WO2005087675A1

WO2005087675A1 - Antibacterial glass and method for producing antibacterial glass

Info

Publication number: WO2005087675A1
Application number: PCT/JP2005/004292
Authority: WO
Inventors: Yoshiaki Kamiya; Shinobu Kanamaru
Original assignee: Koa Glass Co., Ltd.
Priority date: 2004-03-15
Filing date: 2005-03-11
Publication date: 2005-09-22
Also published as: JP5845209B2; JP2013155114A; CN101298364B; CN101298364A; CN1771207A; JPWO2005087675A1; KR20060012326A; CN100413799C; JP5378647B2; KR100657123B1

Abstract

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

Description

Specification

Antibacterial glass and method for producing antibacterial glass

Technical field

The present invention relates to an antibacterial glass for a washing machine that can elute silver ions by coming into direct contact with water during or after washing of an antibacterial object (an antibacterial glass for a washing machine having an antifungal property). The present invention relates to an antibacterial glass suitable as such, and a method for producing such an antibacterial glass.

More specifically, an antibacterial glass suitable as an antibacterial glass for a washing machine or the like for performing antibacterial treatment with silver ions during or after washing of an antibacterial object, and when it comes into direct contact with water. The present invention relates to an antibacterial glass capable of releasing a predetermined amount of silver ions quickly and for a long period of time, and a method for producing such an antibacterial glass.

Background art

[0002] In recent years, antibacterial glass having a predetermined particle size has been used for building materials, home appliances (including TVs, personal computers, mobile phones, video cameras, etc.), miscellaneous goods, packaging materials, and the like, in order to impart an antibacterial effect. An antibacterial resin composition mixed in a predetermined amount into fat is used.

As such an antibacterial resin composition, there is disclosed a synthetic resin molded article containing borosilicate antibacterial glass that elutes silver ions in the resin (for example, see Patent Document 1).

More specifically, the strong synthetic resin molded body is made of SiO

2, B O or two 23, one of P O

twenty five

The above network-forming oxide and Na 0

2, K 0

2, CaO, one or two or more kinds of {η} network-modified oxides and 100 parts by weight of a glass solid that also acts as a monovalent Ag in a weight of 100 parts by weight of AgO.

2

. It is composed of synthetic resin containing borosilicate antibacterial glass containing 20 parts by weight. Then, in the examples of the patent publication, SiO: 40 mol ^_0/0, BO: 50 mol%

2 2 3

2 parts by weight of Ag O was added to 100 parts by weight of a mixture consisting of Na 0: 10 mol%,

twenty two

An antibacterial resin composition containing an antibacterial glass having an average particle size of 20 m or less in a synthetic resin is disclosed.

[0003] Further, as an antibacterial resin composition, the particle size having antibacterial properties is 10-1000 μm, and the thickness is 0.

A resin composition containing glass flakes of 120 m in length is disclosed (for example, Patent Document More specifically, as the composition of the glassy glass flakes, when BO is contained, S

twenty three

iO: 20-60% by weight, BO: 30-70% by weight, NaO: 5-35% by weight, AgO: 0.5-3

2 2 3 2 2% by weight, when not containing B O, SiO: 55—80% by weight, AIO: 0.5—

2 3 2 2 3

30% by weight, Na 0: 19.5-42% by weight, Ag 0: 0.5-3% by weight.

twenty two

[0004] In addition, when immersed in boiling water at 100 ° C for 500-1000 hours and then immersed in water or an acid at 20 ° C for 24 hours, the silver ion elution amount is 0.5 ngZcm ² Zday or more. An antibacterial water-containing product containing an ion-containing inorganic antibacterial agent and an inorganic filler is disclosed (for example, see Patent Document 3).

More specifically, in the resin, P O: 56-59 mol%, MgO + CaO + ZnO: 33-38

twenty five

mol%, Al O: 6-8 mol% glass composition with 0-5 wt% Ag O

2 3 2

Disclosed antibacterial water-based products composed of 0.5 to 5% by weight of inorganic antibacterial agent containing silver ion and 2 to 20% by weight of inorganic filler with average particle size of 2 to 20m Have been.

[0005] Further, as an application of the antibacterial glass, an antibacterial resin composition has been proposed which exemplifies electric appliances such as a dishwasher, a dish dryer, a refrigerator, a washing machine, and a pot (for example, see Patent Documents). 4 and 5).

That is, during molding榭脂constituting mosquitoesゝmowing appliances, average particle diameter of 20 m or less of Z nO: 40- 80 mole ^_0/0, SiO: 5-35 mol%, CaO: 5-30 mol ⁰ / ₀ anti-bacterial gala

2

Suya, also mean particle size of 20 m or less of ZnO: 5 4- 60 mole ^_0/0, BO: 25-32 mole ^_0/0

twenty three

, SiO: 7-12 mol%, alkali metal oxides: an antimicrobial glass consisting 5-8 mole ^_0/0,

2

Antibacterial resin compositions containing a predetermined amount of each.

Further, as an application of antibacterial glass, a glass water treating agent used in a water treatment device such as a water storage tank or a cooling tower has been proposed (for example, see Patent Document 6).

That is, it is a phosphate glass having a longest diameter of 10 mm or more, and its weight composition ratio is (R 0 + RO) / PO = 0.4-1.2, ROZ (RO + RO) = 0-10 (R is Ca ゝ Na

2 2 3 2 2 3

Etc.) When the initial dissolution rate is A and the final dissolution rate is B, the glass water treatment agent has a BZA≥1Z3 and a metal ion content of 0.005-5% by weight. Patent Document 1: Japanese Patent Application Laid-Open No. 1-313531 (Claims) Patent Document 2: Japanese Patent Application Laid-Open No. 7-25635 (Claims)

Patent Document 3: JP-A-10-72530 (Claims)

Patent Document 4: Japanese Patent Application Laid-Open No. 2000-3238 (Claims)

Patent Document 5: Japanese Patent Application Laid-Open No. 2000-3239 (Claims)

Patent Document 6: Japanese Patent Publication No. 7-63701 (Claims)

Disclosure of the invention

Problems to be solved by the invention

[0006] However, since the antibacterial resin compositions disclosed in Patent Documents 15 are all formed by adding antibacterial glass to the resin, the antibacterial resin compositions are disclosed. Glass was configured to be able to release silver ions for the first time by indirect contact with water that has penetrated into the resin.

