KR102460894B1 - deodorant glass - Google Patents

Abstract

The present invention provides a deodorant with high convenience because it can deodorize more quickly than a conventional deodorant, can exhibit a stable deodorizing effect for a long time, does not aggregate even as a powder, and has a high degree of freedom regarding product shape and usage mode it was made to The deodorant of the present invention consists of CuO-containing alkali-alkaline earth-borosilicate glass or CuO-containing alkali-alkaline earth-silicate glass, and CuO powder as a raw material is added in the range of the following formula (x mol%), and the particle size of the deodorizing glass (D ₅₀ ) was set 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

Description

deodorant glass

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

BACKGROUND ART In recent years, interest in a comfortable living environment has increased, and the demand for various deodorants is increasing.

Among the odors that are a problem in residential environments, sulfur-based odors such as hydrogen sulfide and methyl mercaptan are reluctant as those imparting a strong unpleasant feeling. In particular, methyl mercaptan is known as an odor causative substance in which a putrefactive odor is felt even at a low concentration of about ppb, and development of a technology related to the deodorization has been demanded.

As a technique related to the deodorization, any one of silver, copper, and iron is contained in a soluble glass containing P ₂ O ₅ as a main component, and PO ₄ ^2- ions, Ag ⁺ ions, Cu ^{2 +} ions, and Fe ^{2+ ions} A technique for deodorizing sulfur-based odors by setting the dissolution rate to a specific range (Patent Document 1), or a technique for removing odor-causing substances such as methyl mercaptan with a deodorant in which copper oxide is dispersed in activated carbon (Patent Document 2) This is disclosed.

However, since the technique of Patent Document 1 is a technique using a sulfidation reaction of Ag ⁺ ions, Cu ^{2 +} ions, Fe ^{2+ ions} and sulfur components generated by dissolution, when an equilibrium state is reached, no further reaction proceeds. , a problem that a continuous deodorizing effect cannot be expected, and a soluble glass agent containing P ₂ O ₅ as a main component lacks chemical durability, particularly water resistance, so, for example, when it is in a powder form, it is easy to aggregate and difficult to handle. There was a problem that the convenience was poor due to restrictions regarding this and usage mode.

Although the specific action|action of copper oxide is not described in patent document 2, it is estimated that the odor substance removal efficiency of activated carbon is improved by the catalytic action. However, in the technique of Patent Document 2, there is a problem that copper oxide dispersed in activated carbon is poisoned (catalyst deterioration) by reaction with a odor-causing substance, and the duration of the deodorizing effect is still insufficient.

Moreover, as a function of a deodorant, it was originally preferable that it can deodorize more rapidly, but there also existed a problem that the deodorizing speed was not considered with the conventional deodorant.

Patent Document 1: Japanese Patent Laid-Open No. Hei 4-67868 Patent Document 2: Japanese Patent Laid-Open No. 2009-213992

The object of the present invention is to solve the above problem, to perform deodorization more rapidly than conventional deodorants, and to exhibit a stable deodorizing effect for a long time compared to conventional deodorants, and to agglomerate even in powder form It is to provide a deodorant with high convenience due to a high degree of freedom regarding product shape or usage mode.

In the present invention, as a means for solving the above problems, as a deodorizing glass made of "CuO-containing alkali-alkaline earth-borosilicate glass" or "CuO-containing alkali-alkaline earth-silicate glass", CuO powder as a raw material is It is characterized in that it is added in the range (x mol%) of , and the particle size (D ₅₀ ) of the deodorizing glass is set to the following range (y µm)”. For reference, the range prescribed|regulated by the following 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

As said CuO containing alkali-alkaline earth-borosilicate glass, _46-70 mol% of SiO2, 15-50 mol% _{of B2O3} and R2O (R ₌ Li, Na, K) in total, R'O (R'=Mg, Ca, Sr, Ba) is 0-10 mol%, Al ₂ O ₃ is 0-6 mol%, CuO is 0.01-23 mol%, It is preferable to use the thing which satisfies the following formula. . Here, it is more preferable to use what contains 5-20 mol% _{of B2O3} and 10-30 mol% of R2O (R ₌ Li, Na, K). For reference, the range prescribed|regulated by the following 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 is 51-63 mol% of SiO ₂ , 21-39 mol% of B ₂ O ₃ and R ₂ O (R=Li, Na, K) in total, R'O (R'=Mg, Ca) , Sr, Ba) of _2-7 mol%, Al ₂ O ₃ of 0-5.5 mol%, and CuO of 1-13 mol%, _it is preferable to use a thing containing 8-17 mol% of B2O3 , R ₂ O (R = Li, Na, K) 13 to 22 mol%, it is more preferable to use one containing.

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

As said CuO containing alkali-alkaline earth-silicate glass, 50-70 mol% _of SiO2, 10-33 mol% of R2O (R ₌ Li, Na, K), R'O(R'=Mg, Ca) , Sr, Ba) 0-15 mol%, Al ₂ O ₃ 0-6 mol%, CuO 0.01-23 mol% It is preferable to use what satisfy|fills the following formula. For reference, the range prescribed|regulated by the following 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 55 to 70 mol% of SiO ₂ , 12 to 24 mol% of R ₂ O (R=Li, Na, K) in total, R'O (R'=Mg, Ca, Sr, Ba) It is more preferable to set it as what contains _2-10 mol% of Al2O3, _0-5.5 mol% of Al2O3, and 1-20 mol% of CuO.

The said glass composition is 55-65 mol% _of SiO2, 12-20 mol% _of Na2O, _3-7 mol% of CaO, 0-5 mol% _of Al2O3, and 4-13 mol% of CuO. It is more preferable to set it as what it contains.

Conventionally, although various deodorizing glass agents using soluble glass have been developed, "the glass agent which shows the deodorizing effect by a catalytic action" does not exist. As a result of long research, the present inventors have found that "CuO contained in the above ratio in the glass of the above composition functions as a catalyst and promotes the decomposition reaction (oxidation/reduction reaction) of sulfur-based malodorous substances, deodorizing sulfur-based malodorous substances. new knowledge was discovered. This invention was made based on this knowledge, and development to various uses is anticipated as "a novel glass agent which shows the deodorizing effect by a catalytic action".

As described above, in the present invention, CuO contained in glass has a mechanism for accelerating the decomposition reaction of sulfur-based malodorous substances as a catalyst. The capacity (for example, in Patent Document 1, in proportion to the ion concentration for adsorbing the odor component of the sulfur component) can be increased, and the deodorizing effect can be sustained over a long period of time by repeatedly using the catalyst, and functions as a catalyst Poisoning as in the prior art (for example, Patent Document 2) in which CuO is dispersed in activated carbon is unlikely to proceed, and the catalytic function can be stably exhibited over a long period of time.

