KR101024417B1 - Mixed antibacterial glass - Google Patents

Abstract

An object of the present invention is to provide a mixed antimicrobial glass having a small change in weight at the time of use, being convenient for use, and having excellent discoloration preventing effect and discrimination while maintaining the amount of silver ions released in a predetermined range.

Moreover, in order to solve the said subject, the mixed antimicrobial glass which exhibits antimicrobial effect by releasing silver ion and non-microbial glass is mixed antimicrobial glass, The maximum diameter (t1) of colored antimicrobial glass is 3-30. The mixed antimicrobial glass is made into the value within the range of mm, and also contains an inorganic coloring agent as a compounding component, and makes the addition amount of the said inorganic coloring agent into the value within the range of 0.001-0.5 weight% with respect to whole quantity. The purpose is to provide.

Description

Mixed antibacterial glass

The present invention relates to a mixed antimicrobial glass, and more particularly, to a mixed antimicrobial glass comprising a mixed antimicrobial glass containing an inorganic colorant and a non-antibacterial glass, respectively.

In recent years, mixed antimicrobial glass having a predetermined particle size has been used in resins in order to impart an antimicrobial effect in building materials, home appliances (including TVs, PCs, mobile phones, video cameras, etc.), sundries, packaging materials, and the like. Quantitatively mixed antimicrobial resin composition is used.

As such an antimicrobial resin composition, the synthetic resin molded object containing the borosilicate antimicrobial glass which elutes silver ions in resin is disclosed (for example, refer patent document 1).

More specifically, such a synthetic resin molded article is one or two or more types of mesh forming oxides of SiO ₂ , B ₂ O ₃ , P ₂ O ₅ , and one or two of Na ₂ O, K ₂ O, CaO, and ZnO. 100 parts by weight of solids in the glass into mesh modifier oxide species or more, and is configured to include a borosilicate glass which contains the antibacterial of 0.1 to 20 parts by weight of Ag ₂ O in the synthetic resin as the monovalent Ag. In the examples of this patent publication, ₂ parts by weight of Ag ₂ O is used with respect to 100 parts by weight of a mixture of SiO ₂ : 40 mol%, B ₂ O ₃ : 50 mol%, Na ₂ O: 10 mol%. The antimicrobial resin composition which added the antimicrobial glass whose average particle diameter added is 20 micrometers or less in synthetic resin is disclosed.

Moreover, as an antimicrobial resin composition, the resin composition containing the flaky glass whose particle diameter which has antibacterial property is 10-1000 micrometers, and whose thickness is 0.1-20 micrometers is disclosed (for example, refer patent document 2).

Specifically, as the composition of the scaly glass than the case containing a _{B 2 O 3, SiO 2:} 20 ~ 60 _{wt%, B 2 O 3: 30} ~ 70 _{wt%, Na 2 O: 5 ~} 35 By weight%, Ag ₂ O: 0.5 to 3% by weight, in the case of not containing B ₂ O ₃ , SiO ₂ : 55 to 80% by weight, Al ₂ O ₃ : 0.5 to 30% by weight, Na ₂ O: 0.5 to 3% by weight: 19.5 ~ 42 wt%, Ag ₂ O.

In addition, when immersed in boiling water at 100 ° C. for 500 hours to 1000 hours and then immersed in 20 ° C. water or acid for 24 hours, the silver ion-containing inorganic antimicrobial agent having an amount of silver ions of 0.5 ng / cm 2 / day or more, and an inorganic filler The product used in the place using the antimicrobial water to contain is disclosed (for example, refer patent document 3).

More _{specifically, P 2 O 5: 56 ~} 59 mol%, MgO + CaO + ZnO: 33 ~ 38 mol%, Al 2 O 3: for the glass components to 6 ~ 8 mol%, the Ag ₂ O 0 A silver ion-containing inorganic antimicrobial agent having an average particle diameter of 2 to 20 µm blended with -5% by weight is added to the resin in a range of 0.5 to 5% by weight, and additionally, an inorganic filler is added in a range of 5 to 80% by weight. Products for use where antimicrobial water is used are disclosed.

Moreover, as an use of antimicrobial glass, the antimicrobial resin composition which illustrated electrical appliances, such as a dishwasher, a dish dryer, a refrigerator, a washing machine, and a pot, is also proposed (for example, refer patent documents 4-6).

That is, according to the Patent Document 4 or 5, the molding resin constituting such appliances, having an average particle diameter of 20 ㎛ or less ZnO: 40 ~ 80% by mole, SiO _2: 5 ~ 35 mole%, CaO: 5 ~ 30% by mole Similar to the antimicrobial glass, ZnO: 54 to 60 mol%, B ₂ O ₃ : 25 to 32 mol%, SiO ₂ : 7 to 12 mol%, alkali metal oxide: 5 to 8 mol% There is proposed an antimicrobial resin composition containing a predetermined amount of antimicrobial glass.

According to Patent Document 6, the maximum diameter t1 of the antimicrobial glass is set to a value within the range of 1 to 50 mm, and the elution amount of silver ions is set to a value within the range of 0.5 to 100 mg / (g · 24 Hrs). The antimicrobial glass which manufactures silver-ion containing water by making the said antimicrobial glass directly contact water, and performs predetermined | prescribed antibacterial treatment with respect to the antimicrobial substance in the laundry or after washing is disclosed, and its manufacturing method is disclosed.

Moreover, the glass water treatment agent used in water treatment apparatuses, such as a water tank and a cooling tower, is proposed as a use of antibacterial glass (for example, refer patent document 7).

That is, as a phosphate glass with a maximum diameter of 10 mm or more, the weight composition ratio is (RO + R ₂ O) / P ₂ O ₃ = 0.4 to 1.2, R ₂ O / (RO + R ₂ O ₃ ) = 0 to 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 metal ion content flow rate is 0.005 to 5% by weight. Phosphorus glass water treatment agent.

Patent Document 1: Japanese Patent Application Laid-open No. Hei 1-313531 (Scope of Claim)

Patent Document 2: Japanese Patent Application Laid-Open No. 7-25635 (Scope of Claim)

Patent Document 3: Japanese Patent Application Laid-open No. Hei 10-72530 (Scope of Claim)

Patent Document 4: Japanese Unexamined Patent Publication No. 2000-3238 (Scope of Claim)

Patent Document 5: Japanese Patent Application Laid-Open No. 2000-3239 (Scope of Claim)

Patent Document 6: WO 2005/087675 (Scope of Claim)

Patent Document 7: Japanese Patent Publication No. 7-63701 (Scope of Claim)

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

However, since the antimicrobial resin composition disclosed by patent documents 1-6 is comprised by mixing all antimicrobial glass in resin, antimicrobial glass is substantially colorless and transparent, and silver which contains discolors by reaction with chlorine ion etc. Many cases have been opaque.

Therefore, when such an antimicrobial resin composition is used, although the predetermined | prescribed antimicrobial property can be provided to the components of an electrical product, the problem that the external appearance of an electrical product fell significantly during use was seen.

Moreover, in patent documents 1 and 3-5, in order to mix uniformly in resin, 20 micrometers or less are preferable for the average particle diameter of antimicrobial glass, and in patent document 2, although antimicrobial glass is made into flaky glass of predetermined size, A manufacturing problem has been shown that a classification device or the like is used in combination as a manufacturing apparatus and these values must be limited to a predetermined range.

On the other hand, although the antimicrobial glass and glass water treatment agent disclosed by patent documents 6 and 7 have a comparatively large maximum diameter, they are discolored when they are used for electrical appliances using flow water, such as a dishwasher, a dish dryer, or a washing machine. Problems such as a deterioration of the prevention effect or easy breakage were seen.