Therefore, when a high antibacterial resin composition is used, even if it is possible to impart a predetermined antibacterial property to parts of electrical products, etc., it is directly in contact with water during or after washing the antibacterial object. Thus, it was practically difficult to quickly release silver ions by contacting the antibacterial substance and to attach a predetermined amount of silver ions to the antibacterial substance.

In Patent Documents 1 and 3-5, the average particle size of the antibacterial glass is preferably about 20 m or less in order to uniformly mix the resin. In Patent Document 2, the antibacterial glass has a predetermined size. Although the glass flakes were used, there was a manufacturing problem that these values had to be restricted to a predetermined range by using a classifying device or the like as a manufacturing device.

On the other hand, the glass water treatment agent disclosed in Patent Document 6 has a problem that although the longest diameter is relatively large, the amount of silver ion eluted is basically small. Therefore, similar to the antibacterial resin composition disclosed in Patent Documents 1 to 5, the antibacterial object is brought into direct contact with water during or after washing to quickly release silver ions, and It was practically difficult to attach a predetermined amount of silver ions to an antibacterial substance.

[0007] Accordingly, the present inventors have conducted intensive studies and as a result, by restricting the size of the antibacterial glass and the amount of silver ion eluted to a predetermined range, they come into direct contact with water and repeatedly repeat a predetermined amount of water. They have found that silver ions can be released quickly and for a long period of time, and have completed the present invention. That is, according to the present invention, during or after washing the antibacterial substance, it comes into direct contact with water to release a predetermined amount of silver ions quickly and for a long period of time. It is an object of the present invention to provide an antibacterial glass suitable as an antibacterial glass for a washing machine that can be subjected to an antibacterial treatment, and a method for producing such an antibacterial glass. Means for solving the problem

According to the present invention, there is provided an antibacterial glass for releasing silver ions upon direct contact with water and exhibiting an antibacterial effect, and has a maximum diameter (tl) within a range of 1 to 50 mm. And an antibacterial glass having a silver ion elution amount within a range of 0.5 to 100 mgZ (g'24Hrs), which can solve the above-mentioned problem.

That is, according to the antibacterial glass of the present invention, for example, during or after washing of an antibacterial substance, a predetermined amount of silver ions can be released quickly and for a long period of time by direct contact with water. it can. Therefore, a predetermined antibacterial treatment can be repeatedly applied to the antibacterial object. In addition, antibacterial glass having such a size not only facilitates handling, but also causes adjacent glass to come into contact with each other, agglomeration or fusion, despite extremely high solubility. Can be effectively prevented.

[0009] Further, in constituting the antibacterial glass of the present invention, it is preferable that the antibacterial glass for a washing machine is subjected to an antibacterial treatment with silver ions during or after washing of an antibacterial object.

That is, in a washing machine application or the like, a predetermined amount of silver ions can be released over a long period of time, and a predetermined antibacterial effect can be continuously imparted to laundry or the like.

[0010] Further, in constituting the antibacterial glass of the present invention, B O, SiO, and

2 3 2

Ag O and alkali metal oxides are included, and the amount of B O added is

2 2 3

30 60% by weight, SiO addition amount 30 60% by weight, AgO addition amount 25% by weight,

twenty two

In addition, it is preferable that the addition amount of the alkali metal oxidized product be in the range of 5 to 10% by weight.

In other words, since the raw materials of the predetermined boric acid-based antibacterial glass are blended in the respective predetermined amounts, it is possible to release a predetermined amount of silver ions over a long period of time by directly contacting with water. As a result, a predetermined antibacterial effect can be continuously exerted. Further, according to such antibacterial glass for a washing machine, a predetermined antibacterial treatment can be stably applied to an antibacterial object washed with a detergent having low reactivity with a detergent. In the case of strong antibacterial glass, use a relatively large amount of BO as a raw material.

twenty three

Therefore, it may be easy to color depending on the manufacturing conditions and the use conditions. However, antibacterial glass is used, for example, in invisible places such as waterways in a washing machine, or a colored covering material is applied from the surroundings, and as described later, a complex as a coloring inhibitor is used. By adding the forming compound, vigorous coloring problems can be avoided.

[0011] Further, when constituting the antibacterial glass of the present invention, P O, Ag O,

2 5 2 Alkali metal oxides and the total amount of PO

twenty five

Weight percent, 2 to 5 weight percent Ag 2 O, and 15 alkali metal oxides.

2

It is preferred that the value be within the range of 35% by weight.

That is, since a predetermined amount of the phosphoric acid-based antibacterial glass raw material is blended in a predetermined amount, by directly contacting with water, for example, in a washing machine application, a predetermined amount of silver ion And a predetermined antibacterial effect can be continuously imparted to the laundry.

Further, such a phosphate antibacterial glass is excellent in transparency and can release a predetermined amount of silver ions even if it is granular, regardless of whether it is flat. Furthermore, with such a phosphate antibacterial glass, it is possible to obtain an advantage if the production conditions are reduced so that the corrosiveness to a melting furnace or the like during production is reduced.

[0012] Further, in constituting the antibacterial glass of the present invention, a plurality of glass pieces are connected via a thin portion having the same component strength as the antibacterial glass as a whole and having a flat plate shape. It is preferable that it is configured.

That is, since a plurality of flat glass pieces are connected via a predetermined thin portion, the glass pieces are cut into a predetermined size, and the absolute elution amount (elution rate) of silver ions is easily adjusted. be able to. Therefore, the antibacterial glass of the present invention can be cut into an arbitrary size and used in consideration of the environmental conditions and the amount of water to be used or the long-term use time, etc., by adopting a so-called chocolate cut shape. In addition, since it has a predetermined thin portion, it is used as a cut point and has an appropriate size according to the size and shape of the place of use. And antibacterial glass of different shapes.

[0013] Further, in constituting the antibacterial glass of the present invention, it is preferable that a coating member is provided around the antibacterial glass, and that the cartridge is inscribed!

That is, since the cartridge is provided with the predetermined covering member and is cartridge-shaped, not only is it easy to handle and exchange, etc., but even when a relatively strong water flow is used, the water is discharged to the outside together with the water flow. Outflow can be effectively prevented.