Further, according to the present invention, as a raw material, CuO powder is added in the range (x mol%) of the following formula, and the particle size (D ₅₀ ) of the deodorizing glass is set to the following range (y μm), so that in a conventional deodorant, "Quick deodorization" that was not considered can be realized.

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 by 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 making a deodorizing glass product into a powder form and securing a large amount of contact area with a malodorous substance.

Further, the deodorizing glass agent of the present invention is not limited to a sulfur-based malodorous substance, and can be deodorized as long as it is a malodorous substance capable of a dehydrogenation reaction. Specifically, acetic acid and isovaleric acid of lower fatty acids known as body odors (sweat, foot odor), propionic acid, normal butyric acid, and normal valeric acid prescribed by the Malodor Prevention Act, caproic acid and enantic acid of medium chain fatty acids, and old odor Trans-2-nonenal, known as , can also be deodorized. Generally, those having 2 to 4 carbon atoms are referred to as short-chain fatty acids (lower fatty acids), but in the present specification, acetic acid having 1 carbon atom and valeric acid having 5 carbon atoms are also treated as lower fatty acids. The deodorizing mechanism for these lower fatty acids or trans-2-nonenal is highly likely to be similar to the catalytic action for sulfur-based malodorous substances. For example, in the deodorizing glass agent of the present invention, methyl mercaptan is catalytically decomposed to produce a dimer of dimethyl disulfide, but at this time, a dehydrogenation reaction is occurring. Likewise, it is assumed that lower fatty acids are also decomposed by dehydrogenation. Or, since the malodorous gas by a lower fatty acid is known as acidity, it may produce a neutralization reaction with the deodorizing glass agent of this invention containing a lot of alkali. When the reaction amount was calculated from the deodorization test result, since the deodorizing effect more than an equivalent reaction was confirmed, the possibility of simultaneous generation|occurrence|production of the deodorizing effect by a catalytic action and the deodorizing effect by a neutralization reaction is high. However, since trans-2-nonenal is known as a neutral gas, there is a high possibility that the deodorizing effect is not a neutralization reaction but a catalytic action. Moreover, it is not limited to trans-2-nonenal, and the possibility of decomposing|disassembling the palmitoleic acid of a precursor and showing a deodorizing effect is also considered.

Moreover, since the deodorizing glass agent of this invention contains a lot of CuO in glass, the antibacterial effect by CuO can also be exhibited simultaneously.

In addition, in the prior art (for example, Patent Document 1, etc., a deodorizing method in which Ag ⁺ ions, Cu ^{2 +} ions, Fe ^{2 +} ions with high affinity with sulfur components are reacted) using “sulfation reaction”, sulfiding reaction As a result, there was a problem of discoloration of the glass and impairing the aesthetics of the glass, but the present invention uses vitrified CuO as a catalyst to accelerate the decomposition reaction of sulfur-based malodorous substances, thereby improving the deodorizing effect of sulfur-based malodorous substances. Since it is shown, a deodorizing function can be exhibited, without discoloring glass.

As in the invention described in claim 2, 46 to 70 mol% of SiO ₂ , 15 to 50 mol% of B ₂ O ₃ and R ₂ O (R=Li, Na, K) in total, R'O (R'= Mg, Ca, Sr, Ba) 0 to 10 mol%, Al ₂ O ₃ 0 to 6 mol%, CuO 0.01 to 23 mol% by using the glass of the above composition as a deodorizing glass, compared to the prior art. , it is possible to realize a deodorizing glass product having a high degree of freedom regarding product shape and usage mode and high convenience. Specifically, it can exhibit a stable deodorizing effect for a long time, has high chemical durability, is difficult to aggregate when powdered, An excellent deodorizing effect can be exhibited even in an environment (450 degrees C or less), and the deodorizing glass product which is very easy to handle can be implement|achieved.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows the measurement result of Example A.
2 is a graph showing the measurement results of Example B.
3 is a graph showing the measurement results of Example B.
4 is a graph showing the measurement results of Example C.
5 is a graph showing the measurement results of Example D.
6 is a graph showing the measurement results of Example E.
7 is a graph showing the measurement results of Example G.
It is a graph which shows the measurement result 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 CuO addition amount and particle size in Claim 1. FIG.
It is a graph which shows the relationship between the CuO addition amount in Claim 2, and a particle size.
It is a graph which shows the relationship between the CuO addition amount and particle diameter in Claim 7.
13 is a graph showing the measurement results of Example K.

Preferred embodiments of the present invention are shown below.

(Embodiment 1: CuO-containing alkali-alkaline earth-borosilicate glass)

The deodorizing glass agent of this embodiment contains _46-70 mol% of SiO2, 15-50 mol% _{of B2O3} and R2O in _total , R'O (R'=Mg, Ca, Sr, Ba) "Alkali (R ₂ O) - alkaline earth (R'O) - borosilicate glass (B ₂ O ₃ -) containing 0 to 10 mol%, 0 to 6 mol% of Al ₂ O ₃ and 0.01 to 23 mol% of CuO SiO2)", _and can be manufactured by a melt quenching method similarly to a normal glass product. The shape of the glass is made into a powder obtained by pulverizing a preform after obtaining a preform by a melt quenching method. The pulverization as used herein means pulverization by a generally known pulverizer (eg, a ball mill, a bead mill, a jet mill, a CF mill, etc.), and may be dry or wet.

Hereinafter, each glass composition is demonstrated in detail.

(SiO ₂ )

SiO2 becomes a main component which forms the structural frame|skeleton _of glass. The content is 46 to 70 mol%, preferably 51 to 63 mol%. When it is less than 46 mol%, the chemical durability of glass becomes inadequate, and it becomes easy to lose transparency of glass, and is unpreferable. In addition, when it is less than 46 mol%, the water resistance of the glass becomes insufficient, and as a result, copper ions are easily eluted in the presence of moisture (including moisture in the air). It is not preferable because the deodorizing effect by the sulfurization reaction becomes strong. When it exceeds 70 mol%, when melting|fusing point rises, since meltability of glass becomes difficult and a viscosity raise also arises, it is unpreferable.

(B ₂ O ₃ )

_B2O3 is a component which improves the solubility and clarification of glass, _and in a specific composition, it may be a component which forms structural frame|skeleton of glass. B ₂ O ₃ greatly affects the stability of the glass depending on the content thereof, and in the present invention, the reason as a flux of the glass is large. The content is 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%, since _B2O3 volatilizes easily in a melting process, and composition control becomes difficult, it is unpreferable.

