WO2016147850A1 - Deodorant glass agent - Google Patents

Abstract

The present invention is designed to provide a highly convenient deodorant with which it is possible to deodorize more rapidly than with conventional deodorants, and actualize a stable deodorant effect over an extended period of time, the deodorant having a high degree of freedom in terms of product shape and mode of use, and not aggregating even when made into a powder. The deodorant of the present invention comprises CuO-containing alkali-alkaline earth-borosilicate glass or CuO-containing alkali-alkaline earth-silicate glass, a CuO powder being added within the range (× mol%) of the following formula as a raw material, and the particle size (D₅₀) of the deodorant glass agent being within the following range (y μm). y ≤ 4.27x + 0.34 when 0,01 ≤ x ≤ 0.198; y ≤ 5.08x + 0.18 when 0.198 ≤ x ≤ 2.03; and y ≤ 10.5 when 2.03 ≤ x ≤ 23

Description

Deodorant glass agent

The present invention relates to a deodorizing glass agent having a function of deodorizing malodorous substances such as lower fatty acids and body odor components as well as sulfur-based malodorous substances such as hydrogen sulfide and methyl mercaptan.

In recent years, demand for various deodorants has been increasing in response to growing interest in comfortable living environments.

Among the odors that cause problems in the living environment, sulfur-based malodors such as hydrogen sulfide and methyl mercaptan are disliked as giving a strong discomfort. In particular, methyl mercaptan is known as a foul odor-causing substance that can feel a rotten odor even at a low concentration of about ppb, and technical development relating to its deodorization has been conventionally demanded.

As a technique related to the above deodorization, a soluble glass containing P ₂ O ₅ as a main component contains any of silver, copper, and iron, and PO ₄ ^2- ion, Ag ⁺ ion, Cu ²⁺ ion, and Fe ²⁺ ion. The deodorizing substances such as methyl mercaptan are removed by the technology for deodorizing sulfur-based malodors by setting the dissolution rate of the solution within a specific range (Patent Document 1) and the deodorizer in which copper oxide is dispersed in activated carbon. A technique (Patent Document 2) is disclosed.

However, since the technology of Patent Document 1 is a technology that utilizes a sulfurization reaction between Ag ⁺ ions, Cu ²⁺ ions, Fe ²⁺ ions, and sulfur components generated by dissolution, when the equilibrium state is reached, further reactions are not possible. The problem is that a continuous deodorizing effect cannot be expected, and the soluble glass agent mainly composed of P ₂ O ₅ lacks chemical durability, particularly water resistance. There is a problem that it is inferior in convenience because it is restricted in terms of product shape and usage, such as being easy to handle and difficult to handle.

Although the specific action of copper oxide is not described in Patent Document 2, it is assumed that the malodorous substance removal efficiency of the activated carbon is improved by the catalytic action. However, the technique of Patent Document 2 has a problem that the copper oxide dispersed in the activated carbon is poisoned (catalyst deterioration) due to the reaction with the malodor-causing substance, and the duration of the deodorizing effect is still insufficient. there were.

Also, as a function of the deodorant, it is originally preferable to be able to deodorize more quickly, but there is a problem that the deodorization speed is not considered in the conventional deodorant.

Japanese Unexamined Patent Publication No. 4-67868 JP 2009-213992 A

The object of the present invention is to solve the above-mentioned problems, deodorize more quickly than conventional deodorants, and stable deodorizing effect for a long time compared to conventional deodorants. In addition, the present invention provides a deodorant having a high degree of freedom and a high degree of freedom in terms of product shape and use mode without being aggregated even in powder form.

In the present invention, as a means for solving the above problems, a deodorizing glass agent comprising “CuO-containing alkali-alkaline earth-borosilicate glass” or “CuO-containing alkali-alkaline earth-silicate glass”, It is characterized by adopting a configuration in which CuO powder is added as a raw material in the range of the following formula (x mol%) so that the particle size (D ₅₀ ) of the deodorizing glass agent is in the following range (y μm). To do. For reference, the range defined by the following mathematical formula is shown in FIG.
When 0.01 ≦ x ≦ 0.198, y ≦ 4.27x + 0.34
When 0.198 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
When 2.03 ≦ x ≦ 23, y ≦ 10.5

The CuO-containing alkali-alkaline earth-borosilicate glass is composed of 46 to 70 mol% of SiO ₂ and 15 to 50 mol% in total of B ₂ O ₃ and R ₂ O (R = Li, Na, K). , R′O (R ′ = Mg, Ca, Sr, Ba) is 0 to 10 mol%, Al ₂ O ₃ is 0 to 6 mol%, CuO is 0.01 to 23 mol%, and the following formula is satisfied. It is preferable to use one. Here, it is more preferable to use a material containing 5 to 20 mol% of B ₂ O ₃ and 10 to 30 mol% of R ₂ O (R = Li, Na, K). For reference, a range defined by the following mathematical formula is shown in FIG.
When 0.01 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
When 2.03 ≦ x ≦ 23, y ≦ 10.5

The glass composition includes 51 to 63 mol% of SiO ₂ , 21 to 39 mol% in total of B ₂ O ₃ and R ₂ O (R = Li, Na, K), R′O (R ′ = Mg, It is preferable to use a material containing 2 to 7 mol% of Ca, Sr, Ba), 0 to 5.5 mol% of Al ₂ O ₃ and 1 to 13 mol% of CuO, where B ₂ O ₃ is added. It is more preferable to use a material containing 8 to 17 mol% and 13 to 22 mol% of R ₂ O (R═Li, Na, K).

The glass composition is SiO ₂ 53-62 mol%, B ₂ O ₃ 10-17 mol%, Na ₂ O 13-19 mol%, CaO 3-7 mol%, Al ₂ O ₃ 0 It is more preferable to use one containing ˜4.5 mol% and CuO 4˜13 mol%.

The CuO-containing alkali-alkaline earth-silicate glass is composed of 50 to 70 mol% of SiO ₂ , 10 to 33 mol% of R ₂ O (R = Li, Na, K), R′O (R '= Mg, Ca, Sr, Ba) is contained in an amount of 0 to 15 mol%, Al ₂ O ₃ is contained in an amount of 0 to 6 mol%, CuO is contained in an amount of 0.01 to 23 mol%, and the following formula is used. preferable. For reference, the range defined by the following mathematical formula is shown in FIG.
When 0.01 ≦ x ≦ 2.38, y ≦ 4.27x + 0.34
When 2.38 ≦ x ≦ 23, y ≦ 10.5

The glass composition is composed of 55 to 70 mol% of SiO ₂ and 12 to 24 mol% in total of R ₂ O (R = Li, Na, K), R′O (R ′ = Mg, Ca, Sr, Ba). 2) to 10 mol%, Al ₂ O ₃ 0 to 5.5 mol%, and CuO 1 to 20 mol% are more preferable.

The glass composition is 55 to 65 mol% of SiO ₂ , 12 to 20 mol% of Na ₂ O, 3 to 7 mol% of CaO, 0 to 5 mol% of Al ₂ O ₃ , and 4 to 13 mol of CuO. It is more preferable that the content is 1%.

Conventionally, various deodorizing glass agents using soluble glass have been developed, but there is no “glass agent showing a deodorizing effect by catalytic action”. As a result of many years of research, the present inventors have found that “CuO contained in the glass of the above composition in the above ratio functions as a catalyst to promote the decomposition reaction (oxidation / reduction reaction) of sulfur-based malodorous substances, We found a new finding that "deodorizing effect of sulfur-based malodorous substance". The present invention has been made on the basis of this finding, and is expected to develop into various uses as “a novel glass agent exhibiting a deodorizing effect by catalytic action”.