[0014] Another embodiment of the present invention is a method for producing an antibacterial glass for releasing silver ions by directly contacting with water to exhibit an antibacterial effect, comprising the following step (A): (B) A method for producing an antibacterial glass, comprising:

(A) As raw materials, B O, SiO, Ag O, and alkali metal oxide are heated and melted.

2 3 2 2

Melting process to create molten glass

(B) While cooling the molten glass, an antibacterial glass having a predetermined shape with a maximum diameter (tl) of 1 to 50 mm and an elution amount of silver ions of 0.5 to 100 mgZ (g · 24Hrs) is obtained. Molding process

In other words, since the process includes a predetermined manufacturing process, it can release silver ions by coming into direct contact with water and quickly exert an antibacterial effect. As a result, the object to be antibacterial can be washed or washed. Later, an antibacterial glass that releases a predetermined amount of silver ions and can stably perform a predetermined antibacterial treatment on an antibacterial substance can be efficiently obtained.

[0015] Still another embodiment of the present invention relates to a method for producing an antibacterial glass for releasing silver ions upon direct contact with water and exhibiting an antibacterial effect, comprising the following steps (Α (1) A method for producing an antibacterial glass, characterized by containing one (抗菌 ').

(ΑΊ Raw materials, Ρ Ρ, Ag O, and alkali metal oxide

2 5 2

Melting process to make molten glass

(ΒΊ While cooling the molten glass, an antibacterial glass having a predetermined shape with a maximum diameter (tl) of 1 to 50 mm and an amount of silver ion eluted of 0.5 to 100 mgZ (g · 24Hrs) Molding process

In other words, since the phosphoric acid-based antibacterial glass includes a predetermined manufacturing process, the antibacterial effect can be promptly exerted by releasing silver ions by directly contacting with water. The result As a result, it is possible to efficiently obtain an antibacterial glass that releases a predetermined amount of silver ions during or after washing of the antibacterial substance and can stably perform a predetermined antibacterial treatment on the antibacterial substance. .

In carrying out the method for producing an antibacterial glass of the present invention, in the step (B) or the step (ェ), a flat antibacterial glass is formed using a rotating member having a concave portion on the surface. Is preferred.

That is, in step), by using a predetermined rotating member, it is possible to cut chocolate using a so-called thin portion, and to efficiently obtain an antibacterial glass that is easy to handle, adjust in area, shape, and the like. be able to.

In carrying out the method for producing an antibacterial glass of the present invention, between steps (A) and (B), or between (ΑΊ and (で), on a substrate provided with a cooling device. Preferably, the method further includes a step of cooling the antibacterial glass.

That is, since a predetermined cooling step is included, the molten glass without using water can be cooled sufficiently and uniformly, and can be accurately formed into a predetermined shape in the next step. Brief Description of Drawings

[FIG. 1] (a)-(f) are views provided for explaining the shape of the antibacterial glass of the first embodiment.

FIG. 2 is a diagram provided for explaining a relationship between a maximum diameter (tl) of an antibacterial glass and a residual ratio.

FIG. 3 is a diagram provided to explain the relationship with the amount of silver ion eluted with the number of washings.

FIG. 4 is a view showing a washing machine to which the antibacterial glass of the first embodiment is applied.

FIG. 5 is a diagram provided for explaining a shape of an antibacterial glass.

FIG. 6 is a view provided to explain a coating member of antibacterial glass (part 1).

[FIG. 7] (a)-(c) is a diagram provided to explain a coating member of antibacterial glass (part 2).

FIG. 8 is a diagram provided for explaining a shape of an antibacterial glass and a covering member.

FIG. 9 is a diagram provided for explaining a method of using the antibacterial glass.

FIG. 10 is a diagram provided for explaining an antibacterial method for an antibacterial substance. FIG. 11 is a diagram provided for explaining a method for manufacturing the antibacterial glass of the second embodiment (part 1).

FIG. 12 is a diagram provided for explaining a method for manufacturing the antibacterial glass of the second embodiment (part 2)

FIG. 13 is a view provided for explaining a method of manufacturing the antibacterial glass of the third embodiment. (Part 1)

FIG. 14 is a view provided for explaining a method of manufacturing the antibacterial glass of the third embodiment. (Part 2)

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the antibacterial glass, the method for producing the antibacterial glass, and the method for using the antibacterial glass of the present invention will be specifically described mainly for antibacterial glass for a washing machine.

[First Embodiment]

The first embodiment is an antibacterial glass for releasing silver ions in direct contact with water and exhibiting an antibacterial effect, and has a maximum diameter (tl) within a range of 1 to 50 mm. It is an antibacterial glass with a silver ion elution amount in the range of 0.5-100 mg / (g'24Hrs).

[0021] 1. Antibacterial glass

(1) Shape 1

The shape of the antibacterial glass is not particularly limited, but as shown in FIG. 1 (a)-(f), a flat plate having a rectangular shape, a polygonal shape, a circular shape, an elliptical shape, an irregular shape, a perforated shape, etc. It is preferred that it is in the form.

The reason for this is that the antibacterial glass is formed in a flat plate shape such as a rectangular shape or a perforated shape, so that even if it is placed at a predetermined location and brought into direct contact with water, it is washed away by water pressure, This is because it is possible to effectively prevent the power from flowing out of the predetermined location. In addition, if the antibacterial glass is rectangular or the like, it is difficult to coagulate during manufacturing or use, so the size and shape of the antibacterial glass during manufacturing and the control of environmental conditions during use are also considered. This is because it becomes easier. However, as long as the maximum diameter (tl) and the range of the elution amount of silver ions are satisfied, the antibacterial glass can be formed into any shape such as a polyhedral, granular, spherical, elliptical, columnar, or pulverized body. (2) Shape 2

In addition, the maximum diameter (tl) of the antibacterial glass is set to a value within a range of 1 to 50 mm. Here, the maximum diameter (tl) of the antibacterial glass is, for example, the maximum length when an arbitrary line is drawn in the shape of the antibacterial glass as shown in FIGS. Means That is, the maximum diameter (tl) of the antibacterial glass is the maximum diameter in the plane direction when the antibacterial glass is, for example, a flat plate, and the maximum diameter of the particles when the antibacterial glass is granular. .