(R ₂ O(R=Li, Na, K))

R ₂ O (R = Li, Na, K) cleaves the bond between Si and O in the structural skeleton of the glass to form non-crosslinked oxygen, and as a result, reduces the viscosity of the glass, resulting in improved moldability and solubility. It is a component that improves, and is the same flux as B ₂ O ₃ . The content is 10 to 30 mol% in total, preferably 13 to 22 mol%, taking into consideration the content ratio of one or more types of R ₂ O (R=Li, Na, K) with other components. When it exceeds 30 mol%, the chemical durability of glass becomes inadequate. Specifically, the glass agent reacts with moisture in the atmosphere to cause a whitening phenomenon called bloom. It is undesirable because blooming reduces the contact area with the malodorous gas. In addition, the alumina material of the melting furnace is easily eroded.

(B ₂ O ₃ +R ₂ O(R=Li, Na, K))

As mentioned above, B ₂ O ₃ and R ₂ O are used together as a flux. _The total content _{of B2O3} and R2O is 15-50 mol%, Preferably the range of 21-39 mol% becomes a region which shows a deodorizing effect safely. When it is less than 15 mol%, since the meltability of glass becomes inadequate and transparency loss becomes easy to generate|occur|produce at the time of shaping|molding, it is unpreferable. When 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 air). It is undesirable because the deodorizing effect becomes stronger. Moreover, when it exceeds 50 mol%, since it is easy to generate|occur|produce a powdery phase at the time of melting, and the deodorizing effect made of glass becomes inadequate by this, it is unpreferable.

(R'O(R'=Mg, Ca, Sr, Ba))

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

(CuO)

CuO functions as a catalyst and promotes a decomposition reaction (oxidation/reduction reaction) of sulfur-based malodorous substances, thereby exhibiting a deodorizing effect of sulfur-based malodorous substances. The content is 0.01 to 23 mol%, preferably 1 to 13 mol%, more preferably 4 to 13 mol%. When it exceeds 23 mol%, an undissolved substance tends to remain, and since metallic copper tends to precipitate at the time of rapid cooling or processing, it is unpreferable. Since metallic copper also exhibits a deodorizing effect, its precipitation is not a problem from the viewpoint of deodorization, but since discoloration occurs in glass due to precipitation of metallic copper, it is not suitable for use in which discoloration of glass becomes a problem. 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 proceeds 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 has the same weight and the same particle size, the deodorizing ability tends to decrease with the decrease. It is estimated that this originates in the amount of CuO on the glass surface contacting a malodor decreasing. The CuO content and particle size vary depending on the required deodorizing speed and deodorizing capacity, but in the present embodiment, the CuO powder addition amount (x mol%) and the deodorizing glass particle size (D ₅₀ , y μm) are within the range of the following formula By limiting to, "quick deodorization", which had not been considered in conventional deodorizing glass products, was realized.

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 referred to as the specific surface area [m 2 /g], and the larger this value, the finer the particles. Assuming that the particle shape is spherical, if there are n particles of radius r, the total surface area at this time is n4πr ² , and the mass is (n4πr ³ /3)ρ if ρ is the density of the particles, so specific surface area = n4πr ² /(n4πr ³ /3)ρ=3/ρr. Assuming that the radius of the deodorizing glass particles 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) do. That is, when the particle size (diameter) of the deodorizing glass is made fine to 1 µm, the specific surface area becomes 10 times larger. Accordingly, it is naturally assumed that the deodorizing ability increases. From the above, if the particle size can be made small, the addition amount of CuO can be reduced limitlessly. In addition, as the above-mentioned general pulverization technology, fine pulverization down to 0.1 µm is currently limited, but by using a build-up (gas phase method/liquid phase method), it is possible to achieve fine pulverization of 0.1 µm or less.

The deodorizing glass agent of 0.1 micrometer or less can be produced by the sol-gel method, PVD (Physical Vapor Deposition) process, CVD (Chemical Vapor Deposition), and flame pyrolysis process, specifically,. In the sol-gel method of the liquid phase method, glass is produced|generated by adjusting a reaction solution using the alkoxy compound of Si, an alcohol solution, aqueous ammonia, etc. Then, through the process of isolating glass by centrifugation etc., and the process of drying the isolate|separated glass, glass can be obtained. In the case of the sol-gel method, the water resistance is insufficient, and the sulfurization reaction may be higher than the catalytic deodorization action. On the other hand, improvement is possible by making the drying temperature near the glass transition point. In the PVD process of the vapor phase method, glass is produced|generated when glass-making feedstock evaporates in a plasma phase and these are cooled. Regarding CVD and flame pyrolysis treatment, it is the difference between whether the treatment of the raw material is chemical separation or thermal decomposition, respectively. Like PVD, it is formed in a glassy state when cooled. In addition, although it is not a build-up, as a special particle production method, the heated glass powder is immersed in a cooling liquid, and particle|grain formation is possible by irradiating a radio wave to this liquid at that time.

In this invention containing CuO as a glass component, the copper ion which is a transition metal ion is introduce|transduced in the matrix of glass. It is known that copper ions are strongly influenced by the crystal field from surrounding anions when they are introduced into the matrix of glass. A copper ion takes a plurality of ionic states depending on the surrounding environment. Usually, a copper ion exists as Cu ⁺ or ^{Cu2 +} 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 mesh-modifying ions in the structural skeleton of the glass, ^and when many oxygen ions are coordinated thereto, blue is displayed. Cu ⁺ itself is colorless, but when it coexists with Cu ^{2 +} , ion transformation occurs and absorption is enhanced. Moreover, when a copper ^{ion concentration becomes high, about all Cu2+ ,} as a result of becoming impossible to satisfy|fill the coordination of an oxygen ion, the number of unsaturated copper ions of a low coordination number increases. Moreover, the unsaturated ion also increases with a temperature rise. Accordingly, the glass changes from blue to green. Cu ²⁺ shows an absorption band from the visible to the near ^- infrared region (near 800 nm). Generally, as a valence determining factor of a transition metal ion, a melting temperature, oxygen partial pressure in a molten atmosphere, the addition amount of a transition metal ion, and a host glass composition are mentioned. However, there are few reports about the valence control of copper ions by glass composition.

It is known that the water resistance of glass improves by adding alumina in oxide glass. For example, according to a study by Murata, Kurimura, Morinaga et al. (Journal of the Japanese Metallurgical Society, Vol. 61 No. 11 (1997)), the following is confirmed in a specific composition. In general, since silicate-based glass has a higher melting temperature than borate or phosphate-based glass, the redox state of Cu ⁺ -Cu ^{2 +} tends to shift to the reduction side than the other two glass types. By adding alumina to borate or phosphate-based glass, there is an effect that the redox state of Cu ⁺ -Cu ^{2 +} is stabilized on the reducing side. In two-component Na ₂ O-SiO ₂ glass, as the content of Na ₂ O decreases, Cu ⁺ increases relatively, but in three-component alkali-alkaline earth-silicate glass, as the ionic radius of alkaline earth decreases, , there is a report that the amount of Cu ⁺ increases. Moreover, there is also a report that, among transition metals, copper ions are special in the method of influence of valence balance by host glass. However, the effect|action exhibited by each structural component made from glass does not necessarily become a linear change according to a compounding ratio. It is thought that various factors such as bonding between atoms in the amorphous glassy substance and change of bonding nuclei are at work.

