referred to as the fusion operation);
(B) forming process:, be that 1～50mm, silver ions stripping quantity are the antibacterial glass (below be sometimes referred to as forming process) of 0.5～100mg/ (g24Hrs) Yi Bian form maximum diameter (t1) Yi Bian cool off melten glass.
1. fusion operation
Use B 2O 3, SiO 2, Ag 2O, alkalimetal oxide be as starting material, and, for total amount, B 2O 3Addition be 30～60 weight %, SiO 2Addition 30～60 weight %, Ag 2Addition 2～5 weight % of O, the addition of alkalimetal oxide are 5～10 weight %, use universal mixer to be stirred to uniform mixing at revolution under as 250rpm, 30 minutes condition.Then, use melting furnace, heating glass raw material as an example and under 1280 ℃, 3.5 hours condition makes glass melting liquid.
Have again, according to raw-material kind and cooperation ratio, heating condition that can the appropriate change melting furnace.
2. forming process
Forming process is the melten glass that frit obtains through fusion to be made the operation of the antibacterial glass of regulation shape.
Particularly, shown in Figure 11 (a)～(b), use turning unit 20a, the 20b of regulation to make, thereby can utilize the chocolate cutting of thin-walled portion, can be handled, adjust easily the antibacterial glass 10 of area and writing board shape effectively easily.
That is to say, melten glass 22 is dropped between two turning unit 20a, the 20b naturally from the top, and, utilize the recess 24 that is arranged on turning unit 20a surface, can be shaped as the antibacterial glass 10 of regulation.In addition, the centre portions of two turning unit 20a, 20b possesses cooling tube (not shown), and preferably the mode with surface temperature that can controls revolution parts 20a, 20b constitutes.Have, antibacterial glass is configured as oblong-shaped by thin-walled portion again, so, in order to keep specified temperature, to have in order cooling off again, preferably blown a cold wind in the surface of antibacterial glass.
Have, the building mortion shown in Figure 11 (a)～(b) possesses two turning unit 20a, 20b again, as variation, as shown in figure 12, although use planomural parts 20c to replace a turning unit 20b, but it is identical shape basically, also can obtain thin plate shaped antibacterial glass 10.
[the 3rd embodiment]
The 3rd embodiment is the manufacture method of antibacterial glass, and it is to be used for it is characterized in that being implemented the manufacture method of the antibacterial glass of antimicrobial treatment by the washing of antibiont or washing back by silver ions, comprises following operation (A ')～(B '),
(A ') the fusion operation: with starting material P 2O 5, Ag 2The heating of O, alkalimetal oxide makes it fusion, makes melten glass (below be sometimes referred to as the fusion operation);
(B ') forming process:, be that 1～50mm, silver ions stripping quantity are the antibacterial glass (below be sometimes referred to as forming process) of 0.5～100mg/ (g24Hrs) Yi Bian form maximum diameter (t1) Yi Bian cool off melten glass.
1. fusion operation
Use P 2O 5, Ag 2O, alkalimetal oxide be as starting material, and, for total amount, P 2O 5Addition be 30～60 weight %, Ag 2Addition 2～5 weight % of O, the addition of alkalimetal oxide are 5～40 weight %, use universal mixer to be stirred to uniform mixing at revolution under as 250rpm, 30 minutes condition.Then, use melting furnace, heating glass raw material as an example and under 1280 ℃, 3.5 hours condition makes glass melting liquid.
Have again, according to raw-material kind and cooperation ratio, heating condition that can the appropriate change melting furnace.
2. forming process 1
Forming process 1 is the melten glass that frit obtains through fusion to be made the operation of the antibacterial glass of regulation shape, particularly, melten glass is maintained semi-solid state before the completely solidified, forms the operation of plate glass.
Particularly, shown in Figure 13 (a), the melten glass 22 that utilizes aforesaid method to melt is flow in the shaped container 60 of regulation, can be shaped as semi-solid sheet glass 22 '.
At this moment, the material of shaped container 60 has no particular limits, so long as fusing point gets final product than antibacterial glass 10 high materials, but, preferably uses high-melting-point material or thermotolerance materials such as iron, stainless steel, carbon.Particularly, from the lightweight of shaped container 60, the aspect consideration of precise treatment easily, thermotolerance materials such as carbon are suitable constituent material.