Moreover, all the antimicrobial glasses disclosed by patent documents 1-7 were substantially colorless and transparent, and when it provided with the coating member and cartridgeized, the problem that the presence cannot be distinguished from the outside was seen. That is, when cartridgeized and used for an electrical product, it also showed that it was difficult to judge the replacement time and replacement time of antimicrobial glass.

In addition, all the antimicrobial glasses disclosed by patent documents 1-7 are water solubility, and when used as antimicrobial glass for washing machines, since it melt | dissolves and a weight decreases, it can use it in the state accommodated in the predetermined container. There was no problem, and use was inconvenient. That is, problems, such as being unable to maintain the antimicrobial glass accommodated in a predetermined container in the state which sank in the water of a washing machine, or being unable to maintain the external appearance of a predetermined container, were seen.

Thus, the present inventors, as a result of earnestly examining, even when used as a mixed antimicrobial glass for washing machines by mixing a colored antimicrobial glass to which a predetermined amount of an inorganic colorant is added and a non-antibacterial glass which is insoluble and does not change weight. The present invention has been found to be capable of repeatedly emitting a predetermined amount of silver ions while keeping the initial appearance and discrimination while being easy to use while reducing the weight change.

That is, an object of the present invention is to provide a mixed antimicrobial glass which has a small change in weight at the time of use and is convenient for use, while obtaining excellent discoloration preventing effect and discrimination while maintaining the amount of silver ions released in a predetermined range.

Means to solve the problem

According to the present invention, a mixed antimicrobial glass containing antibacterial glass and colored antimicrobial glass that exhibits antibacterial effect by releasing silver ions, wherein the maximum diameter t1 of the colored antimicrobial glass is in the range of 3 to 30 mm. In addition, a mixed antimicrobial glass is provided which contains an inorganic colorant as a compounding ingredient and sets the added amount of the inorganic colorant to a value within the range of 0.001 to 0.5% by weight based on the total amount, thereby solving the above-mentioned problem. have.

That is, according to the mixed antimicrobial glass of this invention, by including the colored antimicrobial glass which added the predetermined amount of inorganic type coloring agent, the initial appearance and discrimination can be maintained, showing a predetermined antimicrobial effect over a long period of time. Therefore, by the action of the inorganic colorant, discoloration of the resin derived from silver ions can be effectively prevented, and its presence can be easily identified from the outside, and the replenishment time of the whole mixed antimicrobial glass or colored antimicrobial glass The timing of exchange can be judged appropriately.

Moreover, in the case of such mixed antimicrobial glass, not only handling becomes easy, but also the function of a non-antibacterial glass can prevent the aggregation of colored antimicrobial glasses effectively, without adding a coagulation inhibitor, such as a silica and a titanium oxide. .

In addition, the non-antibacterial glass can function as a weight adjusting member, and the weight change at the time of use becomes small, and when it is used as a mixed antimicrobial glass for a washing machine, for example, it is kept as it is in the state of the washing machine, The external appearance of a predetermined container can be maintained as it is.

Moreover, in forming the mixed antimicrobial glass of this invention, it is preferable that colored antimicrobial glass is flat form, and to make thickness t2 of the said colored antimicrobial glass into the value within the range of 1-8 mm.

By using the mixed antimicrobial glass containing the colored antimicrobial glass of such thickness (t2), handling becomes easy and can be manufactured stably.

Further, in constructing the mixed antimicrobial glass of the present invention, the inorganic colorant is at least one selected from the group consisting of cobalt oxide, copper oxide, chromium oxide, nickel oxide, manganese oxide, neodium oxide, erbium oxide, and cerium oxide. When the addition amount of an inorganic coloring agent is C1, and the addition amount of silver oxide contained similarly is C2, it is preferable to make the ratio represented by C1 / C2 into the value within the range of 0.01-3.

Thus, by using specific compounds, such as cobalt oxide, as an inorganic type coloring agent, in the coloring antimicrobial glass and further the mixed antimicrobial glass as a whole, the outstanding coloring property can be acquired by comparatively small amount addition. Therefore, the amount of silver ions eluted is less likely to be exerted, so that a predetermined antibacterial effect can be exerted for a certain period of time, and the initial appearance and discrimination can be maintained for a long time.

In addition, by controlling the addition amount of the inorganic colorant in association with the addition amount of the silver oxide, it is possible to exert a predetermined antibacterial effect without additionally suppressing it, while maintaining the initial appearance and discrimination over a long period of time.

Moreover, in forming the mixed antimicrobial glass of this invention, it is preferable to make elution amount of silver ion into the range of 0.01-1.0 mg / (g * 24Hrs) to colored antimicrobial glass.

If the amount of such silver ions is eluted, even when the mixed antimicrobial glass is formed together with the non-antibacterial glass, the initial appearance and discrimination can be maintained while exhibiting a predetermined antimicrobial effect for a longer period.

Moreover, in forming the mixed antimicrobial glass of this invention, it is preferable that a non-antibacterial glass contains soda glass as a main component.

In the case of such non-antibacterial glass, since it is equivalent to the specific gravity of colored antimicrobial glass and is inexpensive, mixed antimicrobial glass can be manufactured stably and economically.

Moreover, in constructing the mixed antimicrobial glass of this invention, it is preferable to make the maximum diameter t3 of non-antibacterial glass into the value within the range of 3-30 mm.

In the case of such non-antibacterial glass, since it becomes substantially the same as the largest diameter t1 of colored antimicrobial glass, it can become easy to mix uniformly with respect to colored antimicrobial glass, and can also make it hard to be localized.

Moreover, in forming the mixed antimicrobial glass of this invention, it is preferable to make the addition amount of a non-antibacterial glass into the value within the range of 10-3000 weight part with respect to 100 weight part of antimicrobial glass.

The addition amount of such non-antibacterial glass can express predetermined antibacterial property as mixed antimicrobial glass, and can control the weight of the whole mixed antimicrobial glass easily.

In addition, in the composition of the mixed antimicrobial glass of the present invention, at the time of washing a fabric using a washing machine, the mixed antimicrobial glass is added to a washing tank of a washing machine to impart predetermined antimicrobial properties to the fabric and the washing tank. As the first permeable member, the periphery of the plurality of mixed antimicrobial glasses is preferably coated, and the periphery of the permeable member is preferably additionally covered by the second permeable member.

If it is the structure of such mixed antimicrobial glass for washing machines, not only convenience of use will be favorable but predetermined antimicrobial property can be efficiently given to a package, a washing tank, etc.

In addition, in the composition of the mixed antimicrobial glass of the present invention, the mixed antimicrobial glass is added to a bath tub that receives bath water and floats in the bath water to impart a predetermined antimicrobial property to the bath water and the bath. Is coated, and it is preferable that the periphery is additionally covered by a water permeable member.

With such a constitution of the mixed antimicrobial glass for baths, not only the convenience of use is improved, but also the predetermined antibacterial property can be efficiently imparted to the bath water and the bathtub.

Moreover, in forming the mixed antimicrobial glass of this invention, it is equipped with a sanitary ware, and is accommodated in the container provided with the water flow path as a mixed antimicrobial glass for providing predetermined antibacterial property with respect to the said sanitary ware. It is desirable to be.

If it is the structure of the mixed antimicrobial glass for sanitary ware, not only convenience of use will be favorable but a predetermined antimicrobial property can be effectively given to a sanitary ware.

Brief description of the drawings

FIG.1 (a)-(f) is a figure provided in order to demonstrate the shape of colored antimicrobial glass.

It is a figure provided in order to demonstrate the relationship of the largest diameter t1 of a colored antimicrobial glass contained in mixed antimicrobial glass, and a residual rate.