(Al ₂ O ₃ )

Al ₂ O ₃ is a component that improves the chemical durability of glass and affects crystal structure stability. In addition, Al ₂ O ₃ acts to suppress the phase separation of the glass to increase the homogeneity of the glass. Since there is a possibility of giving an influence on the redox state of the copper ion in glass by raising a viscosity and addition, the content is 6 mol% or less, It is preferable to set it as 5.5 mol% or less preferably.

Moreover, when CuO addition amount exceeds 23 mol%, copper ion may reduce|restore and metallic copper may precipitate at the time of rapid cooling after glass melting and shaping|molding. Since metallic copper also exhibits a deodorizing effect, although the precipitation does not become a problem from a viewpoint of deodorization, when it precipitates as metallic copper, poisoning will advance. At this time, by making a part _of glass structure comprised by SiO2 into ^{Al3 +} , precipitation of metallic copper can be suppressed.

(Other trace ingredients)

In addition to the above components, as minor 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 O ₃ , La ₂ O ₃ , Y ₂ O ₃ , WO ₃ , MoO ₃ , CoO, or Fe ₂ O ₃ , and the like may also be included. Moreover, you may add F, Cl, _SO3 , _Sb2O3 , SnO2 _, or Ce etc. as _a clarifier.

(Fe ₂ O ₃ )

Since Fe ₂ O ₃ is a component that affects the redox state of copper ions in glass (strengthens Cu ⁺ > Cu ^{2 +} ), the content thereof is 0.5 mol% or less, preferably 0.3 mol% or less. it is preferable

(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 their valence like CuO. When mixed with CuO, _the oxidation-reduction state of the copper ion in glass inclines to acidity by these strong oxidizing components (oxidizing power _Cr2O3 >MnO2>CeO2 ^{) (Cu+} _< ^Cu2 ₊ ⁾ . Although the deodorizing effect is stably obtained in the composition range and manufacturing method of the present invention, when the deodorizing effect is not obtained because the oxidation-reduction state is largely unexpected, (for example, the melting furnace becomes difficult to control the redox state due to erosion. The valence balance _of copper ions can also be controlled by addition _{of Cr2O3} , _MnO2 , CeO2.

In consideration of the above, in this embodiment, the composition range from which a deodorizing effect is acquired stably was specified. That is, after considering the melting temperature range, the redox state, and the composition range, the composition range was specified. When the glass material of the said composition range is manufactured by the melt quenching method, the deodorizing glass material is obtained stably. In particular, it is stably obtained by melting in a tank, melting in an electric furnace, and melting in a small-scale crucible. In the case of soda-lime glass, in the case of tank melting and electric furnace melting, it is known that the copper ion valence balance (Cu ²⁺ /total) is about 15% for the former and about 50% for the latter. Naturally, the valence balance also changes in the composition of this embodiment. Since the deodorizing mechanism is a catalytic action, these chemical states may affect the deodorizing effect, but within the composition range, the difference in the effect is not particularly problematic.

In addition, it is necessary to consider that the oxidation-reduction state differs with melting temperature and melting time. Melting temperature is 1200-1400 degreeC, What is necessary is just to control to 1280-1380 degreeC preferably. The melting time is preferably 6 to 8 hours. As for the glass obtained here, the blue or greenish ^{-blue color by Cu2+ is} confirmed. As mentioned above, in the composition range of this invention, if only a melting temperature and time are taken into consideration, the valence balance of copper ions is not necessarily important. In addition, the valence balance is intentionally changed by heat treatment of the obtained glass material (a thin plate is prepared ^and the color of Cu ²⁺ is confirmed, blue glass, Cu ⁺ >> Cu ²⁺ , the valence balance is changed, ^and the color tone is almost confirmed. Although the deodorizing effect was confirmed (brown (red) glass) in which precipitation of the colloidal metal copper of Cu ⁰ was confirmed, the deodorizing effect was sufficient in all of them. Thus, the deodorizing effect is acquired by setting it as the glass material of the said composition range, and even if it controls the valence balance of copper ion by heat treatment etc. after shaping|molding, the deodorizing effect is maintained.

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

Example

How to make deodorant glass:

After the raw material was prepared, it was melted at a melting temperature of 1350° C. for 8 hours and flowed to obtain a glass having the glass composition shown in Table 1. After melting, natural cooling was performed, but water cooling may also be used. The obtained glass was dry-pulverized using a ball mill, and D ₅₀ (corresponding to 50% of the integrated value when the particle size was cumulatively distributed) = 4.5 µm or less, D ₉₈ (the cumulative value when the particle size was cumulatively distributed) by a particle size meter: 98 %) = 40 µm or less. In addition, particles having a particle diameter (diameter) of 100 μm or more were removed by sieving.

(Example A: Deodorant effect confirmation test for sulfur-based malodor)

Deodorization test method:

A deodorizing glass product (Example 1) having the glass composition of Table 1 and an odor were sealed in a Tedra bag, and the odor concentration in the bag according to the elapsed time was measured with a gas detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

Measurement results and considerations:

As shown in Fig. 1, it was confirmed that hydrogen sulfide, ethyl mercaptan, butyl mercaptan, and 2-mercaptoethanol had a deodorizing effect on any sulfur-based malodor. In addition, as shown in FIGS. 2, 3, 4, 6, 7, and 8, it was confirmed that methyl mercaptan also had a deodorizing effect.

supplement:

The gas detection tube is a method suitable for comparison within the same test, but its quantitative properties are low. In addition, since it is affected by the environment (temperature, humidity), it is not possible to compare it with other tests in quantitative terms. In other words, it is necessary to limit the comparison of results within the same test.

(Example B: Deodorization mechanism elucidation test made of deodorizing glass)

Deodorization test method 1 (nitrogen atmosphere):

The deodorant glass agent (Example 1) and MM (methyl mercaptan) having the glass composition of Table 1 were sealed in a Tedra bag, and immediately after injection of odor, after 2 hours, after 24 hours, MM and DMDS (dimethyl disulfide) Concentrations were determined by gas chromatograph (GC).

The test conditions were as follows.

Tedra Bag Capacity: 5 L

Initial gas (MM) concentration: 100 ppm

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

The above test was commissioned by Kankyo Chemical Kenkyusho Co., Ltd.

Deodorization test method 2 (artificial air atmosphere):

The same test as above was performed in artificial air atmosphere (oxygen concentration 20%, nitrogen concentration 80%).

In the same manner as in the deodorization test method 1, it was entrusted to Kankyo Chemicals Kenkyusho Corporation.