Since the present invention has a mechanism for promoting the decomposition reaction of the sulfur-based malodorous substance using CuO contained in the glass as a catalyst as described above, the conventional technique using the “sulfurization reaction” (for example, Patent Document 1). ), The deodorizing capacity (for example, in Patent Document 1, which is proportional to the ion concentration for adsorbing the malodorous component of the sulfur component) can be increased, and the deodorizing effect can be obtained by repeatedly using the catalyst. It can last for a long period of time, and it is difficult for poisoning to proceed as in the prior art (for example, Patent Document 2) in which CuO functioning as a catalyst is dispersed in activated carbon. Can be demonstrated stably.

Moreover, according to this invention, CuO powder is added as a raw material in the range of the following formula (x mol%), and the particle size (D ₅₀ ) of the deodorizing glass agent is set to the following range (y μm). Thus, it is possible to realize “rapid deodorization”, which has not been considered in the conventional deodorant.
When 0.01 ≦ x ≦ 0.198, y ≦ 4.27x + 0.34
When 0.198 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
When 2.03 ≦ x ≦ 23, y ≦ 10.5

The deodorizing glass agent of the present invention is an “oxidation catalyst-based deodorant” that exhibits a deodorizing effect due to an oxidation catalytic action, and can exhibit an excellent deodorizing effect particularly with respect to methyl mercaptan. In the following description, the function as a catalyst can be more effectively exhibited by securing a large contact area with the malodorous substance by using the deodorizing glass agent in powder form.

It should be noted that the deodorizing glass agent of the present invention is not limited to sulfur-based malodorous substances, but can be deodorized as long as it is a malodorous substance capable of dehydrogenation. Specifically, acetic acid of lower fatty acids known as body odor (sweat, foot odor), isovaleric acid, propionic acid, normal butyric acid, normal valeric acid and caproic acid of medium chain fatty acid defined by the Malodor Control Law, Enanthate and trans-2-nonenal, known as age-related odors, can also be deodorized. In general, those having 2 to 4 carbon atoms are referred to as short-chain fatty acids (lower fatty acids), but in this specification, acetic acid having 1 carbon atom and 5 valeric acids are also treated as lower fatty acids. These deodorizing mechanisms for lower fatty acids and trans-2-nonenal are likely to be similar to the catalytic action for sulfurous malodorous substances. For example, the deodorizing glass agent of the present invention catalytically decomposes methyl mercaptan to produce dimeric dimethyl disulfide, and at this time, a dehydrogenation reaction occurs. Similarly, it is presumed that lower fatty acids are also decomposed by the dehydrogenation reaction. Alternatively, since malodorous gas due to lower fatty acids is known as acidic, there is a possibility of causing a neutralization reaction with the deodorizing glass agent of the present invention containing a large amount of alkali. When the reaction amount was calculated from the deodorization test result, the deodorization effect over the equivalent reaction was confirmed, so that there is a high possibility that the deodorization effect due to the catalytic action and the deodorization effect due to the neutralization reaction occur simultaneously. However, since trans-2-nonenal is known as a neutral gas, it is highly likely that the deodorizing effect is mainly due to a catalytic action rather than a neutralization reaction. In addition to trans-2-nonenal, the precursor palmitoleic acid may be decomposed to exhibit a deodorizing effect.

Moreover, since the deodorizing glass agent of the present invention contains a large amount of CuO in the glass, the antibacterial effect due to CuO can be exhibited at the same time.

In addition, in the prior art using the “sulfurization reaction” (for example, deodorization method in which Ag ⁺ ions, Cu ²⁺ ions, and Fe ²⁺ ions having high affinity with the sulfur component are reacted) Discoloration occurs, and there is a problem that the aesthetics of the glass is impaired. On the other hand, the present invention uses a vitrified CuO as a catalyst to promote the decomposition reaction of the sulfur-based malodorous substance, and the deodorizing effect of the sulfur-based malodorous substance Therefore, the deodorizing function can be exhibited without discoloring the glass.

As in the invention of claim 2, SiO ₂ is 46 to 70 mol%, B ₂ O ₃ and R ₂ O (R = Li, Na, K) in total 15 to 50 mol%, R′O (R '= Mg, Ca, Sr, Ba) 0-10 mol%, Al ₂ O ₃ 0-6 mol%, and glass having the above composition containing CuO 0.01-23 mol% are used as a deodorizing glass agent. By doing so, compared with a prior art, the deodorizing glass agent with a high freedom degree regarding a product shape and a use aspect and high convenience is realizable. Specifically, it can exhibit a deodorizing effect that is stable for a long time, has high chemical durability, is less likely to agglomerate when made into powder, is in the presence of room temperature, oxygen, darkness without light, and in the presence of moisture. An excellent deodorizing effect can be exhibited even in a high-temperature environment (450 ° C. or lower) (in a state where the surface is wet), and an extremely easy-to-handle deodorizing glass agent can be realized.

4 is a graph showing measurement results of Example A. It is a graph which shows the measurement result of Example B. It is a graph which shows the measurement result of Example B. 10 is a graph showing measurement results of Example C. 10 is a graph showing measurement results of Example D. 10 is a graph showing measurement results of Example E. 10 is a graph showing measurement results of Example G. 10 is a graph showing measurement results of Example G. It is a graph which shows the measurement result of Example H. It is a graph which shows the relationship between the amount of CuO addition in Claim 1, and a particle size. It is a graph which shows the relationship between the amount of CuO addition in Claim 2, and a particle size. It is a graph which shows the relationship between the amount of CuO addition in Claim 7, and a particle size. 10 is a graph showing measurement results of Example K.

Hereinafter, preferred embodiments of the present invention will be described.

(Embodiment 1: CuO-containing alkali-alkaline earth-borosilicate glass)
The deodorizing glass agent of the present embodiment is composed of 46 to 70 mol% of SiO ₂ , 15 to 50 mol% in total of B ₂ O ₃ and R ₂ O, R′O (R ′ = Mg, Ca, Sr, Ba ) 0-10 mol%, Al ₂ O ₃ 0-6 mol% and CuO 0.01-23 mol% “alkali (R ₂ O) -alkaline earth (R′O) -borosilicate glass” (B ₂ O ₃ —SiO ₂ ) ”, and can be produced by a melt quenching method in the same manner as a normal glass agent. The shape of the glass agent is a powder obtained by pulverizing after obtaining a pre-molded body by a melt quenching method. The pulverization referred to here means pulverization by a generally known pulverizer (for example, a ball mill, a bead mill, a jet mill, a CF mill, etc.), and may be dry or wet.

Hereinafter, each glass composition will be described in detail.

(SiO ₂ )
SiO ₂ is a main component that forms the structural skeleton of glass. The content thereof is 46 to 70 mol%, preferably 51 to 63 mol%. If it is less than 46 mol%, the chemical durability of the glass becomes insufficient, and the glass tends to devitrify, which is not preferable. Furthermore, if it is less than 46 mol%, the water resistance of the glass becomes insufficient, and copper ions are more likely to elute in the presence of moisture (including moisture in the atmosphere). Since the deodorizing effect by the sulfurization reaction which occurs by this becomes strong, it is not preferable. If it exceeds 70 mol%, the melting point increases, which makes glass melting difficult and also causes an increase in viscosity.

(B ₂ O ₃ )
B ₂ O ₃ is a component that improves the solubility and clarity of the glass, and in a specific composition, it also becomes a component that forms the structural skeleton of the glass. B ₂ O ₃ greatly affects the stability of the glass depending on its content, and in the present invention, the meaning as a flux of glass is large. The content thereof is set to 5 to 20 mol%, preferably 8 to 17 mol% in consideration of the volatilization amount of B ₂ O ₃ . When it exceeds 20 mol%, B ₂ O ₃ is not preferred because it tends to volatilize in the melting process and the composition control becomes difficult.

