JP5114396B2 - Mixed antibacterial glass - Google Patents

Description

  The present invention relates to a mixed antibacterial glass, and in particular, to a mixed antibacterial glass containing a mixture of a colored antibacterial glass added with an inorganic colorant and a non-antibacterial glass.

In recent years, mixed antibacterial glass with a predetermined particle size has been incorporated into resins to provide antibacterial effects in building materials, home appliances (including TVs, personal computers, mobile phones, video cameras, etc.), sundries, and packaging materials. An antibacterial resin composition mixed with a predetermined amount is used.
As such an antibacterial resin composition, a synthetic resin molding containing a borosilicate antibacterial glass that elutes silver ions in the resin is disclosed (for example, see Patent Document 1).
More specifically, such a synthetic resin molding is composed of one or more network forming oxides of SiO ₂ , B ₂ O ₃ , P ₂ O ₅ , Na ₂ O, K ₂ O, CaO, ZnO. Borosilicate antibacterial glass containing 0.1 to 20 parts by weight of Ag ₂ O as monovalent Ag in 100 parts by weight of a glass solid comprising one or more types of network-modified oxide It is configured to include inside. Then, in the examples of the patent publication, _SiO 2: 40 _{mol%, B 2} O 3: 50 _mol%, Na 2 O: on 100 parts by weight of a mixture consisting of 10 mol%, the Ag ₂ O 2 parts An antibacterial resin composition containing an added antibacterial glass having an average particle size of 20 μm or less in a synthetic resin is disclosed.

In addition, as an antibacterial resin composition, a resin composition containing scale-like glass having an antibacterial particle size of 10 to 1000 μm and a thickness of 0.1 to 20 μm is disclosed (for example, see Patent Document 2). .
More specifically, as the composition of the glass flakes, when B ₂ O ₃ is contained, SiO ₂ : 20 to 60% by weight, B ₂ O ₃ : 30 to 70% by weight, Na ₂ O: 5 to 35% by weight, Ag ₂ O: 0.5 to 3% by weight, and when B ₂ O ₃ is not contained, SiO ₂ : 55 to 80% by weight, Al ₂ O ₃ : 0.5 to 30 % By weight, Na ₂ O: 19.5 to 42% by weight, and Ag ₂ O: 0.5 to 3% by weight.

Further, when immersed in water or acid at 20 ° C. for 24 hours after being immersed in boiling water at 100 ° C. for 500 to 1000 hours, the silver ion-containing inorganic system in which the elution amount of silver ions is 0.5 ng / cm ² / day or more An antibacterial wet-around product containing an antibacterial agent and an inorganic filler has been disclosed (for example, see Patent Document 3).
More specifically, Ag ₂ O is compounded in an amount of 0 to 5 wt% with respect to a glass component composed of P ₂ O ₅ : 56 to 59 mol%, MgO + CaO + ZnO: 33 to 38 mol%, and Al ₂ O ₃ : 6 to 8 mol%. The silver ion-containing inorganic antibacterial agent having an average particle diameter of 2 to 20 μm is added to the resin in the range of 0.5 to 5% by weight, and further the inorganic filler is in the range of 5 to 80% by weight. An antibacterial water-based product added in is disclosed.

In addition, antibacterial resin compositions exemplifying electrical products such as dishwashers, dish dryers, refrigerators, washing machines, pots, etc. have been proposed as antibacterial glass applications (see, for example, Patent Documents 4 to 6). .
That is, according to Patent Documents 4 to 5, in a molding resin constituting such an electric product, ZnO having an average particle diameter of 20 μm or less: 40 to 80 mol%, SiO ₂ : 5 to 35 mol%, CaO: 5 to 5 Antibacterial glass composed of 30 mol%, ZnO having an average particle diameter of 20 μm or less: 54 to 60 mol%, B ₂ O ₃ : 25 to 32 mol%, SiO ₂ : 7 to 12 mol%, alkali metal oxide : An antibacterial resin composition containing a predetermined amount of antibacterial glass composed of 5 to 8 mol% has been proposed.
According to Patent Document 6, the maximum diameter (t1) of the antibacterial glass is set to a value within a range of 1 to 50 mm, and the elution amount of silver ions is within a range of 0.5 to 100 mg / (g · 24 Hrs). The antibacterial properties of the antibacterial glass are made by bringing the antibacterial glass into direct contact with water to create silver ion-containing water and subjecting it to antibacterial treatment during or after washing. Glass and its manufacturing method are disclosed.
Furthermore, as an application of antibacterial glass, a glass water treatment agent used in water treatment apparatuses such as water storage tanks and cooling towers has been proposed (for example, see Patent Document 7).
That is, it is a phosphate glass having a longest diameter of 10 mm or more, and the weight composition ratio thereof is (RO + R ₂ O) / P ₂ O ₃ = 0.4 to 1.2, R ₂ O / (RO + R ₂ O ₃ ) = 0-10 (R is Ca, Na, etc.) and when the initial dissolution rate is A and the final dissolution rate is B, B / A ≧ 1/3 and the inclusion of metal ions It is a glass water treatment agent whose amount is 0.005 to 5% by weight.
Japanese Patent Laid-Open No. 1-313531 (Claims) Japanese Patent Laid-Open No. 7-25635 (Claims) JP-A-10-72530 (Claims) JP 2000-3238 A (Claims) JP 2000-3239 A (Claims) WO 2005/087675 (Claims) Japanese Patent Publication No. 7-63701 (Claims)

However, since all of the antibacterial resin compositions disclosed in Patent Documents 1 to 6 are configured by mixing an antibacterial glass in a resin, the antibacterial glass is substantially colorless and transparent. In many cases, the contained silver reacts with chlorine ions to cause discoloration or opacification.
Therefore, when such an antibacterial resin composition is used, there is a problem in that the appearance of the electric product is remarkably lowered during use even though the antibacterial property can be imparted to the parts of the electric product. It was seen.
Moreover, in patent documents 1 and 3-5, in order to mix uniformly in resin, it is assumed that the average particle diameter of fungal glass is preferably 20 μm or less, and in patent document 2, antibacterial glass is scale-like in a predetermined size. Although it was made of glass, there was a problem in manufacturing that a classifier or the like was used as a manufacturing apparatus and these values had to be limited to a predetermined range.
On the other hand, the antibacterial glass and the glass water treatment agent disclosed in Patent Documents 6 and 7 are relatively large in the longest diameter, but are used for electric products that use running water such as a dishwasher, a dish dryer, or a washing machine. When used, there was a problem that the effect of preventing discoloration was inferior or it was easy to crush.
In addition, the antibacterial glasses disclosed in Patent Documents 1 to 7 are all substantially colorless and transparent, and when they are provided with a covering member and formed into a cartridge, the presence cannot be identified from the outside. The problem was seen. That is, there is a problem that it is difficult to determine the replenishment time or replacement time of the antibacterial glass when the cartridge is used in an electric product.
Furthermore, all of the antibacterial glasses disclosed in Patent Documents 1 to 7 are water-soluble, and, for example, when used as an antibacterial glass for a washing machine, they dissolve and decrease in weight. There was a problem that it was unusable and inconvenient when stored in a predetermined container. That is, there has been a problem that the antibacterial glass contained in the predetermined container cannot be held in a state where it is submerged in the water of the washing machine, or the outer shape of the predetermined container cannot be maintained.