FIG. 3 is a view provided to explain the relationship between the amount of silver ions eluted with washing frequency.

It is a figure provided in order to demonstrate the relationship of the addition amount of cobalt oxide and color development property.

5 is a view for explaining the relationship between the amount of cobalt oxide and copper oxide added and the amount of silver ions eluted.

FIG.6 (a)-(b) is a figure provided in order to demonstrate the cartridgeization of mixed antimicrobial glass.

FIG.7 (a)-(c) is a figure provided in order to demonstrate the coating member of mixed antimicrobial glass.

FIG.8 (a)-(b) is a figure provided in order to demonstrate the use aspect of the mixed antimicrobial glass for washing.

9 (a) to 9 (b) are diagrams provided for explaining the use mode of the mixed antimicrobial glass for the bath.

10 (a) to 10 (b) are diagrams provided for explaining the use mode of the mixed antimicrobial glass for sanitary ware.

11 (a) to 11 (b) are diagrams provided for explaining the method for producing a mixed antimicrobial glass (first).

It is a figure provided in order to demonstrate another manufacturing method of mixed antimicrobial glass.

It is a figure which shows an example of the washing machine which applied the mixed antimicrobial glass.

FIG.14 (a)-(b) is a figure provided in order to demonstrate the discoloration prevention effect of four types of mixed antimicrobial glass (No1, 2, 3, 4).

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, embodiment regarding the mixed antimicrobial glass of this invention and its use method is demonstrated concretely.

That is, the mixed antimicrobial glass of this invention is a mixed antimicrobial glass containing the colored antimicrobial glass which exhibits antibacterial effect by releasing silver ion, and a non-antibacterial glass,

The maximum diameter (t1) of the colored antimicrobial glass is set to a value within the range of 3 to 30 mm, and an inorganic coloring agent is contained as a blending component, and the amount of the inorganic coloring agent added is 0.001 to 0.5% by weight based on the total amount. It is mixed antimicrobial glass made into the value within the range of.

1. tinted antimicrobial glass

(1) shape 1

Although the shape of colored antimicrobial glass is not restrict | limited in particular, As shown to FIG. 1 (a)-(f), it is preferable that it is flat form, such as rectangular shape, a polygonal shape, a disk shape, an ellipse shape, a mold release shape, and the perforated shape. .

The reason is that the colored antimicrobial glass is formed into a plate shape such as a rectangular shape or a disc shape, so that even when placed on a predetermined location and directly contacted with water, the colored antimicrobial glass flows down by water pressure and flows out from a predetermined location effectively. This can be prevented. In addition, when colored antimicrobial glass has a rectangular shape etc., since it is hard to aggregate even when colored antimicrobial glass adjoins at the time of manufacture, use, etc., it is environmental conditions at the time of control of size and shape at the time of manufacture of colored antimicrobial glass, and use. This is because the control becomes easier.

Moreover, as shown to Fig.1 (a)-(f), what chamfered along the side which comprises such colored antimicrobial glass is preferable.

The reason for this is that the initial appearance and discrimination can be maintained while exhibiting a predetermined antimicrobial effect for a longer period by using such a shape. Moreover, it is because the moldability and abrasiveness of colored antimicrobial glass can also be improved by setting it as such a chamfer shape.

In addition, in the case of colored antimicrobial glass of such a form, not only the handling and the exchange are easy, but also a relatively strong water flow can be effectively prevented from flowing out or crushing with the water flow.

(2) shape 2

Moreover, the maximum diameter t1 of colored antimicrobial glass is made into the value within the range of 3-30 mm, It is characterized by the above-mentioned. Here, the largest diameter t1 of colored antimicrobial glass means the maximum length at the time of drawing arbitrary lines in the shape of colored antimicrobial glass, for example, as shown to FIG. 1 (a)-(f). do.

That is, when the maximum diameter becomes less than 3 mm, when the maximum diameter is less than 3 mm, when it is placed in a predetermined position and is in direct contact with water, it flows down by water pressure, and easily flows out from the predetermined position, or over a long period of time. This is because it may be difficult to release a predetermined concentration of silver ions, or, moreover, may be easily aggregated during storage.

On the other hand, when this maximum diameter exceeds 30 mm, handling becomes difficult or it becomes difficult to manufacture stably.

Therefore, it is more preferable to make the maximum diameter of colored antimicrobial glass into the value within the range of 4-25 mm, and it is still more preferable to set it as the value within the range of 5-15 mm.

In addition, the largest diameter t1 of such colored antimicrobial glass becomes the largest diameter of a planar direction, when colored antimicrobial glass is a flat plate shape, for example, and when it is spherical, it is a diameter of a sphere.

Moreover, when such colored antimicrobial glass is flat form, it is preferable to make thickness t2 of colored antimicrobial glass into the value within the range of 0.1-10 mm.

The reason is that when the thickness of such colored antimicrobial glass becomes less than 0.1 mm, it becomes difficult to release a predetermined concentration of silver ions, becomes difficult to handle, or furthermore, makes it difficult to stably manufacture. Because there is. On the other hand, when the thickness of such colored antimicrobial glass exceeds 10 mm, it becomes difficult to handle on the contrary, or it becomes difficult to manufacture stably.

Therefore, when such colored antimicrobial glass is flat form, it is more preferable to make thickness of colored antimicrobial glass into the value within the range of 1-8 mm, and it is still more preferable to set it as the value within the range of 2-5 mm.

In addition, the largest diameter t1 and thickness t2 of the colored antimicrobial glass mentioned above can be measured easily using an optical microscope photograph and a rags, for example.

(3) shape 3

Next, the relationship between the largest diameter t1 of the planar direction of colored antimicrobial glass, and the residual ratio at the time of using this colored antimicrobial glass is demonstrated in detail, referring FIG. 2 about the shape of colored antimicrobial glass. The horizontal axis of this FIG. 2 shows the largest diameter (mm) of the planar direction of colored antimicrobial glass in logarithm, and the vertical axis | shaft has remained the colored antimicrobial glass in the Example mentioned later, when using colored antimicrobial glass of each particle diameter. The residual rate (%) measured according to the measurement method of rate is shown.

As is clear from Fig. 2, when the maximum diameter t1 in the planar direction of the colored antimicrobial 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, and can withstand long-term use. I can see that there is.

Next, with respect to the shape of colored antimicrobial glass, referring to FIG. 3, when using the colored antimicrobial glass (15 mm of largest diameters in a planar direction), and antimicrobial glass whose average particle diameter is 20 micrometers, respectively, The change of the washing | cleaning frequency and the amount of silver ion elution is demonstrated in detail. That is, the horizontal axis | shaft of FIG. 3 shows the frequency | count of washing using each colored antimicrobial glass using the washing machine 50 as shown in FIG. 13 mentioned later, and the vertical axis | shaft of FIG. 3 is underwater in each time. The amount of silver ions eluted into (mg / (g · 24Hrs)) is shown. 3, the data about the colored antimicrobial glass of this invention is shown by the solid line A, and the data about the colored antimicrobial glass whose average particle diameter is 20 micrometers are shown by the dotted line B. In addition, in FIG.

As shown in such FIG. 3, since the colored antimicrobial glass of this invention does not flow down by water pressure etc. by the predetermined magnitude | size in a planar direction, a residual amount does not fall significantly. Therefore, even if it uses repeatedly, it turns out that the target elution amount can be maintained. Therefore, it turns out that the colored antimicrobial glass of this invention can endure long-term use.

On the other hand, the antimicrobial glass having an average particle diameter of 20 μm, as shown in Fig. 2, the residual amount of the antimicrobial glass decreases with each use, so as the number of washing increases, the amount of silver ions immediately after the start of use and In comparison, the value of the elution amount is greatly reduced. Therefore, in order to ensure the elution amount of the desired anion, it turns out that it is necessary to replenish antibacterial glass frequently.