Also, the reason for limiting the maximum diameter (tl) of the antibacterial glass is that when the maximum diameter to be pressed is less than lmm, it is placed at a predetermined location and pressed directly by water when pressed against water. It may be easily washed away and force to flow out of a specified location, or it may be difficult to release silver ions of a predetermined concentration for a long period of time, or it may be easy to agglomerate during storage. is there.

On the other hand, if the maximum diameter exceeds 50 mm, handling becomes difficult or stable production becomes difficult.

Therefore, when the shape of the antibacterial glass is flat or the like, it is more preferable to set the maximum diameter to a value in the range of 8 to 30 mm, more preferably to a value in the range of 15 to 20 mm. When the shape of the antibacterial glass is granular, etc., it is more preferable to set the maximum diameter to a value within the range of 3 to 25 mm in consideration of the easiness of production. More preferably, it is set to a value.

When the antibacterial glass has a flat shape, the thickness of the antibacterial glass is preferably in the range of 0.1 to 10 mm.

The reason for this is that when the thickness of the strong antibacterial glass is less than 0.1 mm, it becomes difficult to release silver ions of a predetermined concentration, handling becomes difficult, and stable production This may be difficult. On the other hand, if the thickness of the antibacterial glass exceeds 10 mm, on the other hand, handling becomes difficult, and it becomes difficult to manufacture it stably.

Therefore, if the antibacterial glass is flat, its thickness should be in the range of 0.5-8 mm. It is more preferable to set the value within the range. It is more preferable to set the value within the range of 11 to 5 mm.

The maximum diameter / thickness of the antibacterial glass described above can be easily measured using, for example, an optical microscope photograph or a caliper.

(3) Shape 3

Next, regarding the shape of the antibacterial glass, the relationship between the maximum diameter (tl) of the antibacterial glass in the plane direction and the residual ratio when the antibacterial glass is used will be described in detail with reference to FIG. . The horizontal axis of FIG. 2 shows the maximum diameter (mm) of the antibacterial glass in the plane direction in logarithm, and the vertical axis shows the antibacterial glass in Examples described later when the antibacterial glass of each particle size is used. The residual ratio (%) measured according to the method for measuring the residual ratio of lath is shown.

As is clear from Figure 2, if the maximum diameter (tl) of the antibacterial glass in the planar direction is 5 mm or more, the residual ratio shows a relatively high value, that is, a value of 50% or more. However, it is understood that it can withstand long-term use.

Next, regarding the shape of the antibacterial glass, referring to FIG. 3, the antibacterial glass according to the present invention (maximum diameter in the plane direction of 15 mm) and the antibacterial glass having an average particle diameter of 20 μm were used. The change in the number of washings and the amount of silver ion eluted in this case will be described in detail. That is, the horizontal axis of FIG. 3 indicates the number of washings using each antibacterial glass using the washing machine 50 as shown in FIG. 4, and the vertical axis of FIG. The elution amount of ion (mg / (g'24Hrs)) is shown. Further, in the figure, the data on the antibacterial glass of the present invention is shown by a solid line A, and the data on the antibacterial glass having an average particle diameter of 20 μm is shown by a dotted line B.

As shown in FIG. 3, the antibacterial glass of the present invention (antibacterial glass for a washing machine) has a predetermined maximum diameter in the plane direction and is not washed away by water pressure or the like, so that the residual amount is small. It does not decrease significantly. Therefore, it can be understood that the desired elution amount can be maintained even when used repeatedly. Therefore, it is understood that the antibacterial glass of the present invention is immune to long-term use.

On the other hand, antibacterial glass having an average particle size of 20 m, as shown in Fig. 2 above, reduces the residual amount of antibacterial glass each time it is used. One As a result, the value of the amount of eluted significantly decreased compared to the amount of silver ion eluted immediately after the start of use. Therefore, it is understood that frequent replenishment of the antibacterial glass is necessary in order to secure a desired elution amount of silver ions.

[0024] (4) Shape 4

Further, regarding the shape of the antibacterial glass, as shown in FIGS. 5 (a) and 5 (b), the antibacterial glass is formed as a whole through a thin portion 12 having the same component power as the antibacterial glass. It is preferable that a plurality of glass pieces 10a are connected to each other.

The reason is that the antibacterial glass of a large area is cut into an arbitrary size by so-called chocolate cutting in consideration of the environmental conditions, the amount of water used, or the long-term use time, etc. Because it can be used. That is, a large-area antibacterial glass can be cut into a predetermined size by using a predetermined thin portion, and the amount of silver ion eluted (elution rate) can be easily adjusted.

In addition, since a predetermined thin portion is provided, the size and shape of the antibacterial glass can be appropriately determined in accordance with the size and shape of the place of use by using the cut portion as a cut portion.

[0025] (5) Type 1

Regarding the type of antibacterial glass, it is preferable to use a boric acid antibacterial glass having the following composition. That is, B O

2 3 and SiO

2 and Ag O

2 and alkali metal oxides, and

2 3 Add 30-60 weight

%, The amount of SiO added is 30-60% by weight, the amount of AgO added is 2-5% by weight,

twenty two

It is preferable that the addition amount of the metal oxide is a value within the range of 5 to 10% by weight.

The reason for this is that an antibacterial glass having such a glass composition power can immediately release a predetermined amount of silver ions by directly contacting with water. Further, according to the antibacterial glass having such a glass composition, it is possible to stably perform a predetermined antibacterial treatment on an antibacterial object washed with a detergent having a low reactivity with a detergent. Because we can

[0026] Here, B O basically functions as a network-forming oxide.

twenty three

The invention relates to the function of improving the transparency of antibacterial glass and the uniform release of silver ions. Give.

In addition, SiO functions as a network-modified antioxidant in antibacterial glass.

2

In addition, it functions to prevent yellowing.

Ag O is an essential component in the antibacterial glass, and the glass component dissolves.

2

By eluting silver ions, excellent antibacterial properties can be exhibited for a long period of time. Alkali metal oxides, such as Na O and K O, are basically network-modified oxides.

twenty two

Function while improving the transparency of antibacterial glass and adjusting the melting temperature! , Can also be demonstrated.