Therefore, as a result of intensive studies, the present inventors mixed colored antibacterial glass added with a predetermined amount of an inorganic colorant and non-antibacterial glass that is non-soluble and has no weight change. Thus, even when used as a mixed antibacterial glass for washing machines, the weight change is reduced and the usability is excellent, while a predetermined amount of silver ions is repeatedly applied while maintaining the initial appearance and distinguishability. The present invention has been completed by finding that it can be released.
That is, the present invention provides a mixed antibacterial glass capable of obtaining an excellent anti-discoloration effect and distinctiveness while maintaining a silver ion release amount within a predetermined range while maintaining a small change in weight during use and excellent usability. The purpose is to do.

According to the present invention, a mixed antibacterial glass comprising a colored antibacterial glass that exhibits antibacterial effects by releasing silver ions and a non-antibacterial glass, the maximum diameter (t1) of the colored antibacterial glass Is a value within the range of 3 to 30 mm, and contains cobalt oxide as an inorganic colorant as a blending component, and the added amount of the cobalt oxide is 0.001 to 0.00. A mixed antibacterial characterized by having a value within the range of 5% by weight and a silver ion elution amount in the colored antibacterial glass within a range of 0.01 to 1.0 mg / (g · 24 Hrs) Glass can be provided to solve the above-mentioned problems.
That is, according to the mixed antibacterial glass of the present invention, by including a colored antibacterial glass to which a predetermined amount of an inorganic colorant is added, the initial appearance and identification can be performed while exhibiting a predetermined antibacterial effect over a long period of time. Sex can be maintained. Therefore, the function of the inorganic colorant can effectively prevent discoloration of the resin derived from silver ions, and can easily identify its presence from the outside, and the entire mixed antibacterial glass or colored antibacterial glass It is possible to appropriately determine the replenishment time and replacement time.
In addition, with such a mixed antibacterial glass, not only the handling becomes easy, but the function of the non-antibacterial glass allows the coloring antibacterial glasses to be added to each other without adding an aggregation inhibitor such as silica or titanium oxide. Aggregation can be effectively prevented.
Furthermore, the non-antibacterial glass can function as a weight adjusting member, and the weight change during use becomes small. For example, even when used as a mixed antibacterial glass for a washing machine, It can be held as it is submerged in water, or the outer shape of a predetermined container can be held as it is.
Further, by using cobalt oxide as the inorganic colorant, excellent color developability can be obtained with a relatively small amount of addition in the colored antibacterial glass, and thus the entire mixed antibacterial glass. Accordingly, the amount of silver ions eluted is less affected, and a predetermined antibacterial effect can be exhibited for a certain period, while the initial appearance and distinguishability can be maintained over a long period of time.
In addition, with such an elution amount of silver ions, even when a mixed antibacterial glass is constituted together with a non-antibacterial glass, the initial appearance is exhibited while exhibiting a predetermined antibacterial effect over a longer period of time. And maintain discriminability.

In constituting the mixed antibacterial glass of the present invention, it is preferable that the colored antibacterial glass is flat and the thickness (t2) of the colored antibacterial glass is set to a value in the range of 1 to 8 mm. .
By using the mixed antibacterial glass including the colored antibacterial glass having such a thickness (t2), it is easy to handle and can be stably manufactured.

In constituting the mixed antibacterial glass of the present invention, it is preferable that the non-antibacterial glass contains soda glass as a main component.
Such a non-antibacterial glass is equivalent to the specific gravity of the colored antibacterial glass and is inexpensive, so that the mixed antibacterial glass can be produced stably and economically.

Moreover, when comprising the mixed antibacterial glass of this invention, it is preferable to make the maximum diameter (t3) of a non-antibacterial glass into the value within the range of 3-30 mm.
Such a non-antibacterial glass is substantially equal to the maximum diameter (t1) of the colored antibacterial glass, so that it is not only easily mixed with the colored antibacterial glass but also less likely to be unevenly distributed. be able to.

Moreover, when comprising the mixed antibacterial glass of this invention, it is preferable to make the addition amount of non-antibacterial glass into the value within the range of 10-3000 weight part with respect to 100 weight part of antibacterial glass.
If it is the addition amount of such non-antibacterial glass, while being able to express the predetermined antibacterial property as mixed antibacterial glass, the weight of the whole mixed antibacterial glass can be easily controlled.

In addition, in constituting the mixed antibacterial glass of the present invention, when washing a cloth product using a washing machine, it is put into a washing tub of the washing machine to give a predetermined antibacterial property to the cloth product and the washing tub. A mixed antibacterial glass, wherein a plurality of mixed antibacterial glasses are covered with a first water-permeable member, and a water-permeable periphery is further covered with a second water-permeable member. It is preferable.
Such a mixed antibacterial glass configuration for a washing machine not only improves usability, but also can efficiently impart predetermined antibacterial properties to fabric products, washing tubs, and the like.

In addition, in composing the mixed antibacterial glass of the present invention, it is added to the bath tub filled with bath water and floated on the bath water to give a predetermined antibacterial property to the bath water and tub. The antibacterial glass is preferably coated with a shape-retaining member and further covered with a water-permeable member.
Such a configuration of mixed antibacterial glass for bath not only improves usability, but also can efficiently impart predetermined antibacterial properties to bath water, a bathtub, and the like.

In addition, in constituting the mixed antibacterial glass of the present invention, a container provided with sanitary ware, for providing a predetermined antibacterial property to the sanitary ware, and having a water passage It is preferable to be accommodated in the inside.
Such a configuration of the mixed antibacterial glass for sanitary ware not only improves usability, but also can efficiently impart predetermined antibacterial properties to sanitary ware and the like.

(A)-(f) is a figure provided in order to demonstrate the shape of colored antibacterial glass. It is a figure provided in order to demonstrate the relationship between the maximum diameter (t1) of the coloring antibacterial glass contained in mixed antibacterial glass, and a residual rate. It is a figure provided in order to demonstrate the relationship with the elution amount of the silver ion accompanying the frequency | count of washing. It is a figure provided in order to demonstrate the relationship between the addition amount of cobalt oxide, and color developability. It is a figure provided in order to demonstrate the relationship between the addition amount of cobalt oxide and copper oxide, and the elution amount of silver ion. (A)-(b) is a figure provided in order to demonstrate the cartridge formation of mixed antibacterial glass. (A)-(c) is a figure provided in order to demonstrate the coating | coated member of mixed antibacterial glass. (A)-(b) is a figure provided in order to demonstrate the usage aspect of the mixed antibacterial glass for washing. (A)-(b) is a figure provided in order to demonstrate the usage aspect of the mixed antibacterial glass for bathtubs. (A)-(b) is a figure provided in order to demonstrate the usage aspect of the mixed antibacterial glass for sanitary ware. (A)-(b) is a figure provided in order to demonstrate the manufacturing method of mixed antibacterial glass (the 1). It is a figure provided in order to demonstrate another manufacturing method of mixed antibacterial glass. It is a figure which shows an example of the washing machine to which mixed antibacterial glass is applied. (A)-(b) is a figure provided in order to demonstrate the discoloration prevention effect of four types of mixed antibacterial glass (No1,2,3,4).