(4) Class 1

Moreover, it is preferable to use the colored antimicrobial glass which becomes the following compounding compositions in the state which does not contain an inorganic type coloring agent with respect to the kind of colored antimicrobial glass.

That is, as a first glass composition in the colored antibacterial glass, Ag ₂ O, ZnO, CaO, B ₂ O _3, and comprises a P ₂ O _5, and further, when the whole amount to 100% by weight, Ag ₂ O A value in the range of 0.2 to 5% by weight, a value in the range of 1 to 50% by weight of ZnO, a value in the range of 0.1 to 15% by weight of CaO, and a content of B ₂ O ₃ to 0.1 to values, and the content of P ₂ O ₅ in the range of 15% by weight at the same time a value within the range of 30 to 80% by weight, it is preferred that the weight ratio of ZnO / CaO within the range of 1.1 to 15.

The reason for this is that when such a weight ratio of ZnO / CaO is less than 1.1, yellowing of the colored antimicrobial glass may not be prevented efficiently, while when such a weight ratio of ZnO / CaO exceeds 15, coloring is performed. This is because the antimicrobial glass may become cloudy or yellow on the contrary.

Therefore, it is more preferable to make the weight ratio represented by such ZnO / CaO into the value within the range of 1.2-10, and it is still more preferable to set it as the value within the range of 1.5-8.

As the second glass composition, Ag ₂ O, CaO, B ₂ O ₃ and P ₂ O ₅ were included instead of substantially including ZnO, and when the total amount was 100% by weight, Ag was added. ₂ O content in the range of 0.2 to 5% by weight, CaO content in the range of 15 to 50% by weight, B ₂ O ₃ content in the range of 0.1 to 15% by weight, and P ₂ O a content of ₅ at the same time in the range of 30 to 80% by weight, a colored antibacterial glass the weight ratio of CaO / Ag ₂ O in the range of 5-15.

The reason is that when such a weight ratio of CaO / Ag ₂ O is less than 5, yellowing of the colored antimicrobial glass may not be prevented efficiently, while the weight ratio of CaO / Ag ₂ O is 15. It is because when exceeding, a coloring antimicrobial glass may become cloudy or yellow on the contrary.

Thus, the weight ratio represented by these CaO / Ag ₂ O, and more preferably in the range of 6-12, more preferably in the range of 7-10.

As the third glass composition, Ag ₂ O, CaO, B ₂ O ₃ , P ₂ O _5, and Al ₂ O ₃ , and the content of Al ₂ O ₃ when the total amount was 100% by weight. It is colored antimicrobial glass which made the value within the range of 0.5-10 weight%.

The reason is that by adding Al ₂ O ₃ in this way, deliquescent phenomenon can be effectively suppressed.

That is, when the content of Al ₂ O ₃ is less than 0.5% by weight, the effect of suppressing deliquescent phenomenon may not be expressed. On the other hand, when the content of Al ₂ O ₃ exceeds 10 wt%, and because, in some cases, the antibacterial effect is not expressed.

Thus, it can be said more preferable that the content of this Al ₂ O ₃ in the range of 1-5% by weight.

(5) Class 2

Moreover, an inorganic coloring agent is included in colored antimicrobial glass, and the addition amount of the said inorganic coloring agent is made into the value within the range of 0.001-0.5 weight% with respect to whole quantity, It is characterized by the above-mentioned.

The reason for this is that by adding a predetermined amount of inorganic colorant, the size of the colored antimicrobial glass and the amount of silver ions eluted can be easily limited to a predetermined range.

Therefore, it is possible to maintain the initial appearance and discrimination while exhibiting a predetermined antibacterial effect over a long period of time. That is, discoloration of the resin derived from silver ions can be effectively prevented by the action of the inorganic colorant, and the presence of the coating member can be easily distinguished from the outside even when the cartridge is formed into a cartridge. The timing of replacement and replacement of colored antimicrobial glass can be determined accurately.

In addition, in the case of such a large-scale colored antimicrobial glass, not only the handling becomes easy, but also the combined antimicrobial glass can be effectively prevented from coming into contact with the colored antimicrobial glasses to aggregate.

Therefore, it is more preferable to make the addition amount of the inorganic coloring agent in colored antimicrobial glass into the value within the range of 0.003-0.1 weight% with respect to whole quantity, and it is still more preferable to set it as the value within the range which is 0.005-0.05 weight%.

Here, the influence of the addition amount of the inorganic coloring agent in colored antimicrobial glass is demonstrated with reference to FIG. 4 and FIG.

The horizontal axis of FIG. 4 has shown the addition amount (weight%) of cobalt oxide in colored antimicrobial glass by logarithm, and the vertical axis | shaft has shown the color development (relative value) of colored antimicrobial glass. The coloring property of this colored antimicrobial glass has shown that it is so favorable that a number is large, and it is a value corresponded to the absorbance of visible light.

In addition, the horizontal axis | shaft of FIG. 5 has shown the addition amount (weight%) of the inorganic coloring agent (cobalt oxide and copper oxide) in colored antimicrobial glass by logarithm, and the vertical axis | shaft has the silver ion elution amount (mg /) in colored antimicrobial glass. (g * 24Hrs)) is shown. In addition, in FIG. 5, the characteristic curve to which symbol A was attached is a case where cobalt oxide was used as an inorganic colorant, and the characteristic curve to which symbol B was used is a case where copper oxide is used as an inorganic colorant.

Therefore, as apparent from Fig. 4, when the added amount of cobalt oxide in the colored antimicrobial glass is 0.001% by weight or more, the predetermined color development is obtained, and as the addition amount of cobalt oxide increases, the color development also becomes good, and 0.1% by weight. If it exceeds, it is shown that it is saturated.

On the other hand, as apparent from FIG. 5, as the addition amount of the inorganic colorant (cobalt oxide and copper oxide) in the colored antimicrobial glass increases, the silver ion elution amount (mg / (g · 24Hrs)) tends to decrease gradually. ought.

Therefore, referring to FIG. 4 and FIG. 5, in order to balance the color development in colored antimicrobial glass and the amount of silver ion elution, the addition amount of an inorganic colorant shall be a value within the range of 0.001 to 0.5 weight% with respect to the total amount. You can see that it is valid.

In addition, when considering the addition amount of the inorganic coloring agent contained in colored antimicrobial glass, it is preferable to consider also about the addition amount of silver oxide.

That is, when the addition amount of the inorganic coloring agent contained in colored antimicrobial glass is made into C1, and the addition amount of the silver oxide contained similarly is made into C2, it is preferable to make the ratio represented by C1 / C2 into the value within the range of 0.01-3.

This is because, by controlling the amount of the inorganic colorant added in association with the amount of silver oxide added, the initial appearance and discrimination can be maintained without suppressing the display of the predetermined antibacterial effect. That is, when the ratio represented by C1 / C2 is less than 0.01, the expression of the discoloration prevention effect may be insufficient. On the other hand, when the ratio represented by C1 / C2 exceeds 3, the expression of the antimicrobial effect may be insufficient.

Therefore, it is more preferable to make the ratio represented by C1 / C2 into the value within the range of 0.01-2, and it is still more preferable to set it as the value within the range of 0.05-1.

(6) Class 3

In addition, the type of the inorganic colorant is not particularly limited, but may be cobalt oxide (CoO), copper oxide (CuO), chromium oxide (Cr ₂ O ₃ ), nickel oxide (NiO), and manganese oxide so as to be easily developed in the oxidation atmosphere. (MnO ₂ ), neodymium oxide (Nd ₂ O ₃ ), erbium oxide (Er ₂ O ₃ ), and cerium oxide (CeO ₂ ), such as one kind or a combination of two or more kinds.