In addition, by adding an alkaline earth metal oxide, for example, MgO or CaO, it can function as a network-modified acid oxide, while, like the alkali metal oxide, the antibacterial glass It can also exhibit the function of improving the transparency and the function of adjusting the melting temperature.

2 2 3

Properties or mechanical strength can also be improved.

[0027] (6) Type 2

Regarding the type of antibacterial glass, it is preferable to use a phosphate antibacterial glass having the following composition. That is, as raw materials, P O, Ag O, and alkali metal oxide

2 5 2

And 40% to 70% by weight of P 2 O

It is preferable that the addition amount is within a range of 2 to 5% by weight and the addition amount of alkali metal oxide is within a range of 15 to 35% by weight.

The reason for this is that a phosphate-based antibacterial glass having such a glass composition ability can quickly release a predetermined amount of silver ions by directly contacting with water. In addition, according to the antibacterial glass having such a glass composition power, it has excellent transparency and releases a predetermined amount of silver ions within a predetermined time even if the particles have a predetermined particle size irrespective of a flat shape. It is possible because it is easy to use. Furthermore, such a phosphoric acid-based antibacterial glass can be manufactured and economically reduced in terms of manufacturing conditions, such as reducing the corrosiveness to a melting furnace during manufacturing, or reducing manufacturing costs. You can also get benefits.

[0028] Here, PO basically functions as a network-forming oxide. In the invention, it also relates to the function of improving the transparency of the antibacterial glass and the uniform release of silver ions.

2

twenty two

2 2 3

Properties or mechanical strength can also be improved.

(7) Silver ion elution amount

The elution amount of silver ion in the antibacterial glass is set to a value within the range of 0.5 to 1 OOmgZ (g · 24Hrs).

The reason is that when the elution amount of strong silver ions is less than 0.5 mg / (g'24Hrs), the silver ions of a predetermined concentration can be released quickly when they come into direct contact with water. This can be difficult.

On the other hand, when the elution amount of strong silver ions exceeds 100 mgZ (g'24Hrs), 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 may be difficult to manufacture the same.

Therefore, it is more preferable to set the elution amount of silver ions in the antibacterial glass to a value within the range of 90 mgZ (g'24Hrs), more preferably to a value within the range of 10-70 mgZ (g'24Hrs). More preferred.

The elution amount of silver ions in the antibacterial glass can be measured according to the measurement method described in Example 1 described later.

[0030] 2. Coating members or additives (1) Complex-forming compound

Complex-forming compounds capable of forming a complex with silver ions, such as ammonium sulfate, ammonium nitrate, sodium chloride, sodium thiosulfate, sodium chloride, ammonium sulfate, and ammonium sulfate. It is preferable to add one or a combination of two or more of tylenediaminetetraacetic acid (EDTA), ammonium acetate, ammonium perchlorate, and ammonium phosphate. Addition of such a complex-forming compound can significantly prevent discoloration and coloring of the antibacterial glass.

Note that even when the atmosphere is a strong alkali, for example, a pH value of 10 or more, a complex can be easily formed with silver ions to prevent coloration. It is more preferable to use ammonium nitrate, sodium salt ammonium, and at least one compound selected from the group consisting of sodium thiosulfate.

[0031] The amount of the complex-forming compound to be added is preferably set to a value within the range of 0.01 to 30% by weight based on the total amount.

The reason is that if the amount of the powerful complex-forming compound is less than 0.01% by weight, it may be difficult to effectively prevent discoloration. On the other hand, if the amount of the complex-forming compound exceeds 30% by weight, the antibacterial properties of the antibacterial glass may be reduced or it may be difficult to mix them uniformly.

Therefore, since the balance between the discoloration resistance and the antibacterial property of the strong antibacterial glass is more preferable, the amount of the complex-forming compound to be added is within the range of 0.1 to 20% by weight based on the total amount. The value is more preferably set to a value in the range of 0.5 to 10% by weight.

[0032] (2) Coating member

Further, as shown in FIG. 6, it is also preferable that the covering member has a form in which an antibacterial glass 10 is covered with an inorganic substance and / or an organic substance, or one of the particles 14.

With this configuration, it is possible to easily control the elution rate of silver ions and to improve the anti-aggregation property of the antibacterial glass.

The particles that coat the antibacterial glass include titanium oxide, silicon oxide, and colloidal. Silica, zinc oxide, tin oxide, lead oxide, white carbon, acrylic particles, styrene particles, polycarbonate particles, and the like, alone or in combination of two or more are preferred.

Further, the method of coating the antibacterial glass with the particles is not particularly limited. For example, after uniformly mixing the antibacterial glass and the particles, the mixture is heated at a temperature of 600 to 1200 ° C to form the glass. It is preferable to fix by a force for fusing or a binder.

[0033] It is preferable to provide a cartridge around the antibacterial glass by providing a wrapping member as a covering member or a housing.

The reason for this is that by providing such a covering member, it is possible to facilitate handling during storage and to prevent agglomeration of the antibacterial glass. In addition, in use, the usability is improved, and even when a relatively strong water flow is used, it is possible to prevent the outflow of a predetermined place force. Further, since the cartridge is formed, it can be easily carried out in handling, exchange, and the like.

For example, as shown in FIG. 7 (a), a plurality of antibacterial glasses 10a are packaged using a moisture-proof material such as an aluminum laminated film 16, or as shown in FIG. 7 (b). It is preferable to package the package and further cover the periphery with a perforated member (mesh member) 18, as shown in FIG. 7 (c).

When granular or spherical shape is used as the shape of the antibacterial glass, as shown in FIG. 8 (a), the antibacterial glass is enclosed in a cylindrical housing 18 'whose both end surfaces are covered with a mesh member having a smaller particle size. It is preferable to encapsulate 10 and connect them to form a cartridge as shown in FIG. 8 (b). With such a configuration, it is possible to minimize agglomeration due to contact between the antibacterial glasses, even if the shape is granular or spherical, which is difficult to cover with the covering member. In addition, with such a configuration, the adjustment of the Ag elution amount becomes extremely easy. In particular, the granular antibacterial glass can be composed of phosphoric acid-based glass as a raw material, thereby compensating for the slow dissolution rate by enlarging the glass surface area and obtaining a desired Ag elution amount. It becomes.