(R ₂ O (R = Li, Na, K))
R ₂ O (R = Li, Na, K) breaks the bond between Si and O in the glass structure skeleton to form non-crosslinked oxygen, resulting in a decrease in glass viscosity, moldability and solubility. And a flux similar to B ₂ O ₃ . The content of R ₂ O (R = Li, Na, K) is 10 to 30 mol% in total, preferably 13 to 22 mol%, considering the content ratio with other components. And When it exceeds 30 mol%, the chemical durability of the glass becomes insufficient. Specifically, a whitening phenomenon called bloom is caused by a reaction between the glass agent and moisture in the atmosphere. The occurrence of bloom is undesirable because it reduces the contact area with malodorous gas. In addition, the alumina in the melting furnace is easily eroded.

(B ₂ O ₃ + R ₂ O (R = Li, Na, K))
As mentioned above, both B ₂ O ₃ and R ₂ O are used as fluxing agents. The range in which the total content of B ₂ O ₃ and R ₂ O is 15 to 50 mol%, preferably 21 to 39 mol%, is a region that exhibits a deodorizing effect safely. If it is less than 15 mol%, the meltability of the glass becomes insufficient, and devitrification tends to occur during molding, which is not preferable. If it exceeds 40 mol%, the water resistance of the glass becomes insufficient, and copper ions are more likely to elute in the presence of moisture (including moisture in the atmosphere). Since the deodorizing effect by a sulfurization reaction becomes strong, it is not preferable. On the other hand, if it exceeds 50 mol%, phase separation is likely to occur during melting, and the deodorizing effect of the glass agent becomes insufficient accordingly.

(R'O (R '= Mg, Ca, Sr, Ba))
R′O (R ′ = Mg, Ca, Sr, Ba) is a component that improves the chemical durability of the glass. The total content of one or more of R′O (R ′ = Mg, Ca, Sr, Ba) is 0 to 10 mol%, preferably 2 to 7 mol%. If it exceeds 10 mol%, the viscosity at the time of melting becomes high and the glass tends to be devitrified, which is not preferable. In addition, it is not an essential component in the deodorizing glass agent of this invention, and the content may be 0 mol%.

(CuO)
CuO functions as a catalyst, accelerates the decomposition reaction (oxidation / reduction reaction) of the sulfur-based malodorous substance, and exhibits the deodorizing effect of the sulfur-based malodorous substance. The content thereof is 0.01 to 23 mol%, preferably 1 to 13 mol%, more preferably 4 to 13 mol%. If it exceeds 23 mol%, undissolved material tends to remain, and metal copper tends to precipitate during rapid cooling or processing, which is not preferable. Since metallic copper also shows a deodorizing effect, from the viewpoint of deodorization, its precipitation is not a problem, but it is not suitable for applications where discoloration of glass is a problem because it causes discoloration of glass with the deposition of metallic copper. . Moreover, when it precipitates as metallic copper, poisoning will advance. On the other hand, according to the present invention in which CuO is included as a glass component, poisoning hardly progresses and the catalytic function can be stably exhibited over a long period of time.

When the content of CuO is decreased under the condition that the glass agent has the same weight and the same particle size, the deodorizing ability tends to decrease with the decrease. This is presumed to be caused by a decrease in the amount of CuO on the glass surface that comes into contact with the malodor. Although the content and particle size of CuO vary depending on the required deodorization speed and deodorization capacity, in this embodiment, the added amount of CuO powder (x mol%) and the particle size of the deodorizing glass agent (D ₅₀ , y μm). ) Is limited to the range of the following formula, it is possible to realize “rapid deodorization”, which has not been considered in the conventional deodorizing glass agent.
When 0.01 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
When 2.03 ≦ x ≦ 23, y ≦ 10.5

Regarding the CuO content and particle size, the surface area per unit mass of the powder is said to be the specific surface area [m ² / g]. The larger this value, the finer the particles. When the particle shape is assumed to be spherical, the particle radius r there are n, the total surface area N4paiaru 2 at this ^time, since the mass, when the [rho and density of the particles (n4πr ^3/3) is [rho, the specific surface area ^{= n4πr 2 / (n4πr 3/} 3) ρ = 3 / ρr. Here, assuming that the radius of the deodorant glass agent particle is R and the density is Ρ, the specific surface area is expressed as 3 / ΡR. When R = 5 μm, the specific surface area (2R = 10 μm) = 3 / Ρ (5 μm), and when R = 0.5 μm, the specific surface area (2R = 1 μm) = 3 / Ρ (0.5 μm). That is, when the particle diameter (diameter) of 10 μm of the deodorizing glass agent is reduced to 1 μm, the specific surface area becomes 10 times larger. Along with this, it is naturally assumed that the deodorizing ability is enhanced. From the above, if the particle size can be reduced, the amount of CuO added can be reduced as much as possible. The above-described general pulverization techniques currently limit the fine pulverization up to 0.1 μm, but by using build-up (gas phase method / liquid phase method), the pulverization is 0.1 μm or less. Fine particles can be formed.

Specifically, the deodorizing glass agent of 0.1 μm or less can be produced by a sol-gel method, PVD (Physical Vapor Deposition) treatment, CVD (Chemical Vapor Deposition), or flame pyrolysis treatment. In the sol-gel method of the liquid phase method, glass is produced by adjusting the reaction solution using an Si alkoxy compound, an alcohol solution, aqueous ammonia, or the like. Then, a glass agent is obtained through the process of isolate | separating glass by centrifugation etc. and the process of drying the isolate | separated glass. In the case of the sol-gel method, water resistance is insufficient, and the sulfurization reaction may exceed the catalytic deodorizing action. On the other hand, it can be improved by setting the drying temperature in the vicinity of the glass transition point. In the vapor phase PVD process, glass raw materials evaporate in a plasma state, and glass is produced when they are cooled. The CVD and flame pyrolysis processes also differ depending on whether the raw materials are processed by chemical separation or pyrolysis, and, like PVD, are produced in a glassy state when cooled. In addition, although it is not a build-up, as a special fine particle production method, heated glass powder is immersed in a cooling liquid, and at that time, the liquid can be irradiated with radio waves to form fine particles.

In the present invention in which CuO is included as a glass component, copper ions, which are transition metal ions, are introduced into a glass matrix. It is known that copper ions are strongly affected by crystal fields from surrounding anions when introduced into a glass matrix. Copper ions take a plurality of ion states depending on the surrounding environment, but usually copper ions exist as Cu ⁺ or Cu ^{2+ in} glass. Cu ²⁺ is stable in an oxidizing atmosphere, and Cu ⁺ is stable in a reducing atmosphere. Cu ²⁺ in the glass occupies the position of the network modifying ions of the structural skeleton of the glass, and when a large number of oxygen ions are coordinated to this, it exhibits a blue color. Cu ⁺ itself is colorless, but if it coexists with Cu ²⁺ , ion deformation occurs and absorption is enhanced. Further, as the copper ion concentration increases, it becomes impossible to satisfy the coordination of oxygen ions for all Cu ²⁺ , and as a result, the number of unsaturated copper ions having a low coordination number increases. Moreover, unsaturated ions also increase with increasing temperature. Along with this, the glass changes from blue to green. Cu ²⁺ exhibits an absorption band in the visible to near infrared region (around 800 nm). In general, factors that determine the valence of transition metal ions include melting temperature, oxygen partial pressure in the molten atmosphere, addition amount of transition metal ions, and host glass composition. However, there are few reports on valence control of copper ions by glass composition.