Hereinafter, embodiments relating to the mixed antibacterial glass of the present invention and methods for using the same will be described in detail.
That is, the mixed antibacterial glass of the present invention is a mixed antibacterial glass including a colored antibacterial glass that exhibits an antibacterial effect by releasing silver ions, and a non-antibacterial glass, The maximum diameter (t1) is set to a value within the range of 3 to 30 mm, and the compounding component contains cobalt oxide as an inorganic colorant, and the addition amount of the cobalt oxide is 0 with respect to the total amount. A value within the range of 0.001 to 0.5% by weight and a silver ion elution amount in the colored antibacterial glass within a range of 0.01 to 1.0 mg / (g · 24 Hrs ). It is a mixed antibacterial glass characterized.

1. Colored antibacterial glass (1) Shape 1
The shape of the colored antibacterial glass is not particularly limited. However, as shown in FIGS. 1A to 1F, a rectangular shape, a polygonal shape, a disc shape, an elliptical shape, an irregular shape, a perforated shape, and the like. It is preferable that it is flat form.
The reason for this is that the colored antibacterial glass is formed into a flat plate shape such as a rectangular shape or a disc shape, so that it is washed away by water pressure even when it is placed at a predetermined location and brought into direct contact with water. This is because it is possible to effectively prevent outflow from a predetermined location. In addition, if the colored antibacterial glass is rectangular or the like, the size and shape of the colored antibacterial glass can be controlled because it is difficult to agglomerate even when the colored antibacterial glasses are adjacent to each other during production or use. This is because it becomes easier to control the environmental conditions during use.
Moreover, as shown to Fig.1 (a)-(f), it is preferable that it is chamfered along the edge | side which comprises this colored antibacterial glass.
This is because, by adopting such a shape, the initial appearance and distinguishability can be maintained while exhibiting a predetermined antibacterial effect for a longer period of time. Moreover, it is because it can improve also about the moldability and polishability of colored antibacterial glass by setting it as such a chamfering shape.
Furthermore, if the colored antibacterial glass in such a form, not only is handling and replacement easy, but even when a relatively strong water flow is used, it flows out to the outside along with the water flow, This is because crushing can be effectively prevented.

(2) Shape 2
Further, the maximum diameter (t1) of the colored antibacterial glass is set to a value in the range of 3 to 30 mm. Here, the maximum diameter (t1) of the colored antibacterial glass is, for example, the maximum length when an arbitrary line is drawn in the shape of the colored antibacterial glass, as shown in FIGS. Means.
That is, the reason is that when the maximum diameter is less than 3 mm, when placed at a predetermined location and brought into direct contact with water, it is pushed away by water pressure and tends to flow out of the predetermined location. This is because it may be difficult to release a predetermined concentration of silver ions over a period of time, or may easily aggregate during storage.
On the other hand, when the maximum diameter exceeds 30 mm, it becomes difficult to handle or it becomes difficult to manufacture stably.
Accordingly, the maximum diameter of the colored antibacterial glass is more preferably set to a value within the range of 4 to 25 mm, and further preferably set to a value within the range of 5 to 15 mm.
The maximum diameter (t1) of the colored antibacterial glass is, for example, the maximum diameter in the plane direction when the colored antibacterial glass is flat, and is the diameter of the sphere when it is spherical.

Moreover, when this colored antibacterial glass is flat form, it is preferable to make thickness (t2) of a colored antibacterial glass into the value within the range of 0.1-10 mm.
The reason for this is that when the thickness of the colored antibacterial glass is less than 0.1 mm, it becomes difficult to release a predetermined concentration of silver ions, it becomes difficult to handle, and it is manufactured stably. This is because it may be difficult to do. On the other hand, when the thickness of the colored antibacterial glass exceeds 10 mm, it is difficult to handle or to manufacture stably.
Therefore, when the colored antibacterial glass has a flat plate shape, the thickness of the colored antibacterial glass is more preferably set to a value in the range of 1 to 8 mm, and further to a value in the range of 2 to 5 mm. preferable.
In addition, the maximum diameter (t1) and thickness (t2) of the colored antibacterial glass described above can be easily measured using, for example, an optical micrograph or a caliper.

(3) Shape 3
Next, regarding the shape of the colored antibacterial glass, the relationship between the maximum diameter (t1) in the planar direction of the colored antibacterial glass and the residual rate when the colored antibacterial glass is used will be described in detail with reference to FIG. To do. The horizontal axis of FIG. 2 indicates the maximum diameter (mm) in the planar direction of the colored antibacterial glass as a logarithm, and the vertical axis indicates the coloring in the examples described later when the colored antibacterial glass of each particle size is used. The residual ratio (%) measured according to the method for measuring the residual ratio of antibacterial glass is shown.
As apparent from FIG. 2, if the maximum diameter (t1) in the plane direction of the colored antibacterial glass is a value of 5 mm or more, the residual ratio shows a relatively high value, that is, a value of 50% or more, It is understood that it can withstand long-term use.

Next, with respect to the shape of the colored antibacterial glass, referring to FIG. 3, when the colored antibacterial glass according to the present invention (maximum diameter in the plane direction 15 mm) and the antibacterial glass having an average particle diameter of 20 μm are used, respectively. The change in the number of washings and the elution amount of silver ions will be described in detail. That is, the horizontal axis of FIG. 3 shows the number of times of washing using each colored antibacterial glass using a washing machine 50 as shown in FIG. 13 described later, and the vertical axis of FIG. The elution amount of silver ions (mg / (g · 24Hrs)). In FIG. 3, data about the colored antibacterial glass of the present invention is shown by a solid line A, and data about a colored antibacterial glass having an average particle size of 20 μm is shown by a dotted line B.
As shown in FIG. 3, in the colored antibacterial glass of the present invention, the maximum diameter in the plane direction is a predetermined size and is not swept away by water pressure or the like, so that the residual amount is not significantly reduced. . Therefore, it is understood that a desired amount of elution can be maintained even after repeated use. Therefore, it is understood that the colored antibacterial glass of the present invention can withstand long-term use.
On the other hand, antibacterial glass having an average particle size of 20 μm is used as the number of washing increases as the residual amount of antibacterial glass decreases each time it is used as shown in FIG. Compared with the elution amount of silver ions immediately after the start, the value of the elution amount is greatly reduced. Therefore, it is understood that it is necessary to replenish the antibacterial glass frequently in order to ensure the desired elution amount of silver ions.

(4) Type 1
Moreover, it is preferable to use the colored antibacterial glass which consists of the following compounding compositions in the state which does not contain an inorganic type coloring agent regarding the kind of colored antibacterial glass.
That is, as the first glass composition in the colored antibacterial glass, it contains Ag ₂ O when it contains Ag ₂ O, ZnO, CaO, B ₂ O ₃ and P ₂ O ₅ and the total amount is 100% by weight. A value in the range of 0.2 to 5% by weight, a ZnO content in the range of 1 to 50% by weight, a CaO content in the range of 0.1 to 15% by weight, B The content of ₂ O ₃ is set to a value within the range of 0.1 to 15% by weight, and the content of P ₂ O ₅ is set to a value within the range of 30 to 80% by weight, and the weight ratio of ZnO / CaO is set to A value in the range of 1.1 to 15 is preferable.
The reason for this is that when the weight ratio of ZnO / CaO is less than 1.1, yellowing of the colored antibacterial glass may not be effectively prevented, whereas the weight ratio of ZnO / CaO. If the value exceeds 15, the colored antibacterial glass may become cloudy or, conversely, yellow.
Therefore, the weight ratio represented by ZnO / CaO is more preferably set to a value within the range of 1.2 to 10, and further preferably set to a value within the range of 1.5 to 8.