For example, in the case of cobalt oxide, even in a very small amount of addition, for example, 0.005% by weight, excellent color of ink blue can be obtained, and the initial appearance and discrimination can be maintained without suppressing a predetermined antibacterial effect. .

In addition, in the case of copper oxide, the color development of the sky blue is obtained by the addition of a relatively small amount, and the initial appearance and discrimination can be maintained without suppressing the antibacterial effect.

In addition, in the case of chromium oxide, the addition of a relatively small amount of light green color development is obtained, and the initial appearance and discrimination can be maintained.

In the case of nickel oxide, on the condition that a large amount of potassium component is provided, a dark green color development property can be obtained by a relatively small amount of addition, and the initial appearance and discrimination can be maintained.

In addition, in the case of manganese oxide, vivid purple color development is obtained by the addition of a relatively small amount, subject to the presence of an oxidizing agent, and the initial appearance and discrimination can be maintained.

In addition, in the case of neodium oxide, even if the addition amount is not constant, lavender purple color development is obtained in a wide range, and the initial appearance and discrimination can be maintained. Moreover, when the glass raw material with many iron etc. is used, it is also possible to exhibit the discoloration effect.

In addition, in the case of erbium oxide and cerium oxide, pink color development is obtained, and the initial appearance and discrimination can be maintained.

(7) Silver ion elution amount

Moreover, it is preferable to make elution amount of silver ions in colored antimicrobial glass into the value within the range of 0.01-1.0 mg / (g * 24Hrs).

The reason for this is that when the amount of elution of these silver ions becomes less than 0.01 mg / (g · 24Hrs), a mixed antimicrobial glass is formed, and when directly contacted with water, the silver ions of a predetermined concentration are quickly released. It is because it may become difficult to exert predetermined antibacterial effect.

On the other hand, when the elution amount of such silver ions exceeds 1.0 mg / (g · 24Hrs), it becomes difficult to release a predetermined concentration of silver ions over a long period of time, it becomes difficult to handle or difficult to manufacture stably. For losing.

Therefore, it is preferable to make elution amount of silver ions in colored antimicrobial glass into the value within the range of 0.015-0.5 mg / (g * 24Hrs). Moreover, 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 colored antimicrobial glass can be measured according to the measuring method of Example 1 mentioned later. Moreover, when used for washing machines etc. conventionally, although the elution amount of silver ion in colored antimicrobial glass has been considered as the value within the range of 0.5-100 mg / (g * 24Hrs), the antibacterial effect increases by repeating washing. Therefore, the fact that the equivalent antibacterial effect is obtained also with a smaller amount of silver ions eluting is obtained.

2. Non-antibacterial glass

(1) Type

The type is not particularly limited as long as it is a non-antibacterial glass, that is, a glass which is dissolved by moisture and does not elute silver ions. For example, soda glass, borosilicate glass, lead glass (crystal glass), quartz glass, alumino It is preferable that they are silicate glass and phosphate glass.

More specifically, with respect to the total amount, as the glass mesh component, SiO ₂ or the like is in the range of 35 to 65% by weight, and as the glass mesh formula component, Na ₂ O, K ₂ O, Li ₂ O, CaO, MgO, BaO, _{B 2 O 3, Al 2 O} 3 is a non-antibacterial glass as a main component at least one member of soda glass, which was added in the range of 15 to 35% by weight, such being preferred.

It is also preferable to add a predetermined amount of a colorant, a reducing agent, a ultraviolet absorber, and the like.

(2) shape

The shape of the non-antibacterial glass is not particularly limited, but is preferably spherical, flat, cylindrical or polyhedral.

It is more preferable that a planar shape is flat form, such as a rectangle, a polygon, a disk, an ellipse, a mold release, a hole, etc.

The reason for this is that when the non-antibacterial glass is made into a flat plate such as a rectangle or a disc, and placed on a predetermined location and brought into direct contact with water, not only the non-antibacterial glass but also the colored antibacterial glass flows by water pressure. This is because it can be effectively prevented from descending and flowing out from a predetermined location.

(3) size

In addition, it is preferable to make the largest diameter t3 into the value within the range of 3-30 mm regarding the magnitude | size of non-antibacterial glass.

The reason is that in the case of such non-antibacterial glass, since it becomes substantially equal to the maximum diameter t1 of the colored antimicrobial glass, not only the colored antimicrobial glass can be easily mixed uniformly, but also it is difficult to be localized. to be.

Therefore, since the antimicrobial activity can be balanced and the weight of the whole mixed antimicrobial glass can be controlled in a balanced manner, it is more preferable to set the maximum diameter t3 of the non-antibacterial glass to a value within the range of 5 to 20 mm. It is more preferable to set it as the value within the range of 15 mm.

In addition, when such non-antibacterial glass is flat form, it is preferable to make thickness t4 of non-antibacterial glass into the value within the range of 0.1-10 mm.

The reason is that when the thickness of such non-antibacterial glass is less than 0.1 mm, the mechanical strength may be remarkably lowered, handling becomes difficult, or further, it may be difficult to stably manufacture. On the other hand, when the thickness of such non-antibacterial glass exceeds 10 mm, it becomes difficult to handle on the contrary, or it becomes difficult to manufacture stably.

Therefore, when such non-antibacterial glass is flat form, it is more preferable to make thickness of a non-antibacterial glass into the value within the range of 1-8 mm, and it is still more preferable to set it as the value within the range of 2-5 mm.

(4) addition amount

Moreover, it is preferable to make the addition amount of a non-antibacterial glass into the value within the range of 10-3000 weight part with respect to 100 weight part of colored antimicrobial glass.

The reason for this is that if the amount of such non-antibacterial glass is added, the predetermined antibacterial property can be expressed as the mixed antimicrobial glass, and the weight of the entire mixed antimicrobial glass can be easily controlled. That is, if it is the addition amount of such non-antibacterial glass, since it becomes easy to mix uniformly with colored antimicrobial glass, and it becomes difficult to localize, it is because an antibacterial property can be expressed uniformly and the total weight can be controlled easily. .

Therefore, since the antibacterial activity can be balanced and the weight of the whole mixed antimicrobial glass can be easily and accurately controlled, the amount of the non-antibacterial glass can be added to a value within the range of 30 to 2000 parts by weight based on 100 parts by weight of the colored antimicrobial glass. It is more preferable to set it as the value, It is further more preferable to set it as the value within the range of 50-1000 weight part, It is most preferable to set it as the value within the range of 70-200 weight part.

3. Cover member

(1) covering member

Moreover, it is also preferable to set it as the form which coat | covered the inorganic substance and organic substance around the some mixed antimicrobial glass.

The reason for this is that by configuring in this way, control of the elution rate of silver ions can be made easy, and the aggregation prevention property of mixed antimicrobial glass can be made favorable.

In addition, as a particle | grain which coats mixed antimicrobial glass, 1 type single or 2 types, such as a titanium oxide, silicon oxide, colloidal silica, zinc oxide, tin oxide, lead oxide, a white carbon, an acryl particle, a styrene particle, a polycarbonate particle, etc. The above combination is preferable.

In addition, the method of coating the mixed antimicrobial glass with the particles is not particularly limited, but for example, the mixed antimicrobial glass and the particles are uniformly mixed and then heated to a temperature of 600 to 1200 ° C. to be fused to the glass, or It is preferable to fix the binder via a medium.

In addition, as shown to Fig.6 (a) and (b), about the circumference | surroundings of the mixed antimicrobial glass 10 ', the packaging member 18' as a covering member is provided, or a box body is provided and cartridgeized It is preferable.