It is known that the water resistance of the glass is improved by adding alumina to the oxide glass. For example, according to a study by Murata, Kurimura, Morinaga et al. (The Japan Institute of Metals, Vol. 61, No. 11 (1997)), the following has been confirmed in a specific composition. Since silicate glass generally has a higher melting temperature than borate or phosphate glass, the Cu ⁺ -Cu ²⁺ redox state shifts to the reduction side compared to the other two glass systems. Cheap. By adding alumina to a borate or phosphate glass, there is an effect that the redox state of Cu ⁺ -Cu ²⁺ is stabilized on the reducing side. In the binary Na ₂ O—SiO ₂ glass, as the Na ₂ O content decreases, the Cu ⁺ increases relatively. In the ternary alkali-alkaline earth-silicate glass, the alkali There are reports that the amount of Cu ⁺ increases as the ionic radius of the earth decreases. In addition, among transition metals, there is a report that copper ions are special in terms of how the valence balance is influenced by the host glass. However, the action exhibited by each component of the glass agent does not necessarily change linearly according to the blending ratio. It is considered that various factors such as bonds between atoms in the amorphous glassy material and changes in bond nuclei are acting.

(Al ₂ O ₃ )
Al ₂ O ₃ is a component that improves the chemical durability of the glass and affects the crystal structure stability. Further, Al ₂ O ₃ functions to suppress the phase separation of the glass and increase the homogeneity of the glass agent. It is desirable that the content is 6 mol% or less, preferably 5.5 mol% or less, because the viscosity may increase or the addition may affect the redox state of copper ions in the glass. .

In addition, when CuO addition amount exceeds 23 mol%, a copper ion may be reduce | restored at the time of rapid cooling after glass melting, or a shaping | molding, and metal copper may precipitate. Since metallic copper also exhibits a deodorizing effect, from the viewpoint of deodorization, its precipitation does not become a problem, but when it is deposited as metallic copper, poisoning proceeds. At this time, precipitation of metallic copper can be suppressed by using Al ³⁺ as a part of the glass structure composed of SiO ₂ .

(Other trace components)
In addition to the above components, ZnO, SrO, BaO, TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , P ₂ O ₅ , Cs ₂ O, Rb ₂ O, TeO ₂ , BeO, GeO ₂ , Bi ₂ can be used as trace components. O ₃ , La ₂ O ₃ , Y ₂ O ₃ , WO ₃ , MoO ₃ , CoO, Fe ₂ O ₃ or the like can also be included. Furthermore, F, Cl, SO ₃ , Sb ₂ O ₃ , SnO ₂ , Ce, or the like may be added as a clarifier.

(Fe ₂ O ₃ )
Since Fe ₂ O ₃ is a component that affects the redox state of copper ions in the glass (enhances Cu ⁺ > Cu ²⁺ ), its content is 0.5 mol% or less, preferably 0.3 mol It is desirable to make it below%.

(Cr ₂ O ₃ , MnO ₂ , CeO ₂ )
Cr ₂ O ₃ , MnO ₂ , and CeO ₂ are transition metal ions and are components that can change the valence similarly to CuO. When mixed with CuO, the redox state of the copper ions in the glass tends to be acidic (Cu ⁺ <Cu ²⁺ ) due to these highly oxidizing components (oxidizing power Cr ₂ O ₃ > MnO ₂ > CeO ₂ ). In the composition range and the production method of the present invention, the deodorizing effect is obtained stably, but the redox state is greatly unexpected and the deodorizing effect cannot be obtained (for example, the melting furnace is in a redox state due to corrosion) In other words, the valence balance of copper ions can be controlled by adding Cr ₂ O ₃ , MnO ₂ , or CeO ₂ .

Considering the above, in the present embodiment, the composition range in which the deodorizing effect is stably obtained is specified. That is, the composition range was specified in consideration of the melting temperature range, the oxidation-reduction state, and the composition range. If a glass agent having the above composition range is produced by a melt quenching method, a deodorizing glass agent can be stably obtained. In particular, it can be stably obtained by melting in a tank furnace, melting an electric furnace, or melting a small-scale crucible. Empirically, in the case of soda lime glass, it is known that the valence balance (Cu2 ^{+ /} total) of copper ions is about 15% for the former and about 50% for the latter in tank furnace melting and electric furnace melting. . Naturally, the valence balance also changes in the composition of the present embodiment. Since the deodorizing mechanism is a catalytic action, these chemical states may affect the deodorizing effect, but the difference in the effect is not particularly problematic as long as it is in the above composition range.

Note that it is necessary to consider that the oxidation-reduction state varies depending on the melting temperature and the melting time. The melting temperature may be controlled to 1200 to 1400 ° C, preferably 1280 to 1380 ° C. The melting time is preferably 6 to 8 hours. The glass obtained here is confirmed to be blue or greenish blue by Cu ²⁺ . As described above, in the composition range of the present invention, the valence balance of copper ions is not necessarily important as long as the melting temperature and time are taken into consideration. In addition, the valence balance of the obtained glass agent was intentionally changed by heat treatment (a blue plate in which a thin plate was produced and Cu ²⁺ color was confirmed, the valence balance was changed to Cu ⁺ >> Cu ²⁺ Although almost no color tone was confirmed, brown (red) glass in which precipitation of colloidal metallic copper of Cu ⁰ was confirmed, the deodorizing effect was confirmed. Thus, a deodorizing effect is obtained by using a glass agent having the above composition range, and the deodorizing effect is maintained even if the valence balance of copper ions is controlled by heat treatment or the like after molding.

The deodorizing glass agent by catalytic action may have insufficient immediate effect when the malodor concentration is high. As a temporary trapping agent, it can also be used by mixing with a physical adsorbent (activated carbon, silica gel, zeolite, etc.). Moreover, since malodors do not necessarily exist as a single component, it is possible to use a combination of agents specialized in deodorizing various malodors. It can also be used by mixing with a conventional deodorizing glass agent.

Deodorant glass preparation method:
After preparing the raw materials, it was melted at a melting temperature of 1350 ° C. for 8 hours and poured out to obtain a glass having the glass composition shown in Table 1. After melting, natural cooling was performed, but water cooling can also be used. The obtained glass was dry-pulverized using a ball mill, and D ₅₀ (corresponding to 50% of the cumulative value when the particle size was cumulatively distributed) = 4.5 μm or less with a particle size meter, D ₉₈ (cumulatively distribute the particle size. The integrated value is 98%)) = 40 μm or less. The particles having a particle diameter (diameter) of 100 μm or more were removed by separating with a sieve.

(Example A: Deodorization effect confirmation test for sulfurous malodor)
Deodorization test method:
A deodorizing glass agent (Example 1) having a glass composition shown in Table 1 and malodor were sealed in a Tedlar bag, and the malodor concentration in the bag over time was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
Measurement results and discussion:
As shown in FIG. 1, it was confirmed that there was a deodorizing effect against hydrogen sulfide, ethyl mercaptan, butyl mercaptan, 2-mercaptoethanol, and any sulfur-based malodor. In addition, as shown in FIGS. 2, 3, 4, 6, 7 and 8, it was confirmed that methyl mercaptan also has a deodorizing effect.
Supplement:
The gas detector tube is a method suitable for comparison within the same test, but its quantitativeness is low. In addition, since it is affected by the environment (temperature, humidity), it cannot be compared with other tests quantitatively. In other words, it is necessary only to compare the results within the same test.