Measurement results and considerations:

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 Fig. 2 and Fig. 3 , even in the blank, DMDS was present from the time of 0 hours, but when it was confirmed, contaminants and DMDS were contained in the used gas.

Although natural oxidation occurs slightly in MM→DMDS, the deodorizing glass material clearly promotes the generation of DMDS for blanks. In this reaction, MM dimerizes to become DMDS.

In addition, although there was no sulfur component or the holding time of GC was maintained up to 90 minutes, the presence of anything other than MM and DMDS was confirmed among them, but a peak was not recognized in particular.

If the deodorizing mechanism made of deodorizing glass is a sulfurization reaction like the soluble glass agent of a prior art, coupling|bonding of a sulfur component and a copper component will occur. However, as shown in the GC results, conversion from MM to a separate sulfur component DMDS was confirmed, not binding to copper. It is considered that the conversion amount is also almost equivalent (taking into account the reduction in MM of the blank itself, etc.).

Moreover, as shown in FIG. 3, when oxygen was present, the deodorizing effect became high clearly. It is thought to be a catalyst that promotes the reaction of MM→DMDS through oxygen. CuO, which is known to exhibit a deodorizing mechanism by catalytic action, also promotes the reaction of MM→DMDS through oxygen. It is said that the oxygen adsorbed on the surface passes through it. There is a possibility that the deodorizing glass also exhibits the same catalytic action. Although the deodorizing effect is confirmed even in a nitrogen atmosphere, there is a possibility that the oxygen adsorbed on the glass surface before encapsulation had an effect.

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 deodorizing glass)

Deodorization test method:

Each of the deodorant glass (Example 1), CuO reagent and MM having the glass composition of Table 1 were sealed in a Tedra bag, and the concentration of MM in the bag according to the elapsed time was measured with a gas detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Initial gas (MM) concentration: 55 ppm (8 repetitions at 55 ppm)

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

CuO: Wako reagent, particle size (base value 5 μm), specific surface area 0.38 m 2 /g.

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

Measurement results and considerations:

As shown in FIG. 4, it was confirmed that the deodorizing glass and CuO also converge to about 10 ppm. This is an error of the gas detection tube as DMDS is generated by catalysis (when there is a sulfur component other than MM, it becomes an error factor because it cannot be identified). Separately, MM at the time of procedure was confirmed by GC, but it was confirmed that it was below the detection limit (results omitted). In view of simply the CuO content, the deodorizing glass agent exhibited a high deodorizing effect despite being in about 1/10 of the CuO reagent.

At the time of the 1st repetition, the deodorization speed of CuO exceeded it, but when it became the 8th repetition, the relationship between both reversed and it was confirmed that the deodorization speed of the deodorizing glass product was winning. Specifically, although the deodorizing glass agent maintains the deodorizing speed also in the 8th repetition, it turns out that the deodorizing effect of CuO exists in a fall tendency. It is known that CuO poisons (catalyst deterioration) when deodorizing a sulfur type odor, and it is thought by this influence. In the present Example, it was confirmed that it was in a stable catalyst state by vitrification.

(Example D: Comparison of soluble glass agent and deodorizing glass agent = Comparison of deodorizing glass agent by sulfurization reaction and deodorizing glass agent by catalytic reaction)

How to make soluble glass:

soluble glass 1

Typical soluble glass product (ion pure) commercially available

soluble glass 2

94.26 g of magnesium phosphate, 157.76 g of 89% by weight phosphoric acid, 157.76 g by weight, and 4.0 g of silver oxide are mixed, held at 300°C for 3 hours, and then the dried product is melted at 1300°C for 1 hour to have the glass composition shown in Table 2 below. was prepared, and this was pulverized to obtain 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% by weight phosphoric acid were mixed and held at 300° C. for 3 hours, and then the dried product was melted at 1300° C. for 1 hour to obtain the following Glasses having the glass composition shown in Table 2 were prepared, and this was pulverized to obtain a sample.

soluble glass 4

12.05 g of boric anhydride, 5.62 g of sodium nitrate, 5.26 g of ultrafine silica (product name: Snowtex S), 0.2 g of alumina powder, 21.4 g of copper chloride, and 60 ml of pure water were stirred with a high-speed stirrer to prepare a sol, and then this 3 ml of 10 N aqueous ammonia was added to gel to form a gel, dried at 120°C for 180 minutes in a dryer, and then in a kiln, room temperature→525°C for 30 minutes, 525°C for 10 minutes, 525→950°C for 30 minutes, 950 A glass product having the glass composition shown in Table 2 below was prepared by calcination at a temperature for 30 minutes, which was then pulverized to obtain a sample.

Deodorization test method:

Deodorizing glass made of the glass composition of Table 1 (Example 1), soluble glass made of the glass composition of Table 2, and hydrogen sulfide were sealed in a Tedra bag, and the hydrogen sulfide concentration in the bag according to the elapsed time was measured with a gas detection tube. .

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Initial gas (hydrogen sulfide) concentration: 55 ppm

Temperature: room temperature (20-25°C)

Humidity: about 80%

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

Measurement results and considerations:

As shown in FIG. 5, since the soluble glass agent is deodorizing by sulfurization reaction, it was confirmed that the reaction speed is quick. For this reason, the soluble glass agent was measured even after 10 minutes. The soluble glass 1 and 3 converged in the 1st repetition. It was confirmed that the deodorization limit was almost reached. Moreover, aggregation was confirmed, perhaps because these glass agents have low water resistance and are easy to absorb moisture. As a reference value, Ag ₂ O and CuO conversion values in the sample amount are shown. However, this is in the total amount of glass, and the one which is actually precipitating on the surface shows a deodorizing effect. The soluble glass agent exhibits a sulfidation reaction on the surface (actually, discoloration (yellow to brown) supporting the reaction is confirmed), and beyond that, it is considered that Ag and Cu inside the glass do not contribute to the reaction. Although the soluble glass 3 showed a slight deodorization effect also in the 2nd time of repetition, since it was aggregating, gas may penetrated inside slowly and deodorized. Since the deodorizing glass agent differed from the soluble glass agent in a deodorizing mechanism, although there was less CuO molar amount than the soluble glass 4, durability was high and it was confirmed that the deodorization amount increased.

supplement:

Since it was adjusted under high-humidity conditions, the deodorizing speed improved (compared to another Example) of the deodorizing glass agent promoted by presence of water|moisture content (in all other examples, 50% or less of humidity).

(Example E: relationship between CuO content and deodorizing effect)

How to make deodorant glass:

After the raw material was prepared, it was melted at a melting temperature of 1350°C for 8 hours and flowed to obtain a glass having a glass composition shown in Table 3 below. Although formation after melting was performed by natural cooling, it can also be set as water cooling.