[0034] (3) Surface treatment

In addition, antibacterial glass is dispersed for antioxidant or coloring purposes. Surfactants, stearic acid, myristic acid, sodium stearate, silane coupling agents, etc., hindered phenolic conjugates as anti-irridation agents, pigments as coloring agents, such as hindered amine compounds, etc. It is preferable to add a dye or the like.

Although the amount of these additives is preferably determined in consideration of the effect of addition, etc.

For example, it is more preferable to set each of them to a value in the range of 0.01 to 30% by weight based on the total amount.

[0035] 3. Example usage

In using the antibacterial glass of the present invention, it is preferable to include the following steps (C) to (D).

(C) a step of making silver-ion-containing water by directly contacting the antibacterial glass with water (sometimes referred to as a contacting step)

(D) A step of treating an antibacterial substance with silver ion-containing water and applying an antibacterial treatment (sometimes referred to as an antibacterial step)

Hereinafter, a method of using such antibacterial glass (antibacterial glass for a washing machine) will be specifically described assuming that the antibacterial glass is used for the washing machine 50 shown in FIG.

[0036] (1) Contact step

The method of direct contact between the antibacterial glass and water is not particularly limited.For example, the antibacterial glass can be immersed in water, or the antibacterial glass can be put into a stream of water. It is preferable to make silver-ion-containing water by directly contacting the glass with water.

At this time, for example, when antibacterial glass is used in a washing machine, as shown in FIG. 9, a bypass 26 is provided and the antibacterial glass 10 for the washing machine is placed there, and when necessary, It is preferable to obtain a silver ion-containing water by opening and closing a valve 28 communicating with the bypass 26 to allow water to flow in and directly contact the antibacterial glass 10 for a washing machine.

The reason for this is that, for example, by using silver ion-containing water only in the final stage of washing, silver ions do not flow wastefully. This is because the amount of antibacterial glass used can be restricted efficiently. [0037] (2) Antibacterial process

Further, as shown in FIG. 10, it is preferable that the antibacterial substance 32 is treated by showering or directly immersing the silver ion-containing water 30 to perform an antibacterial treatment.

Note that typical examples of the antibacterial substance include woven fabric, fibrous material, nonwoven fabric, mat-like material, clothing, towels, footwear, and the like.

[Second Embodiment]

The second embodiment is a method for producing an antibacterial glass for performing an antibacterial treatment with silver ions during or after washing of an antibacterial object, which comprises the following steps (A) and (B). This is a method for producing an antibacterial glass characterized by the following.

2 3 2 2

To form a molten glass (hereinafter, sometimes referred to as a melting step).

(B) While cooling the molten glass, a molding step (hereinafter, referred to as the maximum diameter (tl) of 1 to 50 mm and the elution amount of silver ion of 0.5 to 100 mgZ (g'24Hrs)) It may be referred to as a molding step.)

[0039] 1. Melting process

As raw materials, B O, SiO, Ag O, and alkali metal oxides are used.

2 3 2 2

In addition, the amount of B O added was 30 60% by weight, and the amount of SiO

2 3 2

%, The addition amount of Ag 2 O 25 wt%, and the addition amount of alkali metal oxides 5 10

2

Using a universal mixer, the mixture was stirred under a condition of a rotation speed of 250 rpm for 30 minutes until it was uniformly mixed so as to have a value within the range of% by weight. Next, using a melting furnace, as an example, the glass raw material was heated at 1280 ° C. for three and a half hours to prepare a glass melt.

In addition, the heating conditions in the melting furnace can be appropriately changed according to the types and mixing ratios of the raw materials.

[0040] 2. Molding process

The forming step is a step of converting molten glass obtained by melting glass raw materials into antibacterial glass having a predetermined shape.

Specifically, as shown in FIGS. 11 (a) and (b), by manufacturing using predetermined rotating members 20a and 20b, it is possible to cut chocolate using a so-called thin portion. It is possible to efficiently obtain the antibacterial glass 10 whose handling, adjustment of the area and the shape of the flat plate are easy.

That is, the upward force also causes the molten glass 22 to fall naturally between the pair of rotating members 20a and 20b, and also forms the predetermined antibacterial glass 10 using the concave portion 24 provided on the surface of the rotating member 20a. Can be. 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, the antibacterial glass maintains a predetermined temperature because it is formed in a strip shape through a thin portion, so that cooling air is blown on the surface of the antibacterial glass for further cooling. I prefer to put it on.

The forming apparatus shown in FIGS. 11 (a) and 11 (b) has a pair of rotating members 20a and 20b. As a modified example, as shown in FIG. Even if a simple wall member 20c is used, the thin antibacterial glass 10 having substantially the same shape and a thin flat plate shape can be obtained.

[Third Embodiment]

The third embodiment is a method for producing an antibacterial glass for performing an antibacterial treatment with silver ions during or after washing of an antibacterial object, which includes the following steps (Α ′) and (Β ′). A method for producing an antibacterial glass characterized by the following.

(ΑΊ Raw materials, Ρ Ρ, Ag O, and alkali metal oxide

2 5 2

Melting process for producing molten glass (hereinafter sometimes referred to as melting process)

(ΒΊ While cooling the molten glass, a forming process to obtain an antibacterial glass with a maximum diameter (tl) of 1 to 50 mm and a silver ion eluted amount of 0.5 to 100 mgZ (g'24Hrs) It may be called the molding process.)

[0042] 1. Melting process

Use P O, Ag O, and alkali metal oxides as raw materials

2 5 2

The amount of PO added was 30 60% by weight, the amount of Ag O was 25% by weight, and

2 5 2

Using an all-purpose mixer, the mixture is uniformly mixed at a rotation speed of 250 rpm for 30 minutes so that the addition amount of the alkali metal sardine is within a range of 5 to 40% by weight. And stirred until the Then, using a melting furnace, as an example, calorie the glass raw material at 1280 ° C for three and a half hours. Heating produced a glass melt.

[0043] 2. Molding process 1

The forming step 1 is a step of converting a molten glass obtained by melting a glass material into an antibacterial glass having a predetermined shape, and in particular, maintaining the molten glass in a semi-solid state before it is completely cured. This is a step of forming glass-like glass.