(Example B: Deodorization mechanism elucidation test of deodorant glass agent)
Deodorization test method 1 (nitrogen atmosphere):
A deodorizing glass agent (Example 1) having the glass composition shown in Table 1 above and MM (methyl mercaptan) were sealed in a Tedlar bag, immediately after malodor injection, 2 hours and 24 hours later, MM and DMDS (dimethyl disulfide) concentrations. Was measured with a gas chromatograph (GC).
The test conditions were as follows.
Tedlar bag capacity: 5L
Initial gas (MM) concentration: 100ppm
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
The above test was commissioned to the Environmental Science Research Institute.
Deodorization test method 2 (artificial air atmosphere):
The same test as described above was performed in an artificial air atmosphere (oxygen concentration 20%, nitrogen concentration 80%).
In the same manner as in the deodorization test method 1, an environmental science research institute was requested.
Measurement results and discussion:
FIG. 2 shows the result of the deodorization test method 1, and FIG. 3 shows the result of the deodorization test method 2.
As shown in FIGS. 2 and 3, DMDS was present even at blank time from 0 hour, but as a result of confirmation, DMDS was contained in the used gas due to contamination.
Although MM → DMDS undergoes some natural oxidation, the deodorizing glass agent clearly promotes the production of DMDS relative to the blank. In this reaction, MM dimerizes to DMDS.
In addition, the GC retention time was maintained up to 90 minutes for the presence of sulfur components, and the presence of components other than MM and DMDS was confirmed, but no particular peak was observed.
If the deodorizing mechanism of the deodorizing glass agent is a sulfurization reaction like the soluble glass agent of the prior art, the sulfur component and the copper component are combined. However, as a GC result, conversion from MM to another sulfur component DMDS was confirmed instead of bonding with copper. The amount of conversion is also considered to be almost equal (considering the reduction of MM of the blank itself).
Moreover, as shown in FIG. 3, the presence of oxygen clearly increased its deodorizing effect. It is considered that the catalyst promotes the reaction of MM → DMDS through oxygen. CuO, which is known to show a deodorizing mechanism by catalytic action, also promotes the reaction of MM → DMDS via oxygen. It is said to be through oxygen adsorbed on the surface. There is a possibility that the deodorizing glass agent exhibits the same catalytic action. Although the deodorizing effect is confirmed even in a nitrogen atmosphere, oxygen adsorbed on the glass surface before sealing may have been affected.
As the reaction formula, the following formula is assumed.
2CH ₃ —SH + oxidant → CH ₃ —SS—CH ₃ + 2H ⁺ + 2e ⁻

(Example C: Comparative test of CuO and deodorant glass agent)
Deodorization test method:
The deodorizing glass agent (Example 1) which consists of a glass composition of Table 1, each CuO reagent, and MM were enclosed in the Tedlar bag, and the MM density | concentration in a bag accompanying elapsed time was measured with the gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (MM) concentration: 55 ppm (repeated 8 times at 55 ppm)
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
CuO: Wako reagent, particle size (described value 5 μm), specific surface area 0.38 m ² / g.
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
Measurement results and discussion:
As shown in FIG. 4, it was confirmed that both the deodorizing glass agent and CuO converge at about 10 ppm or less. This is an error of the gas detector tube due to the generation of DMDS by catalytic action (when there is a sulfur component other than MM, it becomes an error factor because it cannot be identified). Separately, the MM at the time of convergence was confirmed by GC, but it was confirmed that it was below the detection limit (result omitted). From the CuO content, the deodorizing glass agent showed a high deodorizing effect despite being about 1/10 of the CuO reagent.
At the time of the first repetition, the deodorization speed of CuO was higher, but when it was the eighth repetition, the relationship between the two was reversed and it was confirmed that the deodorization speed of the deodorant glass agent was superior. Specifically, it is understood that the deodorizing glass agent maintains the deodorizing speed even in the eighth repetition, but the deodorizing effect of CuO tends to decrease. CuO is known to be poisoned (catalyst deterioration) when deodorizing sulfur-based malodors, and this is considered to be due to this effect. In the present Example, it was confirmed that it has become a stable catalyst state by vitrification.

(Example D: Comparison of soluble glass agent and deodorant glass agent = comparison of deodorant glass agent by sulfurization reaction and deodorant glass agent by catalytic reaction)
Dissolving glass preparation method:
Dissolvable glass 1
Typical soluble glass agent (Ion Pure) Commercially available soluble glass 2
94.26 g of magnesium phosphate, 157.76 g of 89% by weight phosphoric acid, and 4.0 g of silver oxide were mixed and held at 300 ° C. for 3 hours, and then the dried product was melted at 1300 ° C. for 1 hour. Then, a glass having a glass composition shown in Table 2 below was prepared, and crushed to prepare a sample.
Soluble glass 3
71.36 g of potassium phosphate, 38.05 g of monobasic calcium phosphate, 26.17 g of copper oxide, and 117.72 g of 89 wt% phosphoric acid were mixed and held at 300 ° C. for 3 hours. A glass having the glass composition shown in Table 2 below was prepared by melting at 1300 ° C. for 1 hour, and pulverized to prepare a sample.
Dissolvable glass 4
Anhydrous boric acid 12.05 g, sodium nitrate 5.62 g, ultrafine silica (product name: Snowtex S) 5.26 g, alumina powder 0.2 g, copper chloride 21.4 g, and pure water 60 ml were stirred with a high-speed stirrer. After preparing the sol, 3 ml of 10N ammonia water was added thereto to gel it, dried in a dryer at 120 ° C. for 180 minutes, then in a baking furnace at room temperature → 525 ° C. for 30 minutes, and at 525 ° C. for 10 minutes. Minutes, 525 → 950 ° C. for 30 minutes, and 950 ° C. for 30 minutes to produce a glass agent having the glass composition shown in Table 2 below, which was crushed to prepare a sample.

Deodorization test method:
The deodorizing glass agent (Example 1) which consists of the glass composition of Table 1, the soluble glass and hydrogen sulfide which consist of the glass composition of the said Table 2 are enclosed in a Tedlar bag, and the hydrogen sulfide concentration in the bag over time is gasified. Measured with a detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (hydrogen sulfide) concentration: 55ppm
Temperature: Room temperature (20-25 ° C)
Humidity: About 80%
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
Measurement results and discussion:
As shown in FIG. 5, it was confirmed that the soluble glass agent has a high reaction speed due to deodorization by the sulfurization reaction. For this reason, the soluble glass agent was also measured after 10 minutes. The soluble glasses 1 and 3 converged in the first repetition. It was confirmed that the deodorization limit was almost reached. These glass agents were confirmed to be agglomerated because of their low water resistance and easy moisture absorption. As reference values, Ag ₂ O and CuO equivalent values in the sample amount are shown. However, this is in the total amount of glass, and the amount deposited on the surface actually shows the deodorizing effect. The soluble glass agent exhibits a sulfurization reaction on the surface (in fact, a discoloration (yellow to brown) confirming the reaction was confirmed), and it is considered that Ag and Cu inside the glass do not contribute to the reaction. The soluble glass 3 showed a slight deodorizing effect the second time repeatedly, but because it was agglomerated, there was a possibility that the gas slowly dipped inside and was deodorized. Since the deodorizing glass agent has a different deodorizing mechanism from that of the soluble glass agent, it was confirmed that the deodorizing glass agent has high durability and a large amount of deodorizing despite the fact that the molar amount of CuO is smaller than that of the soluble glass 4. .
Supplement:
Since it was adjusted under high humidity conditions, the deodorizing glass agent promoted by the presence of moisture improved the deodorizing speed (compared to other examples) (all other examples had a humidity of 50% or less) .

(Example E: Relationship between CuO content and deodorizing effect)
Deodorant glass preparation method:
After preparing the raw materials, it was melted at a melting temperature of 1350 ° C. for 8 hours and poured out to obtain a glass having the glass composition shown in Table 3 below. The formation after melting was performed by natural cooling, but can also be performed by water cooling.
The glass composition was confirmed by semi-quantitative measurement using a fluorescent X-ray analyzer. The obtained glass was dry-pulverized using a ball mill and controlled so that D ₅₀ = 4.5 μm or less and D ₉₈ = 40 μm or less by a particle size meter. The particles having a particle size (diameter) of 100 μm or more were removed by sieving.