The reason for this is that by providing such a covering member, handling can be facilitated at the time of storage, or aggregation of the mixed antimicrobial glass can be prevented. Moreover, at the time of use, usability improves, and even when a comparatively strong water flow is used, it can prevent outflow from a predetermined place. This is because the cartridge can be easily handled, replaced, or the like.

In addition, as shown to Fig.7 (a), several mixed antimicrobial glass 10 is packaged using moisture proof materials, such as an aluminum laminated film 16, or as shown to Fig.7 (b), It is also preferable to wrap in a state and to cover the periphery with the perforated member 18 as shown to FIG.7 (c).

(2) surface treatment

Furthermore, for mixed antimicrobial glasses, hindered phenol compounds as antioxidants, such as surfactants, stearic acid, myristic acid, sodium stearate, or silane coupling agents, for the purpose of antioxidation or coloring, It is preferable to add a pigment, a dye, etc. as a coloring agent, such as a hindered amine compound.

Moreover, although it is preferable to determine the addition amount of these additives in consideration of an addition effect etc., it is more preferable to set it as the value within the range of 0.01-30 weight% with respect to whole quantity, respectively.

4. The use of the sun

(1) use of colorless transparent antimicrobial glass

In addition, the mixed antimicrobial glass is used as an aspect, and antimicrobial glass (colorless transparent antimicrobial glass) containing no inorganic colorant is added to the mixed antimicrobial glass in a range of 10 to 90% by weight based on the total amount of the mixed antimicrobial glass. It is preferable to add.

The reason for this is that by using such a colorless transparent antimicrobial glass together, the amount of silver elution of the mixed antimicrobial glass can be adjusted, while the discoloration preventing effect of the colored antimicrobial glass having a large maximum diameter (t1, t3) is relatively large. This is because it can be made inconspicuous about discoloration.

Moreover, by setting it as such a structure, even if the average particle diameter of a colorless transparent antimicrobial glass is a particulate form of 100 micrometers or less, for example, the colored antimicrobial glass with a comparatively large maximum diameter (t1, t3) contacts a colorless transparent antimicrobial glass. This is because it is possible to suppress the agglomeration and to exhibit a predetermined aggregation prevention effect.

Therefore, it is more preferable to add colorless transparent antimicrobial glass in 20 to 80 weight% with respect to the total amount of mixed antimicrobial glass, and it is still more preferable to add in 30 to 70 weight%.

(2) Mixed antimicrobial glass for washing

Moreover, as a usage aspect of mixed antimicrobial glass, it is preferable that it is mixed antimicrobial glass for putting into a washing tank of a washing machine and giving predetermined | prescribed antimicrobial property to a foam and a washing tank at the time of washing of the foam product using a washing machine.

That is, in constructing the mixed antimicrobial glass for washing, as shown in FIG. 8, the plurality of mixed antimicrobial glasses (not shown) are covered with the first water permeable member 17 having a fine grain, and It is preferable that the periphery of the first water permeable member 17 is additionally covered with a coarse second water permeable member 17b. Then, the first water-permeable member 17 is entirely encapsulated, the circumference is sealed by the sealing member 17a, and the mixed antimicrobial glass (not shown) is encapsulated. It was. Moreover, also about the 2nd water permeable member 17b as a whole, it sealed, and a part was sealed by the sealing member 17c, and the 1st water permeable member 17 in which the mixed antimicrobial glass was enclosed was enclosed.

The reason for this is that in the use mode of the mixed antimicrobial glass for a washing machine, the mixed antimicrobial glass coated in this way is simply introduced into the washing tank during washing, so that predetermined antimicrobial activity can be efficiently given to the foam product and the washing tank. Because it can. Moreover, since it was coat | covered by double, even if it stirred in a washing machine, it can prevent that mixed antimicrobial glass outflows easily.

Moreover, as a 1st water permeable member with a fine grain | grain, a felt, a nonwoven fabric, etc. whose pore size is less than 0.1 mm are mentioned, for example. On the other hand, as a grainy 2nd permeable member, the mesh material of the pore size is 0.2 mm or more, More preferably, it is 2 mm-20 mm.

In addition, as a representative example of an antibacterial substance, in the case of a washing machine, a textile, a textile material, a nonwoven fabric, a mat-like thing, clothing, towels, shoes, a quack, etc. are mentioned.

(3) Antibacterial glasses for bath

In another embodiment of the mixed antimicrobial glass, the mixed antimicrobial glass is preferably a mixed antimicrobial glass for putting bath water into a bath tub and giving the bath water a predetermined antimicrobial property.

That is, in constructing the mixed antimicrobial glass for a bath, as shown in FIG. 9, it encloses a some mixed antimicrobial glass (not shown) by the fibrous shape holding member 19a, and it seal | sticks it, It is preferable to cover the circumference further by the water permeable member 19b. And it is preferable to fix the insertion opening of the sealing permeable member 19b with the stopper 19c, for example, to make a ball shape as a whole.

The reason for this is that the mixed antimicrobial glass for the bath can maintain the mixed antimicrobial glass and maintain a predetermined shape as a whole. In addition, in such a use mode, by simply floating or placing in a predetermined place such as a water supply pipe of a bath, a bath tub, a bath water, a water drainage pipe of a bath, and the like, the antibacterial activity can be efficiently This can be given.

Moreover, if the whole shape of the mixed antimicrobial glass for bathrooms is a ball shape as shown in FIG. 9, a grind mill can also be used as a tool.

(4) Mixed antimicrobial glass for sanitary ware

Moreover, as another use aspect of mixed antimicrobial glass, it is preferable that it is a mixed antimicrobial glass provided in a sanitary ware and giving predetermined antibacterial property with respect to the said sanitary ware.

That is, as shown in FIG. 10, it is preferable to accommodate in the container 21 provided with the water passages 21a, 21b, 21c, and 21d. Moreover, it is preferable that the hinge 21g is provided and it is divided | segmented and can open and close. And it is preferable to provide the fixing part 21f which has a hole in order to suspend or fix this container 21 in a predetermined place in the state which accommodated mixed antimicrobial glass.

The reason for this is that the mixed antimicrobial glass for sanitary ware is placed in a predetermined place such as a water supply pipe of the sanitary ware, a water tank of the sanitary ware, a container inside the sanitary ware, or a pipe for water drainage of the sanitary ware. It is because it can provide a predetermined antimicrobial efficiency to sanitary ware etc. only by laying.

(5) Other Uses

In addition, although not shown, the use mode which supplies a mixed antimicrobial glass directly or indirectly to what is called a spray tank or a liquid tank in a humidifier, and supplies an antimicrobial liquid containing silver ions is also preferable. That is, the mixed antimicrobial glass with a small weight change can stably contact water, and can supply an antimicrobial liquid with a constant concentration of silver ions.

Moreover, the form of the mixed antimicrobial glass for sanitary ware as shown in FIG. 10 can also be provided as it is in the vicinity of the food waste of a kitchen sink. In other words, the so-called "slippery" tends to occur in the colander and rubber products in the vicinity where food waste collects, but the mixed antimicrobial glass with a small weight change can stably prevent the occurrence of such "slippery". have.

5. Manufacturing Method

(1) Method of producing colored antimicrobial glass

First, the flat colored antimicrobial glass which exhibits an antibacterial effect by releasing silver ion can be manufactured including following process (A)-(B).

(A) Melting process of heat-melting a raw material and producing colored molten glass containing 0.001-0.5 weight% of inorganic colorant with respect to the total amount.

(B) Molding process made into mixed antimicrobial glass whose largest diameter t1 is 3-30 mm, cooling colored molten glass.