Specifically, as shown in FIG. 13 (a), the molten glass 22 melted by the above-described method is flowed into a predetermined molding container 60 to form a semi-solid glass plate 22 ′. At this time, the material of the molding container 60 is not particularly limited as long as it has a melting point higher than that of the antibacterial glass 10. Preferably, it is used. In particular, a heat-resistant material such as carbon is a preferable constituent material in that it can easily cope with the reduction in the weight and precision of the molding container 60.

In addition, if necessary, a cooling device 61 is attached to the back surface of the molding container 60 to adjust the temperature of the molding container 60 to an optimum value as shown in FIG. A semi-solid state can be created.

By performing these methods, a semi-solid plate-like glass 22, as shown in FIG. 13 (b), can be obtained.

[0044] 2. Molding process 2

The forming step 2 is a step for forming the semi-solid glass plate 22 ′ formed in the forming step 1 into a glass plate having a predetermined thickness.

Specifically, as shown in FIG. 14 (a), the semi-solid glass plate 22, is inserted into the gap between the rotating members 2CT arranged at the interval dl. At this time, by setting the distance dl larger than the thickness d2 of the semi-solid glass plate 22, the antibacterial glass 10 with the distance dl can be formed as shown in FIG. Can be.

[0045] 3. Crushing process

In the crushing step, the antibacterial glass 10 is crushed by a predetermined method to obtain granular, spherical, This is a step of forming into a shape such as a crushed body.

Specifically, after crushing to a certain size using a crushing jig such as a hammer, crushing is performed using a ball milling method or the like. At this time, the desired shape as described above can be obtained by appropriately changing the conditions such as the milling ball diameter and the processing time. Example

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

[Example 1]

1. Preparation of antibacterial resin composition

(1) Melting process

When the total amount is 100% by weight, the composition ratio of B O is 52% by weight and the composition ratio of SiO is 3%.

2 3 2

6% by weight, 9% by weight of NaO and 3% by weight of AgO.

twenty two

Each glass raw material was stirred using a universal mixer at a rotation speed of 250 rpm for 30 minutes until it was uniformly mixed. Next, using a glass melting furnace, the glass raw materials were heated at 1280 ° C. for three and a half hours to produce molten glass.

[0048] (2) Molding process

The molten glass, which has also been taken out of the glass melting furnace, is inserted into the insertion port 4 of the manufacturing apparatus 40 shown in FIG.

Introduced into 2 and made into a flat antibacterial glass for washing machines (rectangular pieces, maximum diameter (tl): 15 mm, thickness (t2): 3 mm) that can be continuously cut with chocolate.

2. Evaluation of antibacterial glass for washing machine

(1) Silver ion dissolution evaluation

10 g of the obtained antibacterial glass for washing machines was immersed in 100 ml of distilled water (20 ° C.) and shaken for 24 hours using a shaker. After the silver ion eluate was separated using a centrifuge, it was further filtered through filter paper (5C) to obtain a measurement sample. Next, the silver ion in the measurement sample was measured by ICP emission spectroscopy, and the amount of silver ion eluted (mgZ

(g'24Hrs)) was calculated.

[0050] (2) Outflow evaluation

0.5mm depth, 5cm area on the surface of stainless steel plate with thickness lmm, area 20cm X 20cm A 5 cm X recess was provided, filled with lOOg (W1) antibacterial glass for washing machines, and tap water with a flow rate of 1 liter Z was sprayed from the side. After this condition was continued for 1 minute, the weight (W2) of the remaining antibacterial glass for a washing machine was measured on the stainless steel plate, and the residual ratio of the antibacterial glass for a washing machine ((W1—W2) ZW1 X 100) was calculated. Then, based on the calculated residual ratio, the outflow property of the antibacterial glass for a washing machine was evaluated according to the following criteria.

A: The residual ratio is 90-100% by weight.

〇: The residual ratio is less than 70-90% by weight.

Δ: The residual ratio is less than 30 to 70% by weight.

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

(3) Antibacterial evaluation

Using the washing machine shown in Fig. 4, the antibacterial property of cotton underwear was evaluated using the obtained antibacterial glass for a washing machine. That is, the cotton underwear was washed with running water containing detergent using the washing machine shown in FIG.

After the washing is completed, as shown in FIG. 9, the valve 28 communicating with the bypass 26 on which the washing machine antibacterial glass 10 is placed is opened and closed to allow water to flow, and the washing machine antibacterial glass 10 and the water are separated. By direct contact, silver ion-containing water was prepared.

Then, as shown in FIG. 10, antibacterial treatment was applied to cotton underwear 32 as a substance to be bacterium by showering silver ion-containing water 30.

The cotton underwear 32 thus obtained was left under environmental conditions of 35 ° C., 95% Rh, and 48 hours, and the antibacterial properties were evaluated under the following conditions.

：: No odor or darkening was observed at all.

〇: Almost no odor or darkening was observed.

Δ: Odor or darkening was partially observed.

X: A noticeable smell or darkening is observed.

[Example 2-5]

In Examples 2-5, as shown in Table 1, the composition ratios of B O and SiO used in Example 1

The same procedure as in Example 1 was carried out except that 2 3 2 was changed, and an antibacterial glass for a washing machine was prepared and evaluated. Valued.

[Comparative Examples 1 to 3]

Comparative Example 1 was the same as Example 1 except that the antibacterial glass for a washing machine obtained in Example 1 was adjusted to granular particles having an average particle size of 20 m using a crusher and a classifier. It was evaluated similarly.

In Comparative Example 2, the antibacterial glass for a washing machine obtained in Example 1 was adjusted to flaky particles having a long diameter of 200 m and a thickness of 30 m using a crushing device and a classification device. Was evaluated in the same manner as in Example 1.

Further, in Comparative Example 3, the antibacterial glass for a washing machine having an average particle diameter of 20 m obtained in Comparative Example 1 was added to polypropylene resin so as to have a concentration of 10% by weight. A resin plate containing antibacterial glass was prepared, and silver ion elution properties and antibacterial properties were evaluated.

[Table 1]

[Example 6]

1. Making antibacterial glass for washing machine

(1) Melting process

When the total amount is 100% by weight, the composition ratio of PO is 70% by weight, and the composition ratio of NaO is 1%. 8% by weight, the composition ratio of CaO is 9% by weight, and the composition ratio of AgO is 3% by weight.