Deodorization test method:
A glass agent (CuO-containing deodorizing glass agent and non-containing glass agent) having the glass composition shown in Table 3 above and MM were sealed in a Tedlar bag, and the MM concentration in the bag over time was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (MM) concentration: 55ppm
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
Measurement results and discussion:
As shown in FIG. 6, it was confirmed that the deodorizing effect converged to less than about 10 ppm in any of Experimental Examples 1 to 6 having different CuO contents. This is an error of the gas detector tube due to the generation of DMDS by catalytic action (when there is a sulfur component other than MM, it becomes an error factor because it cannot be identified).
Moreover, it was confirmed that the deodorizing effect increases (specifically, the deodorizing speed increases) with the CuO content at the same particle size and weight.
This is because the CuO content on the glass surface in contact with the malodor increases with the CuO content.
However, even in Experimental Example 1 having the smallest CuO content, MM having a high concentration of 55 ppm is deodorized, and the deodorizing effect is sufficient.
In Experimental Example 1, when compared at 24 hours, the deodorization speed is inferior to that of Experimental Examples 2 to 6, but the speed can be easily compensated by reducing the particle size and increasing the surface area.

(Example F: Sulfidation and catalytic action accompanying water resistance)
As the glass composition changes, the water resistance changes. At this time, since the deodorizing mechanism may change as it approaches the soluble glass agent, the amount of dissolution was compared with ion pure (Comparative Examples 2 and 3), which is a typical soluble glass agent. Comparative Examples 2 and 3 are “Ion Pure (commercially available)” which is a typical soluble glass agent.
Deodorant glass preparation method:
After the raw material preparation, the glass was melted at a melting temperature of 1350 ° C. for 8 hours and poured out to obtain a glass having a glass composition shown in Table 4 below. The formation after melting was performed by natural cooling, but can also be performed by water cooling.
The glass composition was confirmed by semi-quantitative measurement using a fluorescent X-ray analyzer. The obtained glass was dry-pulverized using a ball mill and controlled so that D ₅₀ = 4.5 μm or less and D ₉₈ = 40 μm or less by a particle size meter. The particles having a particle size (diameter) of 100 μm or more were removed by sieving. In Experimental Examples 7 to 10, the CuO content (mol%) was adjusted to be equal.

Method for confirming glass dissolution:
A 0.1 g sample was immersed in 100 mL of distilled water and kept at room temperature (20 to 25 ° C.) for 24 hours, and the amount of decrease was confirmed.
Judgment method:
Tedlar bag 1L, MM concentration 55ppm, x that has reached the deodorization limit by 8 times repeatedly, deodorization limit has not been reached, but it has been confirmed that the deodorization speed has decreased, △,
The case where sustainability was confirmed even after repeated 8 times was evaluated as ◯.
The specific surface area and particle size of the glass agent during the deodorization test are as shown in Table 4, and the sample weight is 0.1 g.
Judgment results and discussion:
Although Experimental Examples 9 and 10 were confirmed to have a catalytic action, it is thought that the sulfurization reaction in ion elution similar to that of the soluble glass agent worked greatly due to insufficient water resistance.

(Example G: Performance comparison with highly durable inorganic deodorant glass agent (commercially available))
Deodorization test method 1 (sustainability evaluation):
A deodorizing glass agent (Example 1) having the glass composition shown in Table 1 and MM were enclosed in a Tedlar bag, and the MM concentration in the bag over time was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (MM) concentration: As shown in Table 6 Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
As a comparative evaluation object, the same deodorizing test was conducted using an inorganic deodorizing glass agent shown in Table 5 below. These inorganic deodorizing glass agents are all commercially available as highly durable inorganic deodorizing glass agents.

Moreover, the deodorizing test similar to the above was done without a deodorizing glass agent as a blank.
Deodorization test method 2 (water presence condition):
A deodorizing glass agent (Example 1) comprising the glass composition of Table 1, the inorganic deodorizing glass agents 1 and 2 of Table 5, each of the CuO reagent, MM, and distilled water are enclosed in a Tedlar bag, and the bag with the elapsed time The MM concentration inside was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (MM) concentration: 55ppm
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
Distilled water addition amount: 500 μl (wet the entire sample surface)
CuO: Wako reagent, particle size (described value 5 μm), specific surface area 0.38 m ² / g.
Moreover, the deodorizing test similar to the above was done without a deodorizing glass agent as a blank.
Measurement results and discussion:

As shown in Table 6 above, the test was repeated 10 times while changing the initial gas concentration. As shown in FIG. 7, the same tendency was confirmed until the 10th repetition. That is, the inorganic deodorizing glass agent 1 has a high instantaneous deodorizing effect, but converges because it has a deodorizing limit (adsorption limit). The inorganic deodorizing glass agent 2 and Example 1 can be deodorized at a high concentration, and at the same weight, the inorganic deodorizing glass agent 2 has a higher deodorizing speed. Although the inorganic deodorizing glass agent 1 converges, there is reproducibility of the deodorizing effect if the malodor is replaced (reset). In any case, the deodorizing effect is maintained even at the 10th time point in spite of the high concentration of malodor.
Moreover, as shown in FIG. 8, the change in the deodorization tendency was confirmed by the addition of water.
In the inorganic deodorant glass agent 1, it was confirmed that the instantaneous deodorizing effect falls. This is considered to be due to the fact that the instant effect is weakened when the surface is wet because the agent has high physical adsorption. It was confirmed that the inorganic deodorizing glass agent 2 cannot exhibit a sufficient deodorizing effect in a water-existing environment. In this example, it was confirmed that the deodorization speed was significantly improved by adding water. In this example, there is a possibility that a catalyst effect is promoted by the presence of moisture and a deodorization mechanism by a sulfurization reaction is added by ion elution. In this example, the elution amount of copper ions is small, so the former possibility is high. In addition, the deodorization speed was faster than that of CuO in the water addition condition despite the first repetition (see FIG. 4 comparison).
In the blank, although there was a slight decrease, a clear decrease in density was not confirmed. This result indicates that MM was not dissolved in water and the deodorizing effect of each agent could be evaluated.

(Example H: Deodorizing effect confirmation test for lower fatty acids)
Deodorization test method:
A deodorizing glass agent (Example 1) having a glass composition shown in Table 1 and malodor were sealed in a Tedlar bag, and the malodor concentration in the bag over time was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
Measurement results and discussion:
As shown in FIG. 9, it was confirmed that there was a deodorizing effect on any of lower fatty acids such as acetic acid, propionic acid, normal butyric acid, normal valeric acid, and isovaleric acid.

(Example I: Deodorizing effect confirmation test for trans-2-nonenal)
Deodorization test method:
A deodorizing glass agent (Example 1) having the glass composition shown in Table 1, each CuO reagent and trans-2-nonenal were sealed in a Tedlar bag, and the malodor concentration in the bag over time was measured with a high performance liquid chromatograph. .
In the high-performance liquid chromatographic method, the gas in the bag is collected in a DNPH cartridge, the DNPH derivative is eluted through this cartridge through acetonitrile, the obtained eluate is measured with a high-performance liquid chromatograph, and the gas concentration in the bag is determined. calculate.
The test conditions were as follows.
Tedlar bag capacity: 4L
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D ₅₀ = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
CuO: Wako reagent, particle size (described value 5 μm), specific surface area 0.38 m ² / g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
The above test was commissioned to the Japan Food Analysis Center.
Measurement results and discussion:

As shown in Table 7 above, it was confirmed that there was a deodorizing effect on trans-2-nonenal.

(Example J: Examination of particle size and deodorization speed of deodorant glass agent)
Deodorant glass preparation method:
After preparing the raw materials, it was melted at a melting temperature of 1350 ° C. for 8 hours and poured out to obtain a glass having the glass composition shown in Table 8. After melting, natural cooling was performed, but water cooling can also be used. The obtained glass was crushed and adjusted to the particle size shown in Table 8.