That is, according to such a manufacturing method, even if it directly contacts water, the coloring antimicrobial glass which can maintain an initial appearance and discrimination can be efficiently produced, exhibiting a predetermined antimicrobial effect over a long period of time.

Hereinafter, the manufacturing method of colored antimicrobial glass is demonstrated more concretely.

First, as a raw material, it is stirred until it mixes uniformly on the conditions of rotation speed 250 rpm and 30 minutes using the all-purpose mixer so that 1st glass composition and 2nd glass composition mentioned above may be mentioned. At this time, an inorganic colorant such as cobalt oxide is added so as to be 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 the condition of 1280 ° C for 3 hours and a half to produce a glass melt.

In addition, according to the kind and compounding ratio of a raw material, the heating conditions in a melting furnace can be changed suitably.

Next, the molten glass obtained by performing a shaping | molding process and melting a glass raw material is made into the coloring antimicrobial glass of a predetermined shape.

Specifically, as shown in Figs. 11 (a) to 11 (b), by using the predetermined rotating members 20a and 20b, the so-called chocolate cut using the thin portion is possible, and thus the handling, The colored antimicrobial glass 10 in which adjustment of an area and a shape is easy 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 antimicrobial glass is used by using the concave portion 24 provided on the surface of the rotating member 20a. (10) can be molded. In addition, it is preferable that a cooling pipe (not shown) is provided at the center of the pair of rotating members 20a and 20b to control the surface temperature of the rotating members 20a and 20b. Moreover, since colored antimicrobial glass maintains predetermined temperature because it shape | molded in single shape through the thin part, it is preferable to spray cooling air on the surface of antimicrobial glass in order to cool additionally.

Next, a surface polishing process is performed. That is, using the stirring apparatus or grinding apparatus of a V blender, a ball mill, a vibration ball mill, etc., the obtained plate-shaped antimicrobial glass and water or alcohol (isopropyl alcohol etc.) are mixed and stirred at room temperature for about 10 minutes-24 hours, In addition, the foreign matter adhering to the surface of the colored antimicrobial glass is removed to secure a clean surface. In addition, it is preferable to deburring and to chamfer according to the side of flat antimicrobial glass further.

That is, by performing the surface polishing process in this way, the amount of silver eluted increases from the beginning, and the amount of silver eluted is also easily controlled.

(2) Production method of non-antibacterial glass

Also about non-antibacterial glass, it can manufacture similarly to colored antimicrobial glass except not adding an inorganic type coloring agent and a silver oxide raw material.

That is, it can manufacture efficiently by mixing the raw material of non-antibacterial glass, melting, shaping | molding, and grinding | polishing.

(3) mixing process

Next, in the mixing step, the obtained colored antimicrobial glass and the non-antibacterial glass can be uniformly mixed using a mixing apparatus.

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 use, the mixing step may be omitted, and the colored antibacterial glass and the non-antibacterial glass obtained may be separately prepared, and may be naturally mixed in the coating container (coating material) of the mixed antimicrobial glass. That is, in the use mode, such as a mixed antimicrobial glass for washing and a mixed antimicrobial glass for baths, it is vibrated during washing or floating in a bath, and a coloring antimicrobial glass and a non-microbial glass mix naturally.

Hereinafter, the present invention will be described in further detail by 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. Fabrication of Mixed Antimicrobial Glass

(1) Preparation of antimicrobial glass

(1) -1 melting process

As the first glass composition, as shown in Table 1, when the total amount was 100% by weight, Ag ₂ O was 3% by weight, ZnO was 30% by weight, CaO was 20% by weight, and B ₂ O ₃ was 5 The glass raw materials corresponding to the respective glass compositions were uniformized under the conditions of rotational speed of 250 rpm and 30 minutes by using a universal mixer so that the weight%, P ₂ O ₅ was 42% by weight, and CoO was 0.01% by weight. Stir until mixed well.

Next, the glass raw material was heated on the conditions of 1280 degreeC and 3 and a half hours using the glass melting furnace, and the molten glass was produced.

(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 a disc-shaped mixed antimicrobial glass (rectangular small piece, maximum diameter t1: 15 mm, thickness t2) : 4 mm) was molded.

(1) -3 surface polishing process

500 g of the obtained discotic antimicrobial glass was charged into a vibrating ball mill using no media. Next, 500 g of isopropyl alcohol or water was added, and in that state, the oscillation ball mill was operated at room temperature and 30 minutes, and the surface grinding process including a deburring process was performed.

As a result, the fine unevenness was seen before the surface polishing step treatment, and the surface was smoothed and glossy after the surface polishing step treatment.

(2) Preparation of non-antibacterial glass

(2) -1 melting process

When the total amount was 100% by weight, the glass melting furnace had 58.8% by weight SiO ₂ , 27.0% by weight Na ₂ O, 10.0% by weight B ₂ O ₃ , 3.0% by weight CaO, and 1.2 by K ₂ O. Silica sand, soda ash, lime and the like were each added so as to be by weight. Next, the temperature of the glass melting furnace was set to 1350 degreeC, and it melt | dissolved on the conditions of 10 hours.

(2) -2 molding process

The molten glass taken out from the glass melting furnace was introduced into a molding apparatus 40 as shown in FIG. 11 to form a disc shaped non-antibacterial glass (rectangular small piece, maximum diameter t3: 15 mm, thickness t4: 4 mm). ) Was molded.

(2) -3 surface polishing process

500 g of the obtained discotic non-antibacterial glass was put into the vibration ball mill which does not use a media. Subsequently, 500 g of isopropyl alcohol or water was added, and the vibrating ball mill was operated on the conditions of room temperature and 30 minutes in that state, and the surface grinding process including a deburring process was performed.

(3) mixing process

Subsequently, using the ball mill without a dispersion medium, the obtained colored antimicrobial glass and the non-antibacterial glass were uniformly mixed on the conditions of rotation speed 60 rpm and stirring time 10 minutes using a mixing stirring apparatus, It was set as the mixed antimicrobial glass.

2. Evaluation of Mixed Antimicrobial Glass

(1) Silver ion elution evaluation

10 g of the obtained colored antibacterial glass was immersed in 100 ml of distilled water (20 degreeC), and it stirred for 24 hours using the shaker. The silver ion eluate was separated using a centrifugal separator, and further filtered with a filter paper (5C) to prepare a sample. Subsequently, silver ions in the measurement sample were measured by ICP emission spectroscopy to calculate the amount of silver ions eluted in the colored antimicrobial glass (mg / (g · 24Hrs)).

(2) outflow evaluation

On the surface of a stainless steel plate having a thickness of 1 mm and an area of 20 cm x 20 cm, a recess having a depth of 0.5 mm and an area of 5 cm x 5 cm was provided, and therein, 100 g (W1) of mixed antimicrobial glass was filled therein. This 1 L / min tap water was sprayed in the transverse direction. After the state was continued for 1 minute, the weight (W2) of the mixed antimicrobial glass which remained on the stainless steel plate was measured, and the residual ratio ((W1-W2) / W1 * 100) of the mixed antimicrobial glass was computed. And the outflow property of the mixed antimicrobial glass was evaluated on the following references | standards from the computed residual ratio.

(Double-circle): Residual rate is 90-100 weight%.

(Circle): A residual rate is less than 70-90 weight%.

(Triangle | delta): A residual rate is less than 30 to 70 weight%.

X: The residual ratio is less than 30% by weight.

(3) Antibacterial evaluation 1 (bacterial activity value evaluation)

Using the washing machine, the antimicrobial evaluation of the cotton cloth by the obtained mixed antimicrobial glass was performed. That is, 3 kg of cotton cloth was washed for 15 minutes using the washing machine shown in FIG. 13 in the state which mixed 20 g of mixed antimicrobial glass of the use mode shown in FIG. 8 was put into the washing tank of the washing machine. Next, about the cotton cloth after washing, the bacterial activity value regarding Staphylococcus aureus was measured based on JISL1902 (bacterial liquid absorption method). In addition, a bacterial activity value is a numerical value represented by Log (germ number: 1.4 * 10 <^4> )-Log (the number of live bacteria after 48 hours).