In addition,,, shown in Figure 13 (a),, the temperature of shaped container 60 optimum value can be adjusted into, the semi-solid state of vitreousness can be made with regulation by refrigerating unit 61 is installed according to hope at the inner face of shaped container 60.
Have again,, can obtain the semi-solid plate glass 22 ' shown in Figure 13 (b) by implementing these methods.
2. forming process 2
Forming process 2 is operations that the semi-solid sheet glass 22 ' that will be in the forming process 1 be shaped is shaped as the sheet glass of specific thickness.
Particularly, shown in Figure 14 (a), in the space of the turning unit 20 ' that disposes with interval d1, insert semi-solid sheet glass 22 '.At this moment, at interval d1 is provided with forr a short time than the thickness d 2 of semi-solid sheet glass 22 ', thus can be shown in Figure 14 (b) like that, be configured as the antibacterial glass 10 that is spaced apart d1.
3. broken process
Broken process is to utilize prescriptive procedure to make antibacterial glass 10 fragmentations, is configured as granular, spherical, as to pulverize shapes such as body shape operation therefrom.
Particularly, use broken instrument such as hammer to be crushed to a certain degree size after, use ball milled etc. carries out break process.At this moment, by conditions such as appropriate change abrading-ball footpath, treatment times, can obtain aforesaid, desirable shape.
[embodiment]
Below, utilize embodiment, illustrate in greater detail the present invention.But, the following description is to give an example to of the present invention, and the present invention is not limited to these records.
[embodiment 1]
1. the making of antibacterial resin composition
(1) fusion operation
When being 100 weight %, with B with total amount 2O 3Ratio of components be 52 weight %, SiO 2Ratio of components be 36 weight %, Na 2The ratio of components of O is 9 weight %, Ag 2The ratio of components of O is the mode of 3 weight %, uses universal mixer that each frit is stirred to uniform mixing at revolution under as 250rpm, 30 minutes condition.Then, use glass melting furnace, heating glass raw material under 1280 ℃, 3.5 hours condition makes melten glass.
(2) forming process
To import in the insertion mouth of the manufacturing installation 40 shown in Figure 11 (a) from the melten glass that takes out the glass melting furnace, make and to implement chocolate that cut, flat use in washing machine antibacterial glass (rectangular-shaped small pieces, maximum diameter (t1): 15mm, thickness (t2): 3mm) continuously.
2. the evaluation of use in washing machine antibacterial glass
(1) the silver ions stripping property is estimated
The use in washing machine antibacterial glass 10g that obtains is immersed in the distilled water (20 ℃) of 100ml, uses vibrator vibration 24 hours.After using centrifuge separator to isolate the silver ions dissolution fluid, use filter paper (5C) to filter again, obtain measuring sample.Then, the silver ions of measuring in the sample is measured, calculated silver ions stripping quantity in the use in washing machine antibacterial glass (mg/ (g24Hrs)) with ICP Emission Spectrophotometer method.
(2) outflow property evaluation
At thickness is that 1mm, area are that the degree of depth is set is that 0.5mm, area are the recess of 5cm * 5cm for the stainless steel plate surface of 20cm * 20cm, fill 100g (W1) use in washing machine antibacterial glass there, under this state, from transverse direction winding-up flow 1 liter/minute tap water.This state continuance after 1 minute, is determined the weight (W2) of the use in washing machine antibacterial glass that remains on the stainless steel plate, calculate the residual rate ((W1-W2)/W1 * 100) of use in washing machine antibacterial glass.Then, according to following standard, estimate the outflow of use in washing machine antibacterial glass by the residual rate that calculates.
◎: residual rate is 90 weight %～100 weight %.
Zero: residual rate is for being equal to or greater than 70 weight % and less than 90 weight %.
△: residual rate is for being equal to or greater than 30 weight % and less than 70 weight %.
*: residual rate is less than 30 weight %.
(3) germ resistance evaluation
Use washing machine shown in Figure 4, implement the germ resistance evaluation for the cotton underwear that the use in washing machine antibacterial glass that utilizes gained is handled.That is to say, use washing machine shown in Figure 4, utilize the tap water that adds washing composition, washing cotton underwear.
End as shown in Figure 9, opens and closes the valve 28 that is communicated with the bypass pipe 26 that is placed with use in washing machine antibacterial glass 10 after washing, and allows water flow into, and use in washing machine antibacterial glass 10 is directly contacted with water, makes to contain silver ionized water.
Then, as shown in figure 10, contain silver ionized water 30 by spray conduct is implemented antimicrobial treatment by the cotton underwear 32 of antibiont.
The cotton underwear 32 that so obtains is placed under 35 ℃, 95%Rh, 48 hours envrionment conditions, with following condition evaluating germ resistance.
◎: the generation that does not observe stink and stain fully.
Zero: the generation that does not almost observe stink and stain.
△: observe the generation of a part of stink and stain.
*: observe the generation of significant stink and stain.
[embodiment 2～5]
Among the embodiment 2～5, as shown in table 1, except changing employed B among the embodiment 1 2O 3And SiO 2Ratio of components outside, other are operated similarly to Example 1, make the use in washing machine antibacterial glass respectively, estimate.
[comparative example 1～3]
In comparative example 1, use shredding unit and sorting equipment that the use in washing machine antibacterial glass of gained among the embodiment 1 is adjusted to the granular particle that median size is 20 μ m, in addition, estimate in the same manner with embodiment 1.
In addition, in the comparative example 2, using shredding unit and sorting equipment that the use in washing machine antibacterial glass of gained among the embodiment 1 is adjusted to major diameter is that 200 μ m, thickness are the flakey particle of 30 μ m, in addition, estimates in the same manner with embodiment 1.
Have again, in the comparative example 3, be that the use in washing machine antibacterial glass of 20 μ m adds in the acrylic resin, make that concentration is 10 weight % the median size that obtains in the comparative example 1, make the resin sheet that is mixed with the use in washing machine antibacterial glass, implement the silver ions stripping property and estimate and the germ resistance evaluation.
[table 1]
[embodiment 6]
1. the making of use in washing machine antibacterial glass
(1) fusion operation
When being 100 weight %, with P with total amount 2O 5Ratio of components be 70 weight %, Na 2The ratio of components of O is that the ratio of components of 18 weight %, CaO is 9 weight %, Ag 2The ratio of components of O is the mode of 3 weight %, uses universal mixer that each frit is stirred to uniform mixing at revolution under as 250rpm, 30 minutes condition.Then, use glass melting furnace, heating glass raw material under 1280 ℃, 3.5 hours condition makes melten glass.
(2) forming process
To import from the melten glass that takes out the glass melting furnace in the shaped container 60 shown in Figure 13 (a), after making the semi-solid sheet glass, by implementing building mortion and the pulverizing process shown in Figure 13 (b), obtain granulous use in washing machine antibacterial glass (maximum diameter (t1): 5mm, path (t2): 1mm).
2. the evaluation of use in washing machine antibacterial glass
Among the embodiment 6, carry out the evaluation of (1) silver ions stripping property, (2) outflow property evaluation and (3) germ resistance evaluation in the same manner with embodiment 1.
Have again, under 25 ℃, 8 hours condition, 10g use in washing machine antibacterial glass is immersed in 1 liter of pure water, then, from water, take out use in washing machine antibacterial glass, gravimetry (W3), calculate weight decrement ((10-W3)/10 * 100), as the persistence evaluation.
◎: the weight decrement is less than 10%.
Zero: the weight decrement is equal to or greater than 10% and less than 20%.
△: the weight decrement is equal to or greater than 20% and less than 50%.
*: the weight decrement is greater than 50%.
[embodiment 7～9, comparative example 4～6]
In embodiment 7～9, comparative example 4～6, as shown in table 2, change the P that uses among the embodiment 6 2O 5, CaO, Na 2In addition the ratio of components of O, makes the use in washing machine antibacterial glass respectively in the same manner with embodiment 6, estimates.
[table 2]
Figure A20071019545900261
Industrial utilizability
The silver ion that utilizes according to the present invention is to implemented the antibacterial glass of antimicrobial treatment by antibacterial, flat In the shape such as tabular or granular, maximum diameter (t1) is very big, so, for example in by the washing of antibacterial Or after the washing, directly contact with the water that is used for utilizing silver ion to implement antimicrobial treatment, thus can be rapidly and Emit for a long time the silver ion of ormal weight. In addition, according to the manufacture method of antibacterial glass of the present invention, In tabular or the shape such as granular, can effectively obtain greatly antibacterial glass of maximum diameter (t1).
And then, according to the using method of antibacterial glass of the present invention, with tabular or granular maximum Directly (t1) greatly antibacterial glass directly contact with water and obtain silver ion water, utilize this argentiferous from Sub-water is processed by antibacterial, thereby, to for example the washing in can be brought into play the antibiotic of regulation by antibacterial Effect.
Have again, according to antibacterial glass of the present invention, not only can be in this wise as the use in washing machine antibiotic property Glass uses, and also can be used for preferably requiring to emit rapidly and for a long time when directly contacting with water The purposes of the silver ion of ormal weight, for example, dish cleaning machine, vegetable washer, purifier, humidification The purposes such as device, humidity feedway, antiseptic solution feeding device, deodorant liquid feedway.

Claims (7)

1. antibacterial glass, it is to be used for directly contacting the flat antibacterial glass of emitting silver ions and bringing into play antibacterial effect with water, it is characterized in that:
Maximum diameter (t1) is 1～50mm,
Thickness is 0.1～10mm, and the silver ions stripping quantity is 0.5～100mg/ (g24Hrs),
And contain B 2O 3, SiO 2, Ag 2O, alkalimetal oxide be as starting material, for total amount, and B 2O 3Addition be 30～60 weight %, SiO 2Addition be 30～60 weight %, Ag 2The addition of O is that the addition of 2～5 weight %, alkalimetal oxide is 5～10 weight %,
Aforementioned silver ions stripping quantity be by with the 10g glass-impregnated in 20 ℃ 100ml distilled water, recorded in 24 hours with vibrator vibration.
2. antibacterial glass according to claim 1 is characterized in that, it is to be used for utilizing silver ions to implement the antibacterial glass of antimicrobial treatment after by the washing of antibiont or washing.
3. antibacterial glass according to claim 1 and 2 is characterized in that, described antibacterial glass all is a tabular, constitutes by with the thin-walled portion of this antibacterial glass identical component a plurality of sheet glass being connected.
4. antibacterial glass according to claim 1 and 2 is characterized in that, possesses coating material on every side, by boxlikeization.
5. the manufacture method of antibacterial glass, it is to be used for directly contacting the manufacture method of emitting silver ions and bringing into play the antibacterial glass of antibacterial effect with water, it is characterized in that, comprises following operation (A)～(B):
(A) fusion operation: with starting material B 2O 3, SiO 2, Ag 2O and alkalimetal oxide heating make it fusion, make B for total amount 2O 3Addition be 30～60 weight %, SiO 2Addition be 30～60 weight %, Ag 2The addition of O is that the addition of 2～5 weight %, alkalimetal oxide is the melten glass of 5～10 weight %;
(B) forming process: Yi Bian cool off melten glass, to form on one side flat, maximum diameter (t1) and be 1～50mm, thickness be 0.1～10mm, have the regulation shape and the silver ions stripping quantity is the antibacterial glass of 0.5～100mg/ (g24Hrs), aforementioned silver ions stripping quantity be by with the 10g glass-impregnated in 20 ℃ 100ml distilled water, recorded in 24 hours with vibrator vibration.
6. the manufacture method of antibacterial glass according to claim 5 is characterized in that, in operation (B), uses the surface to possess the turning unit of recess, is configured as flat antibacterial glass.
7. the manufacture method of antibacterial glass according to claim 5 is characterized in that, between operation (A) and operation (B), further comprises antibacterial glass is being possessed refrigerative operation on the substrate of refrigerating unit.
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KR100657123B1 (en) 2006-12-13
JPWO2005087675A1 (en) 2008-01-24
KR20060012326A (en) 2006-02-07
WO2005087675A1 (en) 2005-09-22
CN101298364B (en) 2011-02-16
CN1771207A (en) 2006-05-10
JP5378647B2 (en) 2013-12-25
JP2013155114A (en) 2013-08-15
CN100413799C (en) 2008-08-27

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