The glass composition was confirmed by semi-quantitative measurement using a fluorescence X-ray analyzer. The obtained glass was dry-pulverized using a ball mill, and it controlled so that it might become D ₅₀ =4.5 micrometers or less, and D ₉₈ =40 micrometers or less by a particle size meter. In addition, particles having a particle diameter (diameter) of 100 μm or more were removed by sieving.

Deodorization test method:

Glass (CuO-containing and non-deodorizing glass) and MM having the glass composition of Table 3 were sealed in a Tedra bag, and the concentration of MM in the bag according to the elapsed time was measured with a gas detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Initial gas (MM) concentration: 55 ppm

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

Measurement results and considerations:

As shown in FIG. 6, it was confirmed that the deodorizing effect converges to about 10 ppm in all of Experimental examples 1-6 from which content of CuO differs. This is an error of the gas detection tube as DMDS is generated by catalysis (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 rises (specifically, the deodorization speed rises) according to CuO content at the time of a copper particle diameter and same weight.

This is because the CuO content of the glass surface in contact with the odor also increases with the CuO content.

However, even in Experimental Example 1 with the smallest CuO content, MM at a high concentration of 55 ppm is deodorized, and the deodorizing effect is sufficient.

Experimental Example 1 is inferior to Experimental Examples 2 to 6 in deodorization speed when compared at the time point of 24 hours, but the speed can be easily supplemented by decreasing the particle size and increasing the surface area.

(Example F: Sulfidation and Catalysis according to Water Resistance)

As the glass composition changes, the water resistance changes. At this time, since there is a possibility that a deodorization mechanism may change when it approaches a soluble glass-made, Ion Pure (comparative examples 2 and 3) which is a typical soluble glass-made and the dissolved amount were compared. Comparative Examples 2 and 3 are "Ion Pure (commercial products)" which are representative soluble glass products.

How to make deodorant glass:

After the raw material was prepared, it was melted at a melting temperature of 1350° C. for 8 hours and flowed to obtain a glass having a glass composition shown in Table 4 below. Although formation after melting was performed by natural cooling, it can also be set as water cooling.

The glass composition was confirmed by semi-quantitative measurement using a fluorescence X-ray analyzer. The obtained glass was dry-pulverized using a ball mill, and it controlled so that it might become D ₅₀ =4.5 micrometers or less, and D ₉₈ =40 micrometers or less by a particle size meter. In addition, particles having a particle diameter (diameter) of 100 μm or more were removed by sieving. Experimental Examples 7-10 were adjusted so that CuO content (mol%) might become equal.

How to check the amount of glass melt:

0.1 g of the sample was immersed in 100 mL of distilled water and maintained at room temperature (20-25° C.) for 24 hours, and the amount of decrease was confirmed.

Judgment method:

Tedra bag 1 L, MM concentration 55 ppm, that reached the deodorization limit until after 8 repetitions ×, that the deodorization limit was not reached, but a decrease in the deodorization speed was confirmed △, and the persistence was confirmed even after 8 repetitions thing was evaluated as ○.

The specific surface area and particle size of the glass material during the deodorization test are shown in Table 4, and the sample weight is 0.1 g.

Judgment Results and Considerations:

Although the catalytic action of Experimental Examples 9 and 10 was also confirmed, since water resistance is inadequate, it is thought that the sulfurization reaction in ion elution similar to a soluble glass agent acted large.

(Example G: performance comparison with inorganic deodorizing glass with high durability (commercial product))

Deodorization test method 1 (persistence evaluation):

A deodorizing glass product (Example 1) and MM having the glass composition of Table 1 were sealed in a Tedra bag, and the concentration of MM in the bag according to the elapsed time was measured with a gas detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Initial gas (MM) concentration: as shown in Table 6

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

As a comparative evaluation object, the same deodorizing test as above was performed using the inorganic type deodorizing glass agent shown in following Table 5. In addition, all of these inorganic type deodorizing glass agents are marketed as inorganic type deodorizing glass products with high durability.

In addition, as a blank, the same deodorization test as above was performed without a deodorizing glass agent.

Deodorization test method 2 (moisture presence condition):

Deodorizing glass products (Example 1) having the glass composition of Table 1, inorganic deodorizing glass products 1 and 2 of Table 5, CuO reagents, MM, and distilled water are respectively enclosed in a Tedra bag, and the concentration of MM in the bag according to the elapsed time is gas It was measured with a detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Initial gas (MM) concentration: 55 ppm

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

Distilled water addition amount: 500 μl (wet the entire surface of the sample)

CuO: Wako reagent, particle size (base value 5 μm), specific surface area 0.38 m 2 /g.

In addition, as a blank, the same deodorization test as above was performed without a deodorizing glass agent.

Measurement results and considerations:

As shown in Table 6 above, when repeated 10 times while changing the initial gas concentration, the same tendency was confirmed up to the 10th repetition as shown in FIG. 7 . That is, although the inorganic type deodorizing glass 1 has a high instantaneous deodorizing effect, since there exists a deodorization limit (adsorption limit), it converges. The inorganic deodorizing glass 2 and Example 1 can be deodorized at a high concentration, and when the same weight is the same, the deodorizing speed of the inorganic deodorizing glass 2 exceeds the deodorizing speed. Although the inorganic deodorizing glass 1 converges, if the odor is replaced (reset) and used, the deodorizing effect is reproducible. In any case, despite the high concentration of the odor, the deodorizing effect is continued even at the 10th time point of repetition.

Moreover, as shown in FIG. 8, the change in the deodorization tendency was confirmed by the addition of water|moisture content.

In the inorganic type deodorizing glass 1, it was confirmed that the instantaneous deodorizing effect fell. Since this is a high physical adsorption agent, it is thought that it originates in the instantaneous effect weakening when the surface gets wet. It was confirmed that the inorganic type deodorizing glass agent 2 was not able to exhibit a sufficient deodorizing effect in a water|moisture content presence environment. In this Example, it was confirmed that the deodorization speed improved significantly by adding water. In the present Example, there is a possibility that the deodorization mechanism by the sulfurization reaction was added by promoting the catalytic effect by the presence of moisture or by ion elution. In this Example, since the amount of copper ion elution is small, the former possibility is high. In addition, under the condition of adding water, the deodorization speed was faster than that of CuO despite the first repetition (refer to the comparison of FIG. 4 ).

In addition, in the blank, although there was a slight decrease, no significant decrease in concentration was observed. This result indicates that MM was not dissolved in water, but that the deodorizing effect of each formulation could be evaluated.

(Example H: Deodorizing effect confirmation test for lower fatty acids)

Deodorization test method:

A deodorizing glass product (Example 1) having the glass composition of Table 1 and an odor were sealed in a Tedra bag, and the odor concentration in the bag according to the elapsed time was measured with a gas detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

Measurement results and considerations:

As shown in FIG. 9 , it was confirmed that acetic acid, propionic acid, normal butyric acid, normal valeric acid, isovaleric acid and all lower fatty acids had a deodorizing effect.