All the glasses of Experimental Examples 11 to 18 shown in Table 8 have a sufficient deodorant absolute amount. However, the deodorizing speed required varies depending on the use of the deodorizing glass agent.
For example, in a living environment, it is said that several ppb of methyl mercaptan is generated in a toilet. Assuming 10 ppb, suppose you want to deodorize all in one minute.
As shown in FIG. 6 above, Experimental Examples 2 to 6 can deodorize 55 ppm in 24 hours. (The secondary product dimethyl disulfide is ignored, and methyl mercaptan is considered to be capable of deodorizing about 55 ppm) In calculation (55 ppm / 24 h / 60 m), the deodorizing amount per minute is 38 ppb. Moreover, since Experimental Example 1 can deodorize 55 ppm in 48 hours, the amount of deodorization per minute is 19 ppb in calculation (55 ppm / 48 h / 60 m).
As can be seen from FIG. 6, the deodorization speed is expected to be even faster (it appears to be more gradual on the graph at the measurement timing), so the deodorization amount per minute is higher than the calculated value above. Is expected.
The evaluation result in FIG. 6 is preferably a speed with a margin for the toilet space because of the effect of the small volume and the glass agent alone.
If deodorization of 55 ppm is possible in 24 hours, the speed is about 4 times the environmental concentration of 10 ppb to be deodorized. If deodorization of 55 ppm is possible in 48 hours, the speed is about twice.
In Table 8, “A judgment” is about 4 times (allowable range up to −5%), and “B judgment” is about twice (allowable range up to −5%).
Measurement results and discussion:
Deodorant glass agent particle size (D ₅₀ ) y (μm), CuO addition amount x (mol%),
When 0.01 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
When 2.03 ≦ x ≦ 23, y ≦ 10.5
In this range, it was confirmed that quicker deodorization was performed.
Note that the particle diameter of the deodorant glass agent _{(D 50) y (μm)} , in order to "powder" form of deodorant glass agent, was made the upper limit 10.5 [mu] m.

(Example K: Mother composition and deodorizing effect)
Deodorant glass preparation method:
After preparing the raw materials, it was melted at a melting temperature of 1350 ° C. for 8 hours and poured out to obtain a glass having the glass composition shown in Table 9 below. The formation after melting was performed by natural cooling, but can also be performed by water cooling.
The glass composition was confirmed by semi-quantitative measurement using a fluorescent X-ray analyzer. The obtained glass was dry-ground using a ball mill and adjusted to the particle size shown in Table 9. The particles having a particle size (diameter) of 100 μm or more were removed by sieving.

Deodorization test method:
Experimental examples 19 to 29 of glass agents having the glass composition shown in Table 9 above and MM were sealed in a Tedlar bag, and the MM concentration in the bag over time was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (MM) concentration: 70ppm
Temperature: Room temperature (18-22 ° C)
Deodorant glass agent weight: 0.1g
Moreover, the same operation as the above was performed without a deodorizing glass agent as a blank.
Measurement results and discussion:
As shown in FIG. 13, when the content of CuO is the same, the deodorizing effect is sufficiently exhibited regardless of the mother composition. It can also be seen that a slight difference in CuO content than the mother composition affects the deodorization speed. In Experimental Examples 19 to 20, although the deodorization speed does not depend on the CuO content, it seems that the influence of the particle size has occurred (however, the measurement error is also sufficiently considered because of the gas detection tube).
Glass dissolution amount confirmation method, glass component elution amount confirmation method:
A 0.1 g sample was immersed in 100 mL of distilled water and kept at room temperature (18-22 ° C.) for 24 hours, and then the amount of decrease was confirmed. This result was taken as the glass dissolution amount.
After holding for 24 hours, only distilled water was collected by suction filtration and diluted to 250 mL. With respect to this adjustment liquid, the component concentration eluted using an ICP emission spectroscopic analyzer (Optima 2000 DV) was measured. The measurement was performed based on the method defined in JIS K0116 (2003), and the detection lower limit was set at 0.01 ppm. Moreover, the high concentration component was further diluted as necessary. The measured value was corrected to a concentration in 100 ml of distilled water, and this result was taken as the elution amount.
Particle size confirmation method:
It measured using the particle size meter (MicrotracII). For those whose specific surface area was not confirmed by actual measurement values, the specific surface area CS (specific surface area assuming all spherical shapes) calculated from the particle size measurement results was shown.
All results and discussion:
Within the composition range of Table 9, it was found that when the CuO content is the same, the influence on the deodorizing effect given by the mother composition is not much different. However, there was a difference between the amount dissolved and the amount eluted. When used as a deodorant, elution and dissolution have never been less in terms of aggregation, effects on surrounding materials, and safety. Empirically, it is desirable that the glass dissolution amount in this test be 10% or less.

(Embodiment 2: CuO-containing alkali-alkaline earth-silicate glass)
The deodorizing glass agent of the present embodiment includes 50 to 70 mol% of SiO ₂ , 10 to 33 mol% of R ₂ O (R = Li, Na, K), and R′O (R ′ = Mg, Ca, Sr). Ba) in an amount of 0 to 15 mol%, Al ₂ O _{3 in an amount} of 0 to 6 mol%, and CuO in an amount of 0.01 to 23 mol% “alkali (R ₂ O) -alkaline earth (R′O) -silicate” It is made of “acid glass (SiO ₂ )” and can be produced by a melt quenching method in the same manner as a normal glass agent. The shape of the glass agent is a powder obtained by pulverizing after obtaining a pre-molded body by a melt quenching method. The pulverization referred to here means pulverization by a generally known pulverizer (for example, a ball mill, a bead mill, a jet mill, a CF mill, etc.), and may be dry or wet.

Hereinafter, each glass composition will be described in detail.
(SiO ₂ )
SiO ₂ is a main component that forms the structural skeleton of glass. Its content is 50 to 70 mol%, preferably 55 to 70 mol%. If it is less than 50 mol%, the chemical durability of the glass becomes insufficient, and the glass tends to devitrify, which is not preferable. Furthermore, if it is less than 50 mol%, the water resistance of the glass becomes insufficient, and copper ions are more likely to elute in the presence of moisture (including moisture in the atmosphere). Since the deodorizing effect by the sulfurization reaction which occurs by this becomes strong, it is not preferable. If it exceeds 70 mol%, the melting point increases, which makes glass melting difficult and also causes an increase in viscosity.

(R ₂ O (R = Li, Na, K))
R ₂ O (R = Li, Na, K) breaks the bond between Si and O in the glass structure skeleton to form non-crosslinked oxygen, resulting in a decrease in glass viscosity, moldability and solubility. And a flux similar to B ₂ O ₃ . The content of R ₂ O (R = Li, Na, K) is 10 to 33 mol% in total, preferably 12 to 24 mol%, taking into consideration the content ratio with multiple components. And When it exceeds 33 mol%, the chemical durability of the glass becomes insufficient. Specifically, a whitening phenomenon called bloom is caused by a reaction between the glass agent and moisture in the atmosphere. The occurrence of bloom is undesirable because it reduces the contact area with malodorous gas. In addition, the alumina in the melting furnace is easily eroded.

(R'O (R '= Mg, Ca, Sr, Ba))
R′O (R ′ = Mg, Ca, Sr, Ba) is a component that improves the chemical durability of the glass. The content of one or more of R′O (R ′ = Mg, Ca, Sr, Ba) is 0 to 15 mol%, preferably 2 to 10 mol% in total. If it exceeds 15 mol%, the viscosity at the time of melting becomes high and the glass tends to be devitrified, which is not preferable. In addition, it is not an essential component in the deodorizing glass agent of the invention, and its content may be 0 mol%.