2

These glass raw materials were stirred using a universal mixer at a rotation speed of 250 rpm for 30 minutes until they were uniformly mixed. Next, using a glass melting furnace, the glass raw material was heated at 1280 ° C. for three and a half hours to produce a molten glass.

(2) Forming Step

The molten glass taken out of the glass melting furnace was poured into a molding vessel 60 shown in FIG. 13 (a) to form a semi-solid glass plate. As a result, granular antibacterial glass for washing machines (maximum diameter (tl): 5 mm, minimum diameter (t2): 1 mm) was obtained.

2. Evaluation of antibacterial glass for washing machine

In Example 6, similarly to Example 1, (1) evaluation of silver ion dissolution, (2) evaluation of outflow property, and (3) evaluation of antibacterial property were performed.

Furthermore, after immersing 10 g of antibacterial glass for a washing machine in 1 liter of pure water at 25 ° C for 8 hours, take out the antibacterial glass for a washing machine from the water and measure the weight (W3). The weight loss rate ((10-W3) Z10X100) was calculated and evaluated for sustainability.

：: Weight loss rate is less than 10%.

〇: Weight loss rate is less than 10-20%.

Δ: Weight loss rate is less than 20-50%.

X: Weight loss rate is 50% or more.

[Examples 7-9, Comparative Examples 4-1-6]

In Examples 7-9 and Comparative Examples 4-6, as shown in Table 2, the P O used in Example 6

23, except that the composition ratio of CaO and NaO was changed, the antibacterial

2

A functional glass was prepared and evaluated.

[Table 2] Example 6 Example 7 Example 8 Example 9 Comparative Example 4 Comparative Example 5 Comparative Example 6

PA 70 64.5 66.5 68 72 60 71

Na ₂ 0 18 22.5 20.5 20 15 27 24

S

CaO 9 10 10 9 10 10 2 pairs

Composition Ag ₂ 0 3 3 3 3 3 3 3 Shape ¾ Granular Granular Granular ¾L Granular Granular Maximum diameter (t1) 5mm 5mm 5mm 5mm 5mm 5mm 5mm Resin None None None None None None None Elution amount 84 79 62 97 0.3 282 406

(mg / g / 24Hr)

Outflow O O O 〇 X ◎ ◎

Antibacterial ◎ ◎ ◎ ◎ X ◎ ◎

Sustained O O O ◎ ◎ X X

Industrial applicability

According to the antibacterial glass for subjecting the antibacterial substance of the present invention to antibacterial treatment with silver ions, the maximum diameter (tl) is extremely large in a flat or granular shape. By bringing silver ions into direct contact with water for antibacterial treatment during or after washing, a predetermined amount of silver ions can be released quickly and for a long period of time. Further, according to the method for producing an antibacterial glass of the present invention, an antibacterial glass having an extremely large maximum diameter (tl) in a flat or granular shape can be efficiently obtained.

Furthermore, according to the method of using the antibacterial glass of the present invention, silver obtained by directly contacting water with a flat or granular antibacterial glass having an extremely large maximum diameter (tl). By treating the antibacterial substance with the ion-containing water, for example, a predetermined antibacterial effect can be exerted on the antibacterial substance during washing.

According to the antibacterial glass of the present invention, when the antibacterial glass for a washing machine is brought into direct contact with water, which is forced by force, a predetermined amount of silver ions is rapidly and for a long period of time. Suitable to be used in applications where it is required to discharge the water, for example, dishwashers, vegetable washer, water purifier, humidifier, humidity supply, disinfectant supply, deodorant supply, etc. Can be.

Claims

The scope of the claims

[1] An antibacterial glass for releasing silver ions upon direct contact with water and exerting an antibacterial effect, and having a maximum diameter (tl) within a range of 1 to 50 mm. Antibacterial glass characterized in that the amount of silver ion eluted is within the range of 0.5—100 mg / (g · 24Hrs)

[2] The antibacterial glass according to claim 1, which is an antibacterial glass for performing antibacterial treatment with silver ions during or after washing of an antibacterial object.

[3] Including B O, SiO, Ag O, and alkali metal oxides as raw materials,

2 3 2 2

30 60% by weight of B O, 30 60% by weight of SiO,

2 3 2

25% by weight of Ag 2 O and 5 10% by weight of alkali metal oxide

2

3. The antibacterial glass according to claim 1, wherein the value is within a range of%.

[4] As raw materials, include P 2 O, Ag 2 O, and alkali metal oxides.

2 5 2

On the other hand, the addition amount of PO was 40 70% by weight, the addition amount of AgO was 25% by weight, and

2 5 2

3. The antibacterial glass according to claim 1 or 2, wherein the amount of addition of the rukari metal oxide sardine is within a range of 15 to 35% by weight.

[5] A claim characterized in that the antibacterial glass is entirely flat, and a plurality of glass pieces are connected via a thin portion made of the same component as the antibacterial glass. Item 5. The antibacterial glass for a washing machine according to item 1 to item 4.

[6] The antibacterial glass for a washing machine according to any one of claims 1 to 5, wherein the antibacterial glass for a washing machine is provided with a covering member around the periphery thereof and is cartridge-shaped.

[7] A method for producing an antibacterial glass for releasing silver ions upon direct contact with water and exhibiting an antibacterial effect, comprising the following steps (A) and (B). Manufacturing method of antibacterial glass.

2 3 2 2

Melting process to create molten glass

[8] A method for producing an antibacterial glass for releasing silver ions in direct contact with water and exhibiting an antibacterial effect, comprising the following steps (Α ')-(Β') This is a method for producing an antibacterial glass characterized by the following.

(ΑΊ Raw materials, Ρ Ρ, Ag O, and alkali metal oxide

2 5 2

Melting process to make molten glass

9. The flat plate-shaped antibacterial glass is formed by using a rotating member having a concave portion on the surface in the step (B) or (ΒΊ). The method for producing an antibacterial glass described in (1).

[10] The method further comprises a step of cooling the antibacterial glass between the steps (A) and (B), or between (及び and (ΒΊ), on a substrate provided with a cooling device. The method for producing an antibacterial glass according to any one of claims 7 to 9.