JPH0763701B2 - Glass water treatment material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a glass water treatment material containing a highly safe inorganic antibacterial agent. The present invention relates to a water treatment material composed of soluble glass containing components.

[0002]

2. Description of the Related Art Conventionally, in water storage tanks, cooling towers, solar systems, etc., unless regularly cleaned or sterilized, algae and bacteria are generated, resulting in reduced thermal conductivity, localized corrosion of inner walls, and water flow. Sometimes hindered people. In addition, in pools and the like, in addition to algae and bacteria, Escherichia coli and the like were sometimes propagated. In order to prevent these pollutions, regular cleaning is performed, sterilization with an organic tin compound, or chlorine sterilization is performed, but there are many places that are difficult to clean. There were problems such as large equipment required or the sustainability of effects being short.

Therefore, it has been proposed to use zeolite on which silver is supported, or a powder of soluble glass or an agglomerate of 10 mm or less as disclosed in Japanese Patent Laid-Open No. 62-10098. However, the effects of these substances are sufficient at the initial stage of use, but the effects are diminished with the passage of time, and the desired effects cannot be obtained.

[0004]

The present invention does not have the above-mentioned problems, that is, when soluble glass is used as a water treatment material, the effect is that in the initial stage and the final stage, The present invention intends to provide a water treatment material made of glass that does not change significantly and the soluble glass lasts until it is completely dissolved.

[0005]

[Means for Solving the Problems] In order to solve the above problems, the present inventors investigated the relationship between the time course of soluble glass and the amount of dissolved components, and found that the amount of dissolved components increased significantly with time. The present invention has been completed by studying a method that does not change. That is, it is a soluble glass containing at least one component of metal ions of Ag ⁺ , Cu ⁺ , Cu ⁺² , and Zn ⁺² , and is a rectangular parallelepiped, a cube, a plate, or a spherical body.
It has a shape expressed in dimensions and its longest diameter is 10
mm or more, and the composition is (RO +
R ₂ O) / P ₂ O ₅ = 0.4 to 1.2, R ₂ O / (RO
+ R ₂ O ₃ ) = 0 to 10 and the content of the metal ion is 0.005 to 5% by weight. And again, the initial dissolution rate (A) (dissolution
From the start of the
The term corresponding to the initial 20%. same as below. )
And dissolution rate (B) in the final stage (as opposed to the initial period)
It refers to the period corresponding to 20% of the final stage. same as below. ) With
The relationship is B / A ≧ 1/3.

[0006] The soluble glass used in the present invention is at least one of borosilicate type and phosphate type, but is preferably phosphate type glass. Although glass is generally a durable material, it can be easily dissolved in water by weakening the network structure that is its skeleton.
In order to weaken the network structure, it is possible to increase the amount of the glass-modified oxide or increase the amount of boric acid or phosphoric acid. The production method of the soluble glass is the same as the production method of a normal glass, heating the batch adjusted to the target composition,
It should be made glass. Further, it may be a glass using a sol-gel method which has become a hot topic recently and is not particularly limited. On the other hand, silver and copper containers have been known since ancient times to prevent food spoilage. This is because a very small amount of metal ions are eluted from these metals. Silver is about 2 in solution
It is said that it exhibits bactericidal activity at about 0 μg / l. Even in a very small amount, silver ions, copper ions, and the like have a function called oligodynamy that prevents the growth of fungi and the like, and show strong bactericidal activity by binding to active enzyme centers in cells such as bacteria and fungi.

In the meltable glass of the present invention, the components contained in the melted glass change little between the start of use and the end of use (the elution amount at the end of use is 1/2 or more of the value at the start of use).
It is something that is not allowed. For this reason, when the shape of the soluble glass is three-dimensional close to a sphere, the soluble glass is divided into several layers and the solubility of the surface glass is made smaller than that of the internal glass. As a result, the glass gradually dissolves, the shape becomes smaller, and when the surface area becomes smaller,
The dissolution of the internal glass begins, and the solubility of the internal glass is higher than that of the external glass. Therefore, even if the surface area becomes small, the elution amount does not change. Further, it is a matter of course that increasing the content of only the components effective for antibacterial properties toward the inside as the glass composition is included in the composition change.

In the case of a flat glass plate, the thickness (d) is 1 / the long side (a) or the short side (b) of the flat plate.
It must be 2 or less. In this way, since the glass has a small thickness, the surface area of the glass does not change much when the glass dissolves, so that the amount of the component eluted from the glass does not change much. The dissolution rate of the glass in this case is the dissolution rate (A) at the initial stage (the period corresponding to 20% of the initial period in the period from the start of dissolution until the entire amount is dissolved) and the final stage (the initial period and On the contrary, the last 20
The glass water treatment material is characterized in that the relationship with the dissolution rate (B) in a period corresponding to%) is B / A ≧ 1/3. Next, examples will be described to clarify the present invention.