(Example I: Deodorization effect confirmation test for trans-2-nonenal)

Deodorization test method:

Each of the deodorant glass agent (Example 1) having the glass composition of Table 1, CuO reagent, and trans-2-nonenal were sealed in a Tedra bag, and the odor concentration in the bag according to the elapsed time was measured by a high performance liquid chromatograph.

In the high performance liquid chromatography method, the gas in the bag is collected in a DNPH cartridge, the DNPH derivative is eluted from the cartridge through acetonitrile, and the resulting eluate is measured by a high performance liquid chromatography to calculate the gas concentration in the bag.

The test conditions were as follows.

Tedra Bag Capacity: 4 L

Temperature: room temperature (20-25°C)

Deodorizing glass weight: 0.1 g

Deodorizing glass particle size: D ₅₀ =4.21 μm

Deodorizing glass specific surface area: 1.54 m2/g

CuO: Wako reagent, particle size (reference value 5 μm), specific surface area 0.38 m 2 /g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

The said test was requested to the Nippon Shokuhin Bunseki Center, a general foundation.

Measurement results and considerations:

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

(Example J: Examination of the particle size and deodorization speed of deodorizing glass)

How to make deodorant glass:

After the raw material was prepared, it was melted at a melting temperature of 1350°C for 8 hours and flowed to obtain a glass having the glass composition shown in Table 8. After melting, natural cooling was performed, but water cooling may also be used. The obtained glass was grind|pulverized and it adjusted to the particle size of Table 8.

In any of the glasses of Experimental Examples 11 to 18 shown in Table 8, the absolute amount of deodorization is sufficient. However, the required deodorization speed differs depending on the use of the deodorizing glass agent.

For example, in the living environment, it is said that several ppb of methyl mercaptan is generated in the bathroom. Assuming 10 ppb, let's say you want to deodorize everything in 1 minute.

As shown in FIG. 6, in Experimental Examples 2 to 6, 55 ppm deodorization is possible in 24 h. (Ignoring dimethyldisulfide of the secondary product, methylmercaptan is considered to be deodorizing about 55 ppm) By calculation (55 ppm/24 h/60 m), the amount of deodorization per minute is 38 ppb. In addition, since Experimental Example 1 can deodorize 55 ppm in 48 h, in calculation (55 ppm/48 h/60 m), the deodorization amount per minute is 19 ppb.

As can be seen from FIG. 6 , since it is expected that the deodorization speed is actually faster (it is shown gently on the graph at the timing of the measurement), it is expected that the amount of deodorization per minute is higher than the above-mentioned calculated value.

Since the evaluation result of FIG. 6 is an effect with a small capacity|capacitance and glass single-piece|unit to the last, about the toilet space, the speed with margin is preferable.

If it is possible to deodorize 55 ppm at 24 h, it is about 4 times more than 10 ppb of the environmental concentration to be deodorized, and if 55 ppm deodorization is possible at 48 h, it is about 2 times the speed.

In Table 8, what was about 4 times (tolerable range to -5%) was "A judgment", and what was about 2 times (tolerable range to -5%) was made into "B judgment".

Measurement results and considerations:

Deodorizing glass 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 the range of , it was confirmed that faster deodorization was performed.

In addition, about the particle _diameter (D50) y (micrometer) of the deodorizing glass, 10.5 micrometer was made into the upper limit in order to set it as the deodorizing glass of a "powder".

(Example K: imitation properties (母組成) and deodorant effect)

How to make deodorant glass:

After the raw material was prepared, it was melted at a melting temperature of 1350°C for 8 hours and flowed to obtain a glass having a glass composition shown in Table 9 below. Although formation after melting was performed by natural cooling, it can also be set as water cooling.

The glass composition was confirmed by semi-quantitative measurement using a fluorescence X-ray analyzer. The obtained glass was dry-pulverized using a ball mill, and the particle size of Table 9 was adjusted. In addition, particles having a particle diameter (diameter) of 100 μm or more were removed by sieving.

Deodorization test method:

Glass Experimental Examples 19 to 29 and MM having the glass composition of Table 9 were sealed in a Tedra bag, and the concentration of MM in the bag according to the elapsed time was measured with a gas detection tube.

The test conditions were as follows.

Tedra Bag Capacity: 1 L

Initial gas (MM) concentration: 70 ppm

Temperature: room temperature (18-22°C)

Deodorizing glass weight: 0.1 g

In addition, as a blank, the operation similar to the above was performed without a deodorizing glass product.

Measurement results and considerations:

As shown in FIG. 13, when the content of CuO is equal, the deodorizing effect is fully expressed regardless of the imitation composition. Moreover, it turns out that the difference in CuO content slightly rather than a imitation|imitation property is affecting the deodorization speed. In Experimental Examples 19-20, although the deodorization speed|rate did not depend on CuO content, it is thought that the influence of the particle size arose (however, the measurement error is also considered enough because of a gas detection tube).

How to check the amount of dissolved glass, How to check the amount of elution of free components:

0.1 g of the sample was immersed in 100 mL of distilled water and maintained at room temperature (18 to 22° C.) for 24 hours, and the amount of decrease was confirmed. This result was made into the amount of glass melt|dissolution.

After holding for 24 hours, only distilled water was collected by suction filtration and diluted in 250 mL. With respect to this adjustment solution, the concentration of the eluted component was measured using an ICP emission spectrometer (Optima2000DV). The measurement was performed based on the method prescribed|regulated to JISK0116 (2003), and the lower limit of detection was set to 0.01 ppm. In addition, the high-concentration component was further diluted as needed. The measured value was corrected for the concentration in 100 ml of distilled water, and this result was taken as the elution amount.

How to check particle size:

It was measured using a particle size meter (Microtrac II). For those in which the specific surface area was not confirmed as an actual measured value, the specific surface area (CS) calculated from the particle size measurement results (specific surface area when all spherical shapes are assumed) is shown.

Full results and considerations:

Within the composition range of Table 9, when CuO content was equal, it became clear that the influence on the deodorizing effect provided by a imitation composition does not have a big difference. However, a difference was confirmed in the dissolution amount and the elution amount. When used as a deodorant, it is best to have less dissolution and dissolution from the viewpoint of aggregation, influence on surrounding materials, and safety. Empirically, it is preferable that the amount of glass melt in this test be 10% or less.