Further, as a second glass composition, instead free of ZnO _{substantially,} Ag 2 O, _CaO, include B 2 _{O 3} and _P 2 _{O 5,} and, when the total amount was 100 wt%, The content of Ag ₂ O is in the range of 0.2 to 5% by weight, the content of CaO is in the range of 15 to 50% by weight, and the content of B ₂ O ₃ is 0.1 to 15% by weight. %, And the content of P ₂ O ₅ is set to a value within a range of 30 to 80% by weight, and the weight ratio of CaO / Ag ₂ O is set to a value within a range of 5 to 15 Antibacterial glass.
The reason for this is that when the weight ratio of such CaO / Ag ₂ O becomes a value of less than 5, yellowing of the colored antibacterial glass may not be effectively prevented, while the CaO / Ag ₂ O This is because if the weight ratio exceeds 15, the colored antibacterial glass may become cloudy or, conversely, yellow.
Accordingly, the weight ratio represented by CaO / Ag ₂ O is more preferably a value within the range of 6 to 12, and further preferably a value within the range of 7 to 10.

Further, as a third glass _composition, Ag 2 _{O, CaO,} include _{B 2 O 3, P 2 O} 5 and _Al 2 _{O 3,} and, when the total amount was 100 wt%, of _Al 2 _{O 3} It is a colored antibacterial glass having a content in the range of 0.5 to 10% by weight.
This is because it is possible to effectively suppress the deliquescence phenomenon by adding Al ₂ O ₃ as described above.
That is, when the content of Al ₂ O ₃ is less than 0.5% by weight, the effect of suppressing the deliquescence phenomenon may not be exhibited. On the other hand, when the content of Al ₂ O ₃ exceeds 10% by weight, the antibacterial effect may not be exhibited.
Therefore, it can be said that it is more preferable to set the content of Al ₂ O ₃ to a value within the range of 1 to 5% by weight.

(5) Type 2
In addition, the colored antibacterial glass contains an inorganic colorant, and the addition amount of the inorganic colorant is set to a value within the range of 0.001 to 0.5% by weight with respect to the total amount. Features.
This is because the size of the colored antibacterial glass and the elution amount of silver ions can be easily limited to a predetermined range by adding a predetermined amount of an inorganic colorant.
Therefore, the initial appearance and distinguishability can be maintained while exhibiting a predetermined antibacterial effect over a long period of time. In other words, the action of the inorganic colorant can effectively prevent the resin discoloration prevention effect derived from silver ions, and even if it is provided with a covering member and made into a cartridge, its presence from the outside. It can be easily identified, and the replenishment time and replacement time of the colored antibacterial glass can be accurately determined.
In addition, these large forms of colored antibacterial glass not only facilitate handling, but also effectively prevent the colored antibacterial glass from contacting and aggregating by simply combining with non-antibacterial glass. This is because it can be done.
Therefore, the addition amount of the inorganic colorant in the colored antibacterial glass is more preferably set to a value within the range of 0.003 to 0.1% by weight with respect to the total amount, 0.005 to 0.05. More preferably, the value is within the range of% by weight.

Here, the influence of the addition amount of the inorganic colorant in the colored antibacterial glass will be described with reference to FIGS.
The horizontal axis in FIG. 4 indicates the amount (% by weight) of cobalt oxide added to the colored antibacterial glass in logarithm, and the vertical axis indicates the color developability (relative value) of the colored antibacterial glass. The color developability of the colored antibacterial glass indicates that the larger the number, the better, and a value corresponding to the visible light absorption.
In addition, the horizontal axis of FIG. 5 indicates the amount (% by weight) of the inorganic colorant (cobalt oxide and copper oxide) added to the colored antibacterial glass in logarithm, and the vertical axis indicates the silver ion in the colored antibacterial glass. The elution amount (mg / (g · 24 Hrs)) is shown. In FIG. 5, the characteristic curve with the symbol A is a case where cobalt oxide is used as the inorganic colorant, and the characteristic curve with the symbol B is copper oxide as the inorganic colorant. Is used.
Therefore, as apparent from FIG. 4, if the addition amount of cobalt oxide in the colored antibacterial glass is 0.001% by weight or more, a predetermined color developability is obtained, and further, the addition amount of cobalt oxide increases. The color developability is also good, and when it exceeds 0.1% by weight, it tends to saturate.
On the other hand, as is clear from FIG. 5, as the amount of inorganic colorant (cobalt oxide and copper oxide) added to the colored antibacterial glass increases, the silver ion elution amount (mg / (g · 24 Hrs)) gradually increases. There is a tendency to decrease.
Therefore, referring to FIG. 4 and FIG. 5, in order to balance the color developability in the colored antibacterial glass and the elution amount of silver ions, the addition amount of the inorganic colorant is 0.001 relative to the total amount. It can be understood that it is effective to set the value within a range of ˜0.5% by weight.

In addition, when considering the addition amount of the inorganic colorant contained in the colored antibacterial glass, it is preferable to consider the addition amount of silver oxide.
That is, when the addition amount of the inorganic colorant contained in the colored antibacterial glass is C1, and the addition amount of silver oxide similarly contained is C2, the ratio represented by C1 / C2 is 0.01 to 3 It is preferable to set the value within the range.
The reason for this is that by controlling the amount of inorganic colorant added in association with the amount of silver oxide added, the initial appearance and distinctiveness can be maintained without suppressing the display of a predetermined antibacterial effect. Because it can. That is, when the ratio represented by C1 / C2 is less than 0.01, the expression of the discoloration preventing effect may be poor. On the other hand, if the ratio represented by C1 / C2 exceeds 3, the expression of the antibacterial effect may be poor.
Therefore, the ratio represented by C1 / C2 is more preferably set to a value within the range of 0.01 to 2, and further preferably set to a value within the range of 0.05 to 1.

(6) Type 3
In addition, the type of the inorganic colorant is cobalt oxide (CoO) so as to easily develop color in an oxidizing atmosphere, and is characterized by copper oxide (CuO), chromium oxide (Cr ₂ O ₃ ), nickel oxide (NiO). ), Manganese oxide (MnO ₂ ), neodymium oxide (Nd ₂ O ₃ ), erbium oxide (Er ₂ O ₃ ), cerium oxide (CeO ₂ ) and the like alone or in combination with two or more. .

With cobalt oxide , even if it is added in a very small amount, for example, 0.005% by weight, an excellent brilliant ink blue color developability can be obtained, and the initial appearance and identification can be achieved without suppressing the predetermined antibacterial effect. Sex can be maintained.
Moreover, if it is copper oxide, the sky blue color developability can be obtained with a relatively small amount of addition, and the initial appearance and distinguishability can be maintained without suppressing the antibacterial effect.
Moreover, if it is chromium oxide, the coloring property of a young grass can be obtained with a relatively small amount of addition, and the initial appearance and distinguishability can be maintained.
In addition, if nickel oxide is used, it is possible to obtain an astringent green color developability with a relatively small amount of addition on the condition that the potash component is large, and to maintain the initial appearance and distinguishability.
Further, with manganese oxide, a vivid purple color developability can be obtained with a relatively small amount of addition under the condition that an oxidizing agent is present, and the initial appearance and distinguishability can be maintained.
Further, if neodymium oxide is used, even if the amount of addition varies, a lavender purple color developability can be obtained in a wide range, and the initial appearance and distinguishability can be maintained. Moreover, when the glass raw material with much iron etc. is used, the decoloring effect can also be exhibited.
Furthermore, if erbium oxide or cerium oxide is used, pink color developability can be obtained, and the initial appearance and distinguishability can be maintained.

(7) silver ion elution amount also characterized in that a value within the range of the elution amount of silver ions in the colored antibacterial glass 0.01~1.0mg / (g · 24Hrs).
The reason for this is that when the elution amount of such silver ions is less than 0.01 mg / (g · 24 Hrs), when the mixed antibacterial glass is formed and brought into direct contact with water, the predetermined concentration is rapidly reached. This is because it may be difficult to release silver ions and exert a predetermined antibacterial effect.
On the other hand, when the elution amount of such silver ions exceeds 1.0 mg / (g · 24 Hrs), it becomes difficult to release a predetermined concentration of silver ions over a long period of time, handling becomes difficult, or stable. This is because it becomes difficult to manufacture.
Therefore, it is preferable that the elution amount of silver ions in the colored antibacterial glass is set to a value within the range of 0.015 to 0.5 mg / (g · 24 Hrs). Furthermore, it is more preferable to set it as the value within the range of 0.02-0.4 mg / (g * 24Hrs).
In addition, the elution amount of silver ions in the colored antibacterial glass can be measured according to the measurement method described in Example 1 described later. Further, conventionally, when used in a washing machine or the like, it has been considered that the elution amount of silver ions in the colored antibacterial glass has a good value in the range of 0.5 to 100 mg / (g · 24 Hrs). Since the antibacterial effect increases by repeating, knowledge that the same antibacterial effect can be obtained even with a smaller amount of silver ion elution has been obtained.

2. Non-antibacterial glass (1) types Non-antibacterial glass, that is, glass that dissolves in water and does not elute silver ions is not particularly limited. For example, soda glass, borosilicate glass Lead glass (crystal glass), quartz glass, aluminosilicate glass, and phosphate glass are preferable.
More specifically, with respect to the total amount, SiO ₂ or the like is in the range of 35 to 65% by weight as the glass network component, and Na ₂ O, K ₂ O, Li ₂ O, CaO, MgO as the glass network modifying component. Non-antibacterial glass mainly composed of soda glass obtained by adding at least one of BaO, B ₂ O ₃ , Al ₂ O _{3 and the} like in a range of 15 to 35% by weight is preferable.
In addition, it is also preferable to add a predetermined amount of a colorant, a reducing agent, an ultraviolet absorber and the like.

(2) Shape The shape of the non-antibacterial glass is not particularly limited, but is preferably, for example, spherical, flat, cylindrical, or polyhedral.
Among these, the planar shape is more preferably a flat plate shape such as a rectangle, a polygon, a disc, an ellipse, an irregular shape, a hole, and the like.
This is because the non-antibacterial glass is made into a flat plate shape such as a rectangle or a disk, and even if it is placed in a predetermined place and brought into direct contact with water, only the non-antibacterial glass is used. In addition, the colored antibacterial glass can be effectively prevented from being swept away by water pressure and flowing out from a predetermined location.

(3) Size Regarding the size of the non-antibacterial glass, the maximum diameter (t3) is preferably set to a value within the range of 3 to 30 mm.
The reason for this is that such a non-antibacterial glass is substantially equal to the maximum diameter (t1) of the colored antibacterial glass, so that it is easy to mix uniformly with the colored antibacterial glass. This is because uneven distribution can be made difficult.
Therefore, the antibacterial property can be further expressed in a balanced manner, and the weight of the entire mixed antibacterial glass can be controlled. Therefore, the maximum diameter (t3) of the non-antibacterial glass should be set to a value within the range of 5 to 20 mm. Preferably, the value is in the range of 8 to 15 mm.
Moreover, when this non-antibacterial glass is flat form, it is preferable to make thickness (t4) of a non-antibacterial glass into the value within the range of 0.1-10 mm.
This is because, when the thickness of the non-antibacterial glass is less than 0.1 mm, the mechanical strength is remarkably lowered, handling becomes difficult, and it becomes difficult to manufacture stably. It is because there is a case where it is. On the other hand, if the thickness of the non-antibacterial glass exceeds 10 mm, it is difficult to handle or to manufacture stably.
Therefore, when the non-antibacterial glass is flat, it is more preferable to set the thickness of the non-antibacterial glass to a value in the range of 1 to 8 mm, and further to a value in the range of 2 to 5 mm. preferable.

(4) Addition amount The addition amount of the non-antibacterial glass is preferably set to a value within the range of 10 to 3000 parts by weight with respect to 100 parts by weight of the colored antibacterial glass.
The reason for this is that, with such an added amount of non-antibacterial glass, the predetermined antibacterial property as a mixed antibacterial glass can be expressed and the weight of the entire mixed antibacterial glass can be easily controlled. This is because it can. That is, if such an amount of non-antibacterial glass is added, it becomes easy to mix uniformly with the colored antibacterial glass and is less likely to be unevenly distributed. This is because it can be easily controlled.
Therefore, the antibacterial property can be expressed in a well-balanced manner, and the weight of the entire mixed antibacterial glass can be easily and accurately controlled. Therefore, the added amount of the non-antibacterial glass is reduced to 100 parts by weight of the colored antibacterial glass. On the other hand, it is more preferable to set the value within the range of 30 to 2000 parts by weight, even more preferable to set the value within the range of 50 to 1000 parts by weight, and to set the value within the range of 70 to 200 parts by weight. Is most preferred.

3. Covering member (1) Covering member It is also preferable that the covering member has a form in which a plurality of mixed antibacterial glasses are coated with an inorganic substance and an organic substance.
The reason for this is that by constituting in this way, it is possible to easily control the elution rate of silver ions and to improve the anti-aggregation property of the mixed antibacterial glass.

In addition, as particles covering the mixed antibacterial glass, one kind or two or more kinds of titanium oxide, silicon oxide, colloidal silica, zinc oxide, tin oxide, lead oxide, white carbon, acrylic particles, styrene particles, polycarbonate particles, etc. The combination of is preferable.
Further, the method of coating the mixed antibacterial glass with particles is not particularly limited. For example, the mixed antibacterial glass and the particles are uniformly mixed and then heated to a temperature of 600 to 1200 ° C. to be melted into the glass. It is preferable to fix it via a binder.

Further, as shown in FIGS. 6A and 6B, the surroundings of the mixed antibacterial glass 10 'are provided with a wrapping member 18' as a covering member or a housing to form a cartridge. It is preferable to do.
The reason for this is that provision of such a covering member facilitates handling during storage and prevents aggregation of the mixed antibacterial glass. Further, in use, the usability is improved, and even when a relatively strong water flow is used, it is possible to prevent outflow from a predetermined place. Furthermore, since it is a cartridge, handling and replacement can be easily performed.

  Further, as shown in FIG. 7 (a), a plurality of mixed antibacterial glasses 10 are packaged by using a moisture-proof material such as an aluminum laminated film 16, or in a subdivided state as shown in FIG. 7 (b). It is also preferable to package or further cover the periphery with a perforated member 18 as shown in FIG.

(2) Surface treatment Also for mixed antibacterial glass, for the purpose of preventing oxidation or coloring, a surfactant as a dispersant, stearic acid, myristic acid, sodium stearate, or silane coupling It is preferable to add a pigment, a dye, or the like as a colorant, such as a hindered phenol compound or a hindered amine compound as an antioxidant.
In addition, it is preferable to determine the addition amount of these additives in consideration of the addition effect and the like. For example, each of the additives is set to a value within a range of 0.01 to 30% by weight with respect to the total amount. More preferred.

4). Use mode (1) Combination of colorless and transparent antibacterial glass In addition, as a mode of using mixed antibacterial glass, antibacterial glass (colorless transparent antibacterial glass) containing no inorganic colorant is used for mixed antibacterial glass. It is preferable to further add in the range of 10 to 90% by weight with respect to the total amount of the mixed antibacterial glass.
The reason for this is that a colored antibacterial glass having a relatively large maximum diameter (t1, t3), while the silver elution amount of the mixed antibacterial glass can be adjusted by using such a colorless transparent antibacterial glass in combination. This is because the discoloration-preventing effect can eliminate the discoloration of the colorless and transparent antibacterial glass.
Further, by configuring in this way, even when the average particle diameter of the colorless and transparent antibacterial glass is, for example, fine particles of 100 μm or less, the colored antibacterial glass having a relatively large maximum diameter (t1, t3) This is because the contact between the colorless and transparent antibacterial glasses can be inhibited to exhibit a predetermined anti-aggregation effect.
Therefore, the colorless and transparent antibacterial glass is more preferably added in the range of 20 to 80% by weight, and more preferably in the range of 30 to 70% by weight, based on the total amount of the mixed antibacterial glass.

(2) Mixed antibacterial glass for washing As a usage mode of the mixed antibacterial glass, when washing a cloth product using a washing machine, it is put into a washing tub of the washing machine and predetermined for the cloth product and the washing tub. The antibacterial glass is preferably a mixed antibacterial glass.
That is, in constituting the mixed antibacterial glass for washing, as shown in FIG. 8, a plurality of mixed antibacterial glasses (not shown) are covered with the fine water-permeable first water-permeable member 17. The first water-permeable member 17 is preferably further covered with the second water-permeable member 17b having a coarse mesh. And while making the 1st water-permeable member 17 into a bag shape as a whole, the circumference | surroundings are stitched | sutured by the sealing member 17a, and mixed antibacterial glass (not shown) is enclosed. Further, the second water-permeable member 17b is also formed into a bag shape as a whole, a part thereof is sewn with the sealing member 17c, and the first water-permeable member 17 sealed with the mixed antibacterial glass is sealed. is there.
The reason for this is that, if the mixed antibacterial glass for such a washing machine is used, the coated antibacterial glass coated in this manner is simply put into the washing tub during washing, and the fabric product and the laundry This is because predetermined antibacterial properties can be efficiently imparted to the tank or the like. Moreover, since it coat | covers twice, even if it stirs with a washing machine, it is because it can prevent mixing antibacterial glass flowing out outside easily.
Examples of the fine water-permeable first water-permeable member include felts and nonwoven fabrics having a pore size of less than 0.1 mm. On the other hand, examples of the second water-permeable member having a coarse mesh include a mesh material having a pore size of 0.2 mm or more, more preferably in a range of 2 mm to 20 mm.
In addition, as a typical example of the antibacterial object, in the case of a washing machine, a woven fabric, a fiber material, a nonwoven fabric, a mat-like material, clothes, towels, footwear, underwear, and the like can be given.

(3) Mixed antibacterial glass for bathtubs As another use mode of mixed antibacterial glass, it is put into a bath tub filled with bath water, floated in bath water, and predetermined for bath water and bathtub The antibacterial glass is preferably a mixed antibacterial glass.
That is, in configuring the mixed antibacterial glass for a bathtub, as shown in FIG. 9, a plurality of mixed antibacterial glasses (not shown) are surrounded by a fibrous shape holding member 19a, It is preferable that the periphery is further covered with a water-permeable member 19b. And it is preferable that the insertion port of the bag-like water-permeable member 19b is fixed by a stopper 19c, for example, to be ball-shaped as a whole.
This is because the mixed antibacterial glass for such a bath can be used for holding the mixed antibacterial glass and can maintain a predetermined shape as a whole. In addition, if it is such a use mode, the bath water and the bath water supply pipe, the bath tub, the bath water, the bath water drain pipe, etc. This is because a predetermined antibacterial property can be efficiently imparted to a bathtub or the like.
In addition, if the whole shape of the mixed antibacterial glass for bath is a ball shape as shown in FIG. 9, it can also be used as a scratching tool.

(4) Mixed antibacterial glass for sanitary ware In addition, as another usage mode of the mixed antibacterial glass, mixed antibacterial property for providing sanitary ware with predetermined antibacterial properties in preparation for sanitary ware. Glass is preferred.
That is, as shown in FIG. 10, it is preferable to be accommodated in a container 21 provided with water passages 21a, 21b, 21c, 21d. Moreover, it is preferable that the hinge 21g is provided and the structure can be opened and closed by being divided into two. And it is preferable to provide the fixing | fixed part 21f which has a hole in order to hang | hang or fix this container 21 in a predetermined place in the state which accommodated mixed antibacterial glass.
The reason for this is the use of mixed antibacterial glass for sanitary ware, such as sanitary ware water supply pipe, sanitary ware water tank, sanitary ware container interior, sanitary ware water drain pipe, etc. This is because a predetermined antibacterial property can be efficiently imparted to sanitary ware and the like simply by being placed at a predetermined location.

(5) Other usage modes Although not shown in the drawings, the mixed antibacterial glass is directly or indirectly put into a liquid tank or the like in a so-called spraying device or humidifying device, and contains an antibacterial liquid containing silver ions. Also preferred is a use mode for supplying. That is, the mixed antibacterial glass having a small weight change can stably come into contact with water and can supply an antibacterial liquid having a constant silver ion concentration.
Moreover, the form of the mixed antibacterial glass for sanitary ware as shown in FIG. 10 can be provided as it is in the vicinity of the kitchen sink. In other words, baskets and rubber products in the vicinity of sinks for sinks are prone to so-called “slimming”, but the antibacterial glass with little change in weight should stably prevent the occurrence of such “slinging”. Can do.

5. Manufacturing method (1) Manufacturing method of colored antibacterial glass First, a flat colored antibacterial glass that exhibits an antibacterial effect by releasing silver ions is manufactured including the following steps (A) to (B). Can do.
(A) Melting step of heating and melting the raw material to create a colored molten glass containing 0.001 to 0.5% by weight of an inorganic colorant relative to the total amount (B) Cooling the colored molten glass However, the molding step for producing a mixed antibacterial glass having a maximum diameter (t1) of 3 to 30 mm. That is, according to such a production method, even if it is in direct contact with water, a predetermined amount is obtained over a long period of time. A colored antibacterial glass capable of maintaining the initial appearance and distinguishability while exhibiting the antibacterial effect can be efficiently produced.
Hereinafter, the manufacturing method of colored antibacterial glass will be described more specifically.