(Double-circle): Bacterial activity value is 1 or more.

(Circle): Bacterial activity value is 0.1 or more.

(Triangle | delta): A bacterial activity value is 0.01 or more.

X: Bacterial activity value is less than 0.01.

(4) Antibacterial evaluation 2 (evaluation of bacteriostatic activity value)

Using the washing machine, the antimicrobial evaluation with respect to the cotton cloth by the obtained mixed antimicrobial glass was performed. That is, 3 kg of cotton cloth was wash | cleaned for 15 minutes using the washing machine shown in FIG. Subsequently, the bacteriostatic activity value regarding the Staphylococcus aureus was measured based on JISL 1902 (bacterial liquid absorption method) about the cotton cloth after washing. Incidentally, the bacteriostatic activity value is a numerical value expressed in Log (the number of untreated cells: 6.5 × 10 ⁶ ) -Log (the number of viable cells after 48 hours).

(Double-circle): The bacteriostatic activity value is 5.0 or more.

(Circle): The bacteriostatic activity value is 3.0 or more.

(Triangle | delta): A bacteriostatic activity value is 2.0 or more.

X: bacteriostatic activity value is less than 2.0.

(5) Discoloration prevention effect

As mentioned above, antibacterial evaluation etc. were performed using the washing machine, and the discoloration prevention effect of the obtained mixed antimicrobial glass was evaluated. That is, after performing antimicrobial evaluation for 48 hours using the washing machine shown in FIG. 13, the mixed antimicrobial glass was taken out and the discoloration prevention effect was evaluated on condition of the following.

(Double-circle): No discoloration etc. are observed in mixed antimicrobial glass at all.

(Circle): Discoloration etc. are hardly observed in mixed antimicrobial glass.

(Triangle | delta): Discoloration etc. are observed to the mixed antimicrobial glass a little.

X: Discoloration of remarkable mixed antimicrobial glass, etc. are observed.

EXAMPLES 2-5

In Examples 2 to 5, as shown in Tables 1 to 3, the composition ratio of the colored antimicrobial glass and the addition amount of the inorganic colorant (cobalt oxide) were changed, except that the maximum diameter (t3) of the non-antibacterial glass was changed. In the same manner as in Example 1, mixed antimicrobial glasses were produced and evaluated, respectively.

[Comparative Examples 1-3]

In the comparative example 1, it evaluated similarly to Example 1 except having made the addition amount of the cobalt oxide of the colored antimicrobial glass in Example 1 into 0.0001 weight%.

In Comparative Example 2, iron oxide (Fe ₂ O ₃ ) was added instead of cobalt oxide (CoO) of the colored antimicrobial glass in Example 1, except that the addition amount was 0.0001% by weight. It evaluated similarly to Example 1.

In Comparative Example 3, the amount of cobalt oxide added in the colored antimicrobial glass in Example 1 was evaluated in the same manner as in Example 1 except that 0 wt%, that is, no cobalt oxide was added.

Moreover, the photograph of the mixed antimicrobial glass before evaluation start of the discoloration prevention effect in Comparative Examples 1-3, and the mixed antimicrobial glass after completion of evaluation are shown to numbers 3 and 4 of FIG.

According to the mixed antimicrobial glass of the present invention, even when used for a long time under strict conditions by mixing a colored antimicrobial glass to which a predetermined amount of an inorganic colorant is added and a non-antibacterial glass which is insoluble and does not change in weight, By the content, the weight change is small, and the water can be sufficiently brought into contact with the water, while the predetermined amount of silver ions can be repeatedly released while maintaining the initial appearance and discrimination.

Therefore, for example, antibacterial and bath water in washing can be released quickly, and a predetermined amount of silver ions can be efficiently carried out, and antibacterial and washed baths are repeatedly washed. Also in this, the same antibacterial effect can be exhibited.

Accordingly, the mixed antimicrobial glass of the present invention includes a washing machine, a dishwasher, an iron, a humidifier, a food cleaning tank, a medical appliance cleaner, a water tank for a flush toilet, a barn cleaner, an artificial lawn ground rotary nozzle type cleaner, and a bathtub. It can be used directly or indirectly suitably for various apparatuses and usage modes, such as a circulating water apparatus, a cooling tower for cooling, a sprayer, and a gardening hose.

In particular, in the use mode in which considerable rotational vibration and reciprocating motion are applied to the mixed antimicrobial glass, such as a washing machine or a bathroom, the weight change of the mixed antimicrobial glass is small, and the water can be sufficiently brought into contact with water. It is a suitable use for the mixed antimicrobial glass of this invention from being discolored.

Claims (10)

As a mixed antimicrobial glass containing the colored antimicrobial glass which exhibits antibacterial effect by releasing silver ion, and a non-antibacterial glass, The maximum diameter (t1) of the said colored antimicrobial glass shall be a value within the range of 3-30 mm, and also contains an inorganic coloring agent as a compounding component, and the addition amount of the said inorganic coloring agent is 0.001-0.5 weight with respect to whole quantity. Mixed antimicrobial glass, characterized by the value within the range of%. The method of claim 1, Said colored antimicrobial glass is flat form, The thickness (t2) of the said colored antimicrobial glass is made into the value within the range of 1-8 mm, The mixed antimicrobial glass characterized by the above-mentioned. The method according to claim 1 or 2, The inorganic colorant is at least one compound selected from the group consisting of cobalt oxide, copper oxide, chromium oxide, nickel oxide, manganese oxide, neodium oxide, erbium oxide, and cerium oxide, and the addition amount of the inorganic colorant is C1. When the addition amount of silver oxide contained similarly is set to C2, the ratio shown by C1 / C2 is made into the value within the range of 0.01-3, The mixed antimicrobial glass characterized by the above-mentioned. The method of claim 1, The elution amount of silver ions in the said colored antimicrobial glass is made into the value within the range of 0.01-1.0 mg / (g * 24Hrs), The mixed antimicrobial glass characterized by the above-mentioned. The method of claim 1, Said non-antibacterial glass contains soda glass, The mixed antimicrobial glass characterized by the above-mentioned. The method of claim 1, The mixed antimicrobial glass characterized by setting the maximum diameter (t3) of the said non-antibacterial glass to the value within the range of 3-30 mm. The method of claim 1, The addition amount of the said non-antibacterial glass is made into the value within the range of 10-3000 weight part with respect to 100 weight part of said colored antimicrobial glasses, The mixed antimicrobial glass characterized by the above-mentioned. The method of claim 1, In the washing of cloth products using a washing machine, a mixed antimicrobial glass is added to a washing tank of a washing machine to impart a predetermined antimicrobial property to a cloth and a washing tank. The mixed antimicrobial glass in which the circumference | surroundings of several mixed antimicrobial glass is coat | covered by the 1st water permeable member, and the circumference | surroundings of a water permeable member are further coat | covered with a 2nd water permeable member. The method of claim 1, As a mixed antimicrobial glass for pouring a bath water into a bath tub and floating it in the bath water to impart a predetermined antimicrobial activity to the bath water and the bath, A mixed antimicrobial glass, wherein the periphery is covered by the shape-retaining member and the periphery is additionally covered by the water permeable member. The method of claim 1, A mixed antimicrobial glass provided in a sanitary ware and housed in a container provided with a water passage as a mixed antimicrobial glass for imparting predetermined antimicrobial properties to the sanitary ware.

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