(Embodiment 2: CuO containing alkali-alkaline earth-silicate glass)

The deodorizing glass agent of this embodiment contains 50-70 mol% _of SiO2, 10-33 mol% of R2O (R ₌ Li, Na, K), R'O(R'=Mg, Ca, Sr, Ba) ) 0-15 mol%, Al ₂ O ₃ 0-6 mol%, CuO 0.01-23 mol% "alkali (R ₂ O) - alkaline earth (R'O) - silicate glass (SiO ₂ ) ', and can be manufactured by a melt quenching method, similarly to ordinary glass products. The shape of the glass is made into a powder obtained by pulverizing a preform after obtaining a preform by a melt quenching method. The pulverization as used herein means pulverization by a generally known pulverizer (eg, a ball mill, a bead mill, a jet mill, a CF mill, etc.), and may be dry or wet.

Hereinafter, each glass composition is demonstrated in detail.

(SiO ₂ )

SiO2 becomes a main component which forms the structural frame|skeleton _of glass. The content is 50 to 70 mol%, preferably 55 to 70 mol%. When it is less than 50 mol%, the chemical durability of glass becomes inadequate, and it becomes easy to lose transparency of glass, and is unpreferable. In addition, when it is less than 50 mol%, the water resistance of the glass becomes insufficient, and as a result, copper ions are more likely to elute in the presence of moisture (including moisture in the air). It is not preferable because the deodorizing effect by the sulfurization reaction becomes strong. When it exceeds 70 mol%, when melting|fusing point rises, since meltability of glass becomes difficult and a viscosity raise also arises, it is unpreferable.

(R ₂ O(R=Li, Na, K))

R ₂ O (R = Li, Na, K) cleaves the bond between Si and O in the structural skeleton of the glass to form non-crosslinked oxygen, and as a result, reduces the viscosity of the glass, resulting in improved moldability and solubility. It is a component that improves, and is the same flux as B ₂ O ₃ . The content is 10 to 33 mol% in total, preferably 12 to 24 mol%, considering the content ratio of one or more R ₂ O (R=Li, Na, K) with multiple components. When it exceeds 33 mol%, the chemical durability of glass becomes inadequate. Specifically, the glass agent reacts with moisture in the atmosphere to cause a whitening phenomenon called bloom. It is undesirable because blooming reduces the contact area with the malodorous gas. In addition, the alumina material of 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 glass. The content is 0 to 15 mol% in total, preferably 2 to 10 mol% of one or more kinds of R'O (R'=Mg, Ca, Sr, Ba). When it exceeds 15 mol%, since the viscosity at the time of melting increases and glass loses transparency easily, it is unpreferable. In addition, in the deodorizing glass agent of this invention, it is not an essential component, and the content may be 0 mol%.

(CuO)

Regarding CuO, although it is basically the same as that of Embodiment 1 described above, in this embodiment, the addition amount (x) (mol%) of CuO powder and the particle size (D ₅₀ , y µm) of the deodorizing glass are within the range of the following formula By limiting, "quick deodorization", which had not been considered with conventional deodorizing glass products, was 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 glass and affects crystal structure stability. In addition, Al ₂ O ₃ acts to suppress the powder phase of the glass to increase the homogeneity of the glass. The content is 6 mol% or less, preferably 5.5 mol% or less, since there is a possibility that the oxidation-reduction state of the copper ions in the glass may be affected by raising the viscosity or adding it.

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

In consideration of the above, in this embodiment, the composition range from which a deodorizing effect is acquired stably was specified. That is, after considering the melting temperature range, the redox state, and the composition range, the composition range was specified. When the glass material of the said composition range is manufactured by the melt quenching method, the deodorizing glass material is obtained stably. In particular, it is stably obtained by melting in a tank, melting in an electric furnace, and melting in a small-scale crucible. Generally, in the case of soda-lime glass, in tank melting and electric furnace melting, it is known that the valence balance (Cu ²⁺ /total) of copper ions is about 15% for the former and about 50% for the latter. Naturally, the valence balance also changes in the composition of this embodiment. Since the deodorizing mechanism is a catalytic action, there is a possibility that their chemical state may affect the deodorizing effect, but as long as the composition is within the above composition range, the difference in the effect is not particularly problematic.

In addition, it is necessary to consider that the oxidation-reduction state differs depending on the melting temperature and the melting time. Melting temperature is 1200-1400 degreeC, What is necessary is just to control to 1280-1380 degreeC preferably. The melting time is preferably 6 to 8 hours. As for the glass obtained here, the blue or greenish ^{-blue color by Cu2+ is} confirmed. As described above, in the composition range of the present invention, the valence balance of copper ions is not necessarily important if only the melting temperature and time are taken care of. In addition, the valence balance is intentionally changed by heat treatment of the obtained glass product (a thin plate is prepared and the color of Cu ^{2 +} is confirmed, blue glass, Cu ⁺ >> Cu ^{2 +} , the valence balance is changed and the color tone is almost confirmed. The deodorizing effect of the glass which does not become unusable and the brown (red) glass in which the precipitation of the colloidal metal copper of Cu ⁰ is confirmed was confirmed, and a sufficient deodorizing effect was obtained in any of them. Thus, the deodorizing effect is acquired by setting it as the glass material of the said composition range, and even if it controls the valence balance of copper ion by heat treatment etc. after shaping|molding, the deodorizing effect is maintained.

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

(Example L: Examination of the particle size and deodorization speed of deodorizing glass)

It carried out similarly to Example J of Embodiment 1, and examined a particle diameter and a deodorization speed.

In any of the glasses of Experimental Examples 33 to 45 shown in Table 10, the absolute amount of deodorization is sufficient.

Measurement results and considerations:

Deodorizing glass 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 the range of , it was confirmed that faster deodorization was performed.

In addition, about the particle _diameter (D50) y (micrometer) of the deodorizing glass, 10.5 micrometer was made into the upper limit in order to set it as the deodorizing glass of a "powder".

Claims (9)

A deodorizing glass made of CuO-containing glass,
The said glass is _53-62 mol% of SiO2, 10-17 mol% _{of B2O3} , 13-19 mol% of Na2O, _3-6 mol% of CaO, _{0-4.5 of} Al2O3 mol%, containing 4 to 13 mol% of CuO,
When the content of CuO powder added as a raw material is x mol% and the particle size of the deodorizing glass is y µm, the following formula is satisfied:
When 0.01≤x≤2.03, y≤5.08x+0.18
When 2.03≤x≤23, y≤10.5 A deodorizing glass made of CuO-containing glass,
Said glass contains 55-65 mol% _of SiO2, 12-20 mol% _of Na2O, _3-7 mol% of CaO, 0-5 mol% _of Al2O3, and 4-13 mol% of CuO is to do,
When the content of CuO powder added as a raw material is x mol% and the particle size of the deodorizing glass is y µm, the following formula is satisfied:
When 0.01≤x≤2.38, y≤4.27x+0.34
When 2.38≤x≤23, y≤10.5 delete delete delete delete delete delete delete

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