First, using a universal mixer, the raw material is agitated using a universal mixer at a rotational speed of 250 rpm for 30 minutes until it is uniformly mixed. At this time, an inorganic colorant such as cobalt oxide is added so as to have a value within the range of 0.001 to 0.05% by weight.
Next, using a melting furnace, as an example, the glass raw material is heated under conditions of 1280 ° C. and 3 hours and a half to create a glass melt.
The heating conditions in the melting furnace can be changed as appropriate according to the type of raw materials and the blending ratio.

Next, a molding process is performed, and the molten glass obtained by melting the glass raw material is used as a colored antibacterial glass having a predetermined shape.
Specifically, as shown in FIGS. 11 (a) to 11 (b), by using predetermined rotating members 20 a and 20 b, chocolate cut using a so-called thin portion is possible, The colored antibacterial glass 10 that can be easily adjusted in area and shape can be obtained efficiently.
That is, the molten glass 22 is naturally dropped between the pair of rotating members 20a and 20b from above, and the predetermined mixed antibacterial glass 10 is formed using the recess 24 provided on the surface of the rotating member 20a. Can do. Further, it is preferable that a cooling pipe (not shown) is provided at the center of the pair of rotating members 20a and 20b so that the surface temperature of the rotating members 20a and 20b can be controlled. Furthermore, since the colored antibacterial glass is formed in a strip shape through the thin wall portion, the predetermined temperature is maintained, so that cooling air is blown on the surface of the antibacterial glass for further cooling. It is preferable.

Next, a surface polishing step is performed, that is, using a stirrer or pulverizer such as a V blender, a ball mill, or a vibration ball mill, and the obtained flat antibacterial glass and water or alcohol (isopropyl alcohol, etc.) A clean surface is ensured by mixing and stirring at room temperature for about 10 minutes to 24 hours to remove foreign matter and the like attached to the surface of the colored antibacterial glass. At the same time, it is preferable to deburr and further chamfer along the side of the flat antibacterial glass.
That is, by performing the surface polishing step in this way, the amount of silver elution increases from the beginning, and the control of the silver elution amount is facilitated.

(2) Method for producing non-antibacterial glass Non-antibacterial glass can also be produced in the same manner as colored antibacterial glass, except that no inorganic colorant or silver oxide raw material is added.
That is, it can be efficiently manufactured by mixing, melting, molding, and polishing raw materials of non-antibacterial glass.

(3) Mixing step Next, in the mixing step, the obtained colored antibacterial glass and non-antibacterial glass can be uniformly mixed using a mixing device.
Moreover, as a mixing stirring apparatus, a propeller mixer, a kneader, a ball mill, a sand mill, etc. can be used.
However, depending on the application, the mixing process may be omitted, and the colored antibacterial glass and non-antibacterial glass obtained will be prepared separately, and in the mixed antibacterial glass coating container (clothing material) It is also possible to mix with. That is, in the usage mode such as mixed antibacterial glass for washing and mixed antibacterial glass for bath, it is vibrated during washing or floating in the bath. This is because the glass is naturally mixed.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.

[Example 1]
1. Preparation of mixed antibacterial glass (1) Preparation of antibacterial glass (1) -1 Melting step As shown in Table 1, when the total amount is 100% by weight, Ag ₂ O is 3 wt%, ZnO 30 wt%, CaO 20 wt%, B ₂ O ₃ 5 wt%, P ₂ O ₅ 42 wt%, and CoO as a colorant 0.01 wt% The glass raw material corresponding to each glass composition was stirred using a universal mixer at a rotational speed of 250 rpm for 30 minutes until uniformly mixed.
Next, using a glass melting furnace, the glass raw material was heated under the conditions of 1280 ° C. and 3 hours and a half to prepare a molten glass.

(1) -2 Molding process The molten glass taken out from the glass melting furnace is introduced into a molding apparatus 40 as shown in FIG. 12, and is mixed with a disk-shaped mixed antibacterial glass (rectangular small piece, maximum diameter (t1): 15 mm. , Thickness (t2): 4 mm).

(1) -3 Surface polishing step 500 g of the obtained disc-shaped antibacterial glass was put into a vibration ball mill that does not use media. Next, 500 g of isopropyl alcohol or water was added, and in this state, the vibrating ball mill was operated at room temperature for 30 minutes, and a surface polishing process including a deburring process was performed.
As a result, before the surface polishing process, fine irregularities were observed, but after the surface polishing process, the surface became smooth and glossy.

(2) Preparation of non-antibacterial glass (2) -1 Melting step When the total amount is 100% by weight in a glass melting furnace, SiO ₂ is 58.8% by weight, NaO ₂ is 27.0% by weight, Silica sand, soda ash, lime, and the like were added so that B ₂ O ₃ was 10.0 wt%, CaO was 3.0 wt%, and K ₂ O was 1.2 wt%. Subsequently, the temperature of the glass melting furnace was set to 1350 ° C., and the mixture was heated and melted under conditions of 10 hours.

(2) -2 Molding Step Molten glass taken out from the glass melting furnace is introduced into a molding apparatus 40 as shown in FIG. 11, and is formed into a disk-shaped non-antibacterial glass (rectangular small piece, maximum diameter (t3): 15 mm. , Thickness (t4): 4 mm).

(2) -3 Surface polishing step 500 g of the obtained disc-shaped non-antibacterial glass was put into a vibration ball mill that does not use media. Next, 500 g of isopropyl alcohol or water was added, and in this state, the vibrating ball mill was operated at room temperature for 30 minutes, and a surface polishing process including a deburring process was performed.

(3) Mixing step Next, using a ball mill without a dispersing medium, the obtained colored antibacterial glass and non-antibacterial glass were mixed using a mixing stirrer and a rotation speed of 60 rpm and a stirring time of 10 minutes. Then, the mixed antibacterial glass of Example 1 was obtained by mixing uniformly.

2. Evaluation of Mixed Antibacterial Glass (1) Silver Ion Elution Evaluation 10 g of the obtained colored antibacterial glass was immersed in 100 ml of distilled water (20 ° C.) and shaken for 24 hours using a shaker. The silver ion eluate was separated using a centrifuge, and then filtered through a filter paper (5C) to obtain a measurement sample. Next, the silver ions in the measurement sample were measured by ICP emission spectroscopy, and the silver ion elution amount (mg / (g · 24Hrs)) in the colored antibacterial glass was calculated.

(2) Evaluation of outflow properties A concave portion having a depth of 0.5 mm and an area of 5 cm × 5 cm is provided on the surface of a stainless steel plate having a thickness of 1 mm and an area of 20 cm × 20 cm, and 100 g (W1) of the mixed antibacterial glass is provided there. In the filled state, tap water having a flow rate of 1 liter / min was blown from the lateral direction. After the state was continued for 1 minute, the weight (W2) of the remaining mixed antibacterial glass was measured on the stainless steel plate, and the residual ratio of the mixed antibacterial glass ((W1-W2) / W1 × 100) was determined. Calculated. And from the calculated residual rate, the outflow property of the mixed antibacterial glass was evaluated according to the following criteria.
A: Residual rate is 90 to 100% by weight.
(Circle): A residual rate is 70 to less than 90 weight%.
(Triangle | delta): A residual rate is 30 to less than 70 weight%.
X: The residual rate is less than 30% by weight.