(CuO)
Regarding CuO, it is basically the same as in Embodiment 1 described above, but in this embodiment, the addition amount x (mol%) of CuO powder and the particle size (D ₅₀ , y μm) of the deodorizing glass agent are expressed by the following formulae. By limiting to this range, “rapid deodorization” that was not considered in the conventional deodorizing glass agent can be realized.
When 0.01 ≦ x ≦ 2.38, y ≦ 4.27x + 0.34
When 2.38 ≦ x ≦ 23, y ≦ 10.5

(Al ₂ O ₃ )
Al ₂ O ₃ is a component that improves the chemical durability of the glass and affects the crystal structure stability. Further, Al ₂ O ₃ functions to suppress the phase separation of the glass and increase the homogeneity of the glass agent. It is desirable that the content is 6 mol% or less, preferably 5.5 mol% or less, because the viscosity may increase or the addition may affect the redox state of copper ions in the glass. .

(Other trace components) (Fe ₂ O ₃ ) (Cr ₂ O ₃ , MnO ₂ , CeO ₂ ) is the same as in Embodiment 1 described above.

Considering the above, in the present embodiment, the composition range in which the deodorizing effect is stably obtained is specified. That is, the composition range was specified in consideration of the melting temperature range, the oxidation-reduction state, and the composition range. If a glass agent having the above composition range is produced by a melt quenching method, a deodorizing glass agent can be stably obtained. In particular, it can be stably obtained by melting in a tank furnace, melting an electric furnace, or melting a small-scale crucible. In general, in the case of soda lime glass, it is known that the valence balance of copper ions (Cu ^{2 + /} total) is about 15% for the former and about 50% for the latter in tank furnace melting and electric furnace melting. . Naturally, the valence balance also changes in the composition of the present embodiment. Since the deodorizing mechanism is a catalytic action, these chemical states may affect the deodorizing effect, but the difference in the effect is not particularly problematic as long as it is in the above composition range.

Note that it is necessary to consider that the oxidation-reduction state varies depending on the melting temperature and the melting time. The melting temperature may be controlled to 1200 to 1400 ° C, preferably 1280 to 1380 ° C. The melting time is preferably 6 to 8 hours. The glass obtained here is confirmed to be blue or greenish blue by Cu ²⁺ . As described above, in the composition range of the present invention, the valence balance of copper ions is not necessarily important as long as the melting temperature and time are taken into consideration. In addition, the valence balance of the obtained glass agent was intentionally changed by heat treatment (a blue plate in which a thin plate was produced and Cu ²⁺ color was confirmed, the valence balance was changed to Cu ⁺ >> Cu ²⁺ Although almost no color tone was confirmed, brown (red) glass in which precipitation of colloidal metallic copper of Cu ⁰ was confirmed, the deodorizing effect was confirmed. Thus, a deodorizing effect is obtained by using a glass agent having the above composition range, and the deodorizing effect is maintained even if the valence balance of copper ions is controlled by heat treatment or the like after molding.

As a temporary trapping agent, it can be used by mixing with a physical adsorbent (activated carbon, silica gel, zeolite, etc.). Moreover, since malodors do not necessarily exist as a single component, it is possible to use a combination of agents specialized in deodorizing various malodors. It can also be used by mixing with a conventional deodorizing glass agent.

(Example L: Examination of particle size and deodorization speed of deodorant glass agent)
In the same manner as in Example J of Embodiment 1, the particle size and deodorization speed were examined.

All of the glasses of Experimental Examples 33 to 45 shown in Table 10 have a sufficient deodorizing absolute amount.
Measurement results and discussion:
Deodorant glass agent particle size (D ₅₀ ) y (μm), CuO addition amount x (mol%),
When 0.01 ≦ x ≦ 2.38, y ≦ 4.27x + 0.34
When 2.38 ≦ x ≦ 23, y ≦ 10.5
In this range, it was confirmed that quicker deodorization was performed.
Note that the particle diameter of the deodorant glass agent _{(D 50) y (μm)} , in order to "powder" form of deodorant glass agent, was made the upper limit 10.5 [mu] m.

Claims (9)

1. A deodorizing glass agent comprising CuO-containing alkali-alkaline earth-borosilicate glass or CuO-containing alkali-alkaline earth-silicate glass,
   Deodorant glass agent characterized by adding CuO powder as a raw material in the range of the following formula (x mol%) and setting the particle size (D ₅₀ ) of the deodorant glass agent to the following range (y μm). .
   When 0.01 ≦ x ≦ 0.198, y ≦ 4.27x + 0.34
   When 0.198 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
   When 2.03 ≦ x ≦ 23, y ≦ 10.5
2. The glass is
   The SiO ₂ 46 ~ 70 mol%,
   15 to 50 mol% in total of B ₂ O ₃ and R ₂ O (R = Li, Na, K),
   R′O (R ′ = Mg, Ca, Sr, Ba) 0-10 mol%,
   0 to 6 mol% of Al ₂ O ₃ ,
   0.01-23 mol% CuO
   Contains
   The deodorizing glass agent according to claim 1, which satisfies the following formula.
   When 0.01 ≦ x ≦ 2.03, y ≦ 5.08x + 0.18
   When 2.03 ≦ x ≦ 23, y ≦ 10.5
3. The glass is
   5 to 20 mol% of B ₂ O ₃ ,
   10-30 mol% of R ₂ O (R = Li, Na, K)
   The deodorizing glass agent according to claim 2, which is contained.
4. The glass is
   The SiO ₂ 51 ~ 63 mol%,
   A total of 21 to 39 mol% of B ₂ O ₃ and R ₂ O (R = Li, Na, K),
   2-7 mol% of R′O (R ′ = Mg, Ca, Sr, Ba)
   0 to 5.5 mol% Al ₂ O ₃
   1 to 13 mol% of CuO
   The deodorizing glass agent according to claim 2, which is contained.
5. The glass is
   8 to 17 mol% B ₂ O ₃ ,
   R ₂ O (R = Li, Na, K) 13-22 mol%,
   The deodorizing glass agent according to claim 4, which is contained.
6. The glass is
   SiO ₂ 53-62 mol%,
   10 to 17 mol% B ₂ O ₃
   Na ₂ O 13-19 mol%,
   3-6 mol% CaO,
   0 to 4.5 mol% of Al ₂ O ₃
   4-13 mol% CuO
   The deodorizing glass agent according to claim 2, which is contained.
7. The glass is
   50 to 70 mol% of SiO ₂
   10 to 33 mol% of R ₂ O (R = Li, Na, K)
   0 to 15 mol% of R′O (R ′ = Mg, Ca, Sr, Ba),
   0 to 6 mol% of Al ₂ O ₃ ,
   0.01-23 mol% CuO
   Contains
   The deodorizing glass agent according to claim 1, which satisfies the following formula.
   When 0.01 ≦ x ≦ 2.38, y ≦ 4.27x + 0.34
   When 2.38 ≦ x ≦ 23, y ≦ 10.5
8. The glass is
   55 to 70 mol% of SiO ₂
   A total of 12 to 24 mol% of R ₂ O (R = Li, Na, K),
   2 to 10 mol% of R′O (R ′ = Mg, Ca, Sr, Ba),
   0 to 5.5 mol% Al ₂ O ₃
   1-20 mol% CuO
   The deodorizing glass agent according to claim 7, which is contained.
9. The glass is
   The SiO ₂ 55 ~ 65 mol%,
   12-20 mol% Na ₂ O,
   3-7 mol% CaO,
   0 to 5 mol% of Al ₂ O ₃ ,
   4-13 mol% CuO
   The deodorizing glass agent according to claim 7, which is contained.

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