[0009]

Example 1 A formulation having the following theoretical glass composition was melted,
A 20 mm × 20 mm × 5 mm glass flat plate was prepared. Theoretical glass composition: P ₂ O ₅ 50 mol%, CaO 17.
_{5mol%, Na 2 O32.5mol%,} Ag 2 O
0.1 wt% Also, the basic glass composition is P ₂ O ₅ 50 mol%, CaO
_17.5%, relative to Na 2 O 32.5mol% of the same _tissue, 5 glass you Ag 2 O 3.0 wt%
A glass block of mm × 5 mm × 5 mm was prepared and used as a sample.

An ultrasonic humidifier (humidification amount: 400 cc / hour, water tank capacity: 40)
One was placed in a water tank of 0 cc, humidification time ... 8 hours / day), and its weight change and silver ion concentration were measured for about 3 months.
In addition, all the glasses were completely dissolved in the three months of the test. Table 1 shows the measurement results of the dissolution rate and the silver ion concentration at the initial stage (up to 0 to 18 days) and the final stage (72 to 90 days) after the start of the test.

[0011]

As shown in Table 1, by eluting the shape of the glass to be used and carefully selecting the composition, the components eluted from the soluble glass can be separated at the initial stage and the final stage during the period of use. , In this example, 18/25 or 55/95
It is a value that does not change significantly.
On the other hand, in a conventional product that does not consider the shape factor, this value changes greatly to 1/45 or 1/190.

[0013]

Example 2 Next, an example in which the soluble glass is multilayer glass will be described. First, P ₂ O ₅ 50 mol%, Na
₂ O 35 mol%, the glass of the base composition of _{CaO 15mol%, Ag 2 O 0.02wt} %, Ag 2 O
Three kinds of glass having different silver contents were added and added with 0.1 wt% and Ag ₂ O 1.0 wt% and crushed. next,
Make 4mmφ × 4mmh tablets with the glass of, and cover them with the glass of 8mmφ × 8mmh, and cover them with the glass of
A tablet of mmφ × 12 mmh was prepared. Separately from this, using only glass, 12mmφ × 12mmh
Made tablets. Both tablets were heated at 450 ° C. for 1 hour to be fused.

The glass obtained by fusing these two tablets together was used in Example 1.
In the same manner as in, the sample was placed in a water tank of an ultrasonic humidifier and measured in the same manner. In the case of this sample, it was dissolved in about 40 days, so the period was divided into 5 equal parts, the first 8 days were the initial stage, and the last 8 days were the final stage. Table 2 shows the measurement results of the dissolution rate and the silver ion concentration in each period.

[0015]

As shown in Table 2, since the glass composition has a gradient, the target component (in this case, silver) can be stably eluted without significantly changing the amount. As a result, Will also be stable.

[0017]

As described above, the soluble glass according to the present invention has the following effects because the trace amount of the antibacterial component that is eluted is stable. Compared with the conventional product in which the shape or the structural factor is not considered, in the case of the product of the present invention, since the soluble components are averaged over the entire dissolution period, the effect at the end stage is also low, As long as it is a product, it does not need to be replenished even at a stage where it needs to be newly replenished, so that useless use can be prevented. By selecting the composition of the soluble glass and the antibacterial component, it is possible to freely control the type of antibacterial component and its elution amount.
It can be used for various applications that require water treatment materials. In terms of safety and sustainability of effects, compared to conventional organic tin compounds or chlorine compounds
Are better. Therefore, the present invention is an extremely useful invention that helps improve the environment and promote health by effectively utilizing water resources and improving the quality of water used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C02F 1/50 F

Claims (3)

[Claims] 1. A soluble glass containing at least one component of metal ions of Ag ⁺ , Cu ⁺ , Cu ²⁺ and Zn ²⁺ , which is a three-dimensional shape such as a rectangular parallelepiped, a cube, a flat plate or a spherical body. It has a shape that is expressed and its longest diameter is 10 mm.
Above , and the composition is (RO + R ₂
O) / P ₂ O ₅ = 0.4 to 1.2, R ₂ O / (RO + R
₂ O ₃ ) = 0 to 10 and the dissolution rate (A) in the initial stage (a period corresponding to 20% of the initial period in the period from the start of dissolution until the entire amount is dissolved). , And dissolution rate (B) at the end of the period (as opposed to the initial period, the period corresponding to 20% of the final stage.
same as below. ) With B / A ≧ 1/3, and
Content of the said metal ion is 0.005-5 weight%, The glass water treatment material characterized by the above-mentioned. 2. A rectangular parallelepiped, a cube, a spherical body or the like having a three-dimensionally expressed shape, the structure of which is composed of two or more layers having different compositions, and the inner layer is R ₂ O.
Value of / (RO + R ₂ O ₃ ) or / and Ag ⁺ , Cu
The value of the content of at least one component of ⁺ , Cu ²⁺ and Zn ²⁺ metal ions is set to be larger than that of the outer layer, and the glass material of each layer is formed so as to cover the upper layer, and thereafter, A glass water treatment material characterized by being produced by fusing. 3. The soluble glass has a flat plate shape, and the thickness (d) is 1 of the long side (a) or the short side (b) of the flat plate.
It is / 2 or less, The glass water treatment material of Claim 1 characterized by the above-mentioned.