(3) Antibacterial evaluation 1 (bacterial activity value evaluation)
Using a washing machine, antibacterial evaluation of cotton cloth with the obtained mixed antibacterial glass was performed. That is, using the washing machine shown in FIG. 13, 3 kg of cotton cloth was washed for 15 minutes in a state where the mixed antibacterial glass (20 g) of the usage mode shown in FIG. 8 was put into the washing tub of the washing machine. Subsequently, about the cotton cloth after washing, the bacterial activity value regarding Staphylococcus aureus was measured based on JIS L1902 (bacteria liquid absorption method). The bacterial activity value is a numerical value represented by Log (inoculated number: 1.4 × 10 ⁴ ) −Log (number of viable cells after 48 hours).
A: Bacterial activity value is 1 or more.
○: Bacterial activity value is 0.1 or more.
(Triangle | delta): Bacterial activity value is 0.01 or more.
X: Bacterial activity value is less than 0.01.

(4) Antibacterial evaluation 2 (bacteriostatic activity value evaluation)
Using a washing machine, antibacterial evaluation of cotton cloth with the obtained mixed antibacterial glass was performed. That is, using the washing machine shown in FIG. 13, 3 kg of cotton cloth was washed for 15 minutes in a state where the mixed antibacterial glass (20 g) of the usage mode shown in FIG. 8 was put into the washing tub of the washing machine. Subsequently, the bacteriostatic activity value regarding Staphylococcus aureus was measured about the cotton fabric after washing based on JISL1902 (bacteria liquid absorption method). The bacteriostatic activity value is a numerical value represented by Log (the number of unprocessed bacteria: 6.5 × 10 ⁶ ) −Log (the number of viable bacteria after 48 hours).
A: Bacteriostatic activity value is 5.0 or more.
○: The bacteriostatic activity value is 3.0 or more.
(Triangle | delta): Bacterial activity value is 2.0 or more.
X: Bacterial activity value is less than 2.0.

(5) Discoloration prevention effect As described above, antibacterial evaluation was performed using a washing machine, and the discoloration prevention effect of the obtained mixed antibacterial glass was evaluated. That is, after the antibacterial evaluation was performed for 48 hours using the washing machine shown in FIG. 13, the mixed antibacterial glass was taken out and evaluated for the effect of preventing discoloration under the following conditions.
A: No discoloration or the like is observed in the mixed antibacterial glass.
○: Almost no discoloration or the like is observed in the mixed antibacterial glass.
Δ: Some discoloration or the like is observed in the mixed antibacterial glass.
X: Remarkable discoloration of the mixed antibacterial glass is observed.

[Examples 2 to 5]
In Examples 2 to 5, as shown in Tables 1 to 3, the composition ratio of the colored antibacterial glass and the addition amount of the inorganic colorant (cobalt oxide) were changed, and the maximum diameter (t3) of the non-antibacterial glass was changed. Except for the changes, mixed antibacterial glasses were prepared and evaluated in the same manner as in Example 1.

[Comparative Examples 1-3]
In Comparative Example 1, evaluation was performed in the same manner as in Example 1 except that the amount of cobalt oxide added to the colored antibacterial glass in Example 1 was 0.0001% by weight.
Further, in Comparative Example 2, iron oxide (Fe ₂ O ₃ ) was added instead of cobalt oxide (CoO) of the colored antibacterial glass in Example 1, and the addition amount was 0.0001 wt%. Were evaluated in the same manner as in Example 1.
Furthermore, in Comparative Example 3, evaluation was performed in the same manner as in Example 1 except that the amount of cobalt oxide added to the colored antibacterial glass in Example 1 was 0% by weight, that is, no cobalt oxide was added.
In addition, the numbers 3 and 4 in FIG. 14 show photographs of the mixed antibacterial glass before the start of evaluation of the discoloration prevention effect and the mixed antibacterial glass after the end of evaluation in Comparative Examples 1 to 3, respectively.

According to the mixed antibacterial glass of the present invention, by mixing a colored antibacterial glass to which a predetermined amount of an inorganic colorant is added and a non-antibacterial glass that is non-soluble and has no weight change, Even when used under harsh conditions for a long time, the amount of non-antibacterial glass is reduced and the change in weight is small enough to contact with water while maintaining the initial appearance and distinguishability. The predetermined amount of silver ions can be released repeatedly.
Therefore, for example, it is possible to quickly release a predetermined amount of silver ions to an antibacterial object or bath water being washed, and to efficiently perform a predetermined antibacterial treatment, The same antibacterial effect can be exhibited in the bathtub after use.
Therefore, the mixed antibacterial glass of the present invention includes a washing machine, a dishwasher, an iron, a humidifier, a food washing tank, a medical equipment washing machine, a flush toilet water tank, a barn washing device, and an artificial turf ground rotating nozzle type washing. It can be suitably used directly or indirectly for various devices such as a device, a bath circulating water device, a cooling tower for cooling, a sprayer, and a garden hose.
In particular, in a usage mode where considerable rotational vibration or reciprocating motion is applied to the mixed antibacterial glass, such as a washing machine or a bath, the weight change of the mixed antibacterial glass is reduced, and it is sufficiently in contact with water. On the other hand, since it does not change in appearance, it is suitable for the mixed antibacterial glass of the present invention.

Claims (8)

A mixed antibacterial glass comprising a colored antibacterial glass that exhibits an antibacterial effect by releasing silver ions, and a non-antibacterial glass,
The maximum diameter (t1) of the colored antibacterial glass is set to a value within a range of 3 to 30 mm, and as a blending component, cobalt oxide as an inorganic colorant is contained, and the addition amount of the cobalt oxide is adjusted as a whole. With a value in the range of 0.001 to 0.5% by weight with respect to the amount ,
A mixed antibacterial glass characterized in that an elution amount of silver ions in the colored antibacterial glass is set to a value within a range of 0.01 to 1.0 mg / (g · 24 Hrs) .   The said colored antibacterial glass is flat form, Comprising: The thickness (t2) of the said colored antibacterial glass shall be a value within the range of 1-8 mm, The mixing of Claim 1 characterized by the above-mentioned. Antibacterial glass. The mixed antibacterial glass according to claim 1 or 2, wherein the non-antibacterial glass contains soda glass as a main component. The mixed antibacterial glass according to any one of claims 1 to 3, wherein the maximum diameter (t3) of the non-antibacterial glass is a value within a range of 3 to 30 mm. . Wherein the amount of non-antibacterial glass, to the colored antibacterial glass 100 parts by weight, the first to fourth terms of the claims, characterized in that a value within the range of 10 to 3000 parts by weight The mixed antibacterial glass according to any one of the above. When washing cloth products using a washing machine, mixed antibacterial glass to be put into the washing tub of the washing machine and to impart predetermined antibacterial properties to the cloth product and the washing tub,
The first water-permeable member covers the periphery of the plurality of mixed antibacterial glasses, and the water-permeable periphery is further covered by the second water-permeable member . 6. The mixed antibacterial glass according to any one of items 5 . It is a mixed antibacterial glass that is added to a bath tub filled with bath water, floats on the bath water, and imparts a predetermined antibacterial property to the bath water and tub,
The mixed antibacterial glass according to any one of claims 1 to 5 , wherein the periphery is covered with a shape-retaining member and the periphery is further covered with a water-permeable member. In preparation for sanitary ware, with respect to the sanitary ware, a mixed antibacterial glass for imparting a predetermined antimicrobial, the first term of the claims made housed into a container equipped with a water channel ~ 6. The mixed antibacterial glass according to any one of items 5 .