JP2016027999A - Deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant which can exert stable deodorant effect for a long period of time, as compared to conventional art, and does not flocculate in a powdery state, gives a high degree of freedom in a product shape and usage, and also has high convenience.SOLUTION: A deodorant comprises glass comprising SiOof 46-70 mol%, BOand RO(R=Li, Na, K) of 15-50 mol% in total, R'O(R'=Mg, Ca, Sr, Ba) of 0-10 mol%, and CuO of 0.1-23 mol%.SELECTED DRAWING: None

Description

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

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

  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 be perceived as a bad odor even at a low concentration of about ppb.

As a technique related to the deodorization, a soluble glass containing P ₂ O ₅ as a main component contains silver, copper, or iron, and PO ₄ ²⁻ ions, Ag ⁺ ions, Cu 2 ⁺ ions, or Fe 2 ⁺ ions. 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.

JP-A-4-67868 JP 2009-213992 A

  The object of the present invention is to solve the above-mentioned problems, can exhibit a deodorizing effect that is stable for a long time compared to the prior art, and does not agglomerate even as a powder, and relates to the product shape and usage mode It is to provide a deodorant having a high degree of freedom and high convenience.

The deodorant of the present invention made to solve the above problems is 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%, which is characterized in that it consists of glass containing CuO 0.1 to 23 mol%, the glass _is 5 to B 2 _{O 3} 20 _{mol%, R 2 O (R =} Li, Na, K) is preferably a are those containing 10 to 30 mol%.

The glass composition includes 50 to 63 mol% of SiO ₂ , 23 to 44 mol% in total of B ₂ O ₃ and R ₂ O, and _{2 of} R′O (R ′ = Mg, Ca, Sr, Ba). 7 mol%, preferably to those containing CuO 1 to 13 mol%, _further, B 2 _{O 3} 8 to 18 _{mol%, R 2 O (R =} Li, Na, K) and 15 to 26 mole % Is more preferable.

Said glass composition, the SiO ₂ 51 to 55 _mol%, B 2 _{O 3} 12 to 16 mol%, a Na ₂ O 19 to 22 mol%, the CaO 4.5 to 6.5 mol%, a CuO It is most preferable to contain 4-13 mol%.

B ₂ O ₃ 5 to 20 _{mol%, R 2 O (R =} Li, Na, K) by using a glass of the composition containing 10 to 30 mol% of deodorant, compared to the prior art In addition, it is possible to achieve a highly convenient deodorant with a high degree of freedom in terms of product shape and usage. 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 deodorant can be realized.

  Conventionally, there is no “glass agent showing a deodorizing effect by catalytic action”, and various deodorizers using a soluble glass have been developed. As a result, “CuO contained in the glass of the above composition in the above ratio functions as a catalyst, promotes the decomposition reaction (oxidation / reduction reaction) of the sulfur-based malodorous substance, and exhibits the deodorizing effect of the sulfur-based malodorous substance. ”Was found. 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.

  The deodorant of the present invention can exhibit an excellent deodorizing effect particularly with respect to methyl mercaptan. In addition, the function as a catalyst can be more effectively exhibited by ensuring a large contact area with a malodorous substance by making a deodorizer into powder form.

  The deodorizer 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. Specific examples include lower fatty acids, acetic acid known as body odor (sweat, foot odor), isovaleric acid, propionic acid, normal butyric acid, normal valeric acid, and caproic acid, a medium chain fatty acid, as defined by the Malodor Control Law. Also, enanthic acid and trans-2-nonenal, known as an aging odor, can 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 deodorizer of the present invention catalytically decomposes methyl mercaptan to produce dimer 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 deodorant 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 at the same time. 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. Further, not only trans-2-nonenal, but also the possibility of decomposing the precursor palmitoleic acid and exhibiting a deodorizing effect.

  Moreover, since the deodorizer of this invention contains many CuO in glass, the antimicrobial effect by CuO can also be exhibited simultaneously.

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.

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.

  Preferred embodiments of the present invention are shown below.

Deodorant of the present embodiment, the SiO ₂ from 46 to 70 _mol%, B 2 _{O 3} and _R 15 to 50 mole percent ₂ O in total, R'O (R'= Mg, Ca , Sr, Ba) Is composed of “alkali (R ₂ O) -alkaline earth (R′O) -borosilicate glass (B ₂ O ₃ —SiO ₂ )” containing 0 to 10 mol% and 0.1 to 23 mol% of CuO. In the same manner as ordinary glass agents, it can be produced by a melt quenching method. Although the shape of a glass agent is not specifically limited, For example, it can be set as a molded object or powder. In the case of a molded body (for example, a deodorizing container), a molded body is molded using a mold. In the case of a powder, a pre-molded body is obtained by a melt quenching method and then pulverized to obtain a desired shape. A deodorant can be obtained. 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 46 to 70 mol%, preferably 50 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 is 5 to 20 mol%, preferably 8 to 18 mol%, taking into account 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 is one or two or more of R ₂ O (R = Li, Na, K), taking into consideration the content ratio with multiple components, and a total of 10 to 30 mol%, preferably 15 to 26 mol%. 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 23 to 44 mol%, is a region that safely exhibits the deodorizing effect. 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 45 mol%, the water resistance of the glass becomes insufficient, and copper ions are likely to elute in the presence of moisture (including moisture in the atmosphere), resulting in ion elution rather than deodorizing effect due to catalytic action. 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 content of R′O (R ′ = Mg, Ca, Sr, Ba) is a total of 0 to 10 mol%, preferably 2 to 7 mol%. If it exceeds 10 mol%, the viscosity at the time of melting increases and the glass tends to be devitrified, which is not preferable. In addition, it is not an essential component in the deodorizer of the invention, and its 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 is 0.1 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. The content and particle size of CuO vary depending on the required deodorization speed and deodorization capacity, but from the viewpoint of productivity and manufacturing cost, the particle size is D50 (50% integrated value when the particle size is cumulatively distributed). , Generally referred to as the median diameter) = 0.1 μm or more, preferably D50 = 1 μm or more, and more preferably D50 = 4 μm or more. When the particle size is D50 = 0.1 μm or more, the CuO content is 0.1 mol% or more, and when the particle size is D50 = 1 μm or more, the CuO content is 1 mol% or more and the particle size is D50. When the thickness is 4 μm or more, the CuO content is 4 mol% or more.

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 (R = 10 μm) = 3 / Ρ (5 μm), and when R = 0.5 μm, the specific surface area (R = 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. However, in view of control during production, productivity, and production price, in order to obtain a stable deodorizing ability, it is desirable that the CuO content is 0.1 mol% or more and the particle size is 0.1 μm or more.

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⁺ oxidation-reduction state shifts to the reduction side compared to the other two glass systems. Cheap. By adding alumina to borate or phosphate glass, there is an effect that the redox state of Cu ⁺ -Cu ²⁺ is stabilized on the reducing side. In the two-component Na ₂ O—SiO ₂ glass, Cu ⁺ increases relatively as the Na ₂ O content decreases, and in the three-component 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. Since there is a possibility that the oxidation and reduction state of the copper ions in the glass will be increased by increasing the viscosity, the content is preferably 3.5 mol% or less.

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 , 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 0.2 mol% or less, preferably 0.1 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 invention, the composition range in which the deodorizing effect can be 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 invention. 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, the valence balance of copper ions is not necessarily important in the composition range of the present invention. Moreover, the valence balance of the obtained glass agent was changed intentionally (a thin plate was produced, a blue glass in which the coloration of Cu ²⁺ was confirmed, the valence balance was changed to Cu ⁺ >> Cu ²⁺ and almost the color tone Glass, brown (red) glass in which precipitation of colloidal metallic copper of Cu ⁰ was confirmed), and the deodorizing effect was confirmed. Thus, the deodorizing effect can be obtained by using the glass agent in the above composition range, and the deodorizing effect can be obtained even if the valence balance of copper ions is controlled by heat treatment after molding.

  As described above, the shape of the glass agent is not particularly limited, and it can be used as a deodorizing product in powder or granule as it is in a container such as a cartridge, and has a deodorizing property for fibers, paints, sheets, and molded products. It can be applied and used as a deodorant product. The usage form is not limited to powder, but may be a plate shape or a molded body. The deodorant by catalysis may be insufficient in 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 in combination with conventional deodorants.

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 below. After melting, natural cooling was performed, but water cooling can also be used. 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 by a particle size meter such that D50 = 4.5 μm or less and D98 (corresponding to an integrated value of 98% when the particle size was cumulatively distributed) = 50 μm or less. The particles having a particle size (diameter) of 100 μm or more were removed by sieving.

(Example A: Deodorization effect confirmation test for sulfurous malodor)
Deodorization test method:
A deodorizing glass agent having a glass composition shown in Table 1 and malodor were enclosed 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: D50 = 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, and 6, it was confirmed that methyl mercaptan also has a deodorizing effect.

(Example B: Deodorization mechanism elucidation test of deodorant glass agent)
Deodorization test method 1 (nitrogen atmosphere):
A deodorizing glass agent having the glass composition shown in Table 1 and MM (methyl mercaptan) were sealed in a Tedlar bag, and immediately after malodor injection, 2 hours and 24 hours later, MM and DMDS (dimethyl disulfide) concentrations were measured by gas chromatography (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: D50 = 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:
Each odor eliminating glass agent having a glass composition shown in Table 1, CuO reagent and MM were sealed in a Tedlar bag, and the MM concentration in the bag with the elapsed time was measured with a 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: D50 = 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 cannot be identified, which causes an error). 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 having the glass composition shown in Table 1 and Table 2 and hydrogen sulfide were sealed in a Tedlar bag, and the hydrogen sulfide concentration in the bag with the elapsed time was measured with a gas detector tube.
The test conditions were as follows.
Tedlar bag capacity: 1L
Initial gas (hydrogen sulfide) concentration: 55ppm
Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D50 = 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 shows 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. .

(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 D50 = 4.5 μm or less and D98 = 50 μm or less with 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 7 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 2 having the smallest CuO content, MM having a high concentration of 55 ppm is deodorized, and the deodorizing effect is sufficient.
In Experimental Example 2, when compared at 24 hours, the deodorization speed is inferior to that of Experimental Examples 3 to 7, 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 1 and 2), which is a typical soluble glass agent. Comparative Examples 1 and 2 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 D50 = 4.5 μm or less and D98 = 50 μm or less with a particle size meter. The particles having a particle size (diameter) of 100 μm or more were removed by sieving. In Experimental Examples 8 to 10, the CuO content (mol%) was adjusted to be equal.
Method for confirming glass dissolution amount 0.1 g of the sample was immersed in 100 mL of distilled water and kept at room temperature (20 to 25 ° C.) for 24 hours, and then the amount of decrease was confirmed.
Judgment method Tedlar bag 1L, MM concentration 55 ppm, x that has reached the deodorization limit by 8 times repeatedly, deodorization limit has not been reached, but a decrease in deodorization speed was confirmed △,
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 (commercially available))
Deodorization test method 1 (sustainability evaluation):
The deodorizing glass agent having the glass composition shown in Table 1 and MM were sealed in a Tedlar bag, and the MM concentration in the bag with the elapsed 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 5 Temperature: Room temperature (20-25 ° C)
Deodorant glass agent weight: 0.1g
Deodorant glass agent particle size: D50 = 4.21 μm
Deodorant glass agent specific surface area: 1.54 m ² / g
As a comparative evaluation object, a deodorizing test similar to the above was performed using an inorganic deodorant shown in Table 5 below. These inorganic deodorants are commercially available as highly durable inorganic deodorants.
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):
Deodorant glass agent comprising the glass composition of Table 1, inorganic deodorant 1-2 of Table 5, CuO reagent and MM, distilled water are sealed in a Tedlar bag, and the MM concentration in the bag over time is gas Measured with a 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: D50 = 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 deodorant 1 has a high instantaneous deodorizing effect, but converges because it has a deodorizing limit (adsorption limit). The inorganic deodorant 2 and the examples can be deodorized at a high concentration. At the same weight, the inorganic deodorant 2 has a higher deodorizing speed. Although the inorganic deodorant 1 converges, there is reproducibility of the deodorizing effect if the odor 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 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 deodorant 2 cannot exhibit a sufficient deodorizing effect in a moisture-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. Since this example is an agent having high water resistance, 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).
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 having a glass composition shown in Table 1 and malodor were enclosed 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: D50 = 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:
The deodorizing glass agent having the glass composition shown in Table 1, each of the 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: D50 = 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.

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 ( diameter = 2R = 10 μm) = 3 / Ρ (5 μm), and when R = 0.5 μm, the specific surface area ( diameter = 2R = 1 μm) = 3 / Ρ (0.5 μm) It becomes. 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. However, in view of control during production, productivity, and production price, in order to obtain a stable deodorizing ability, it is desirable that the CuO content is 0.1 mol% or more and the particle size is 0.1 μm or more.

The deodorant of the present invention made to solve the above problems is a vitreous deodorant excellent in sustainability, and is composed of 50 to 63 mol% of SiO ₂ , B ₂ O ₃ and R ₂ O (R = Li, Na, K) is made of glass containing 23 to 44 mol% in total, R'O (R '= Mg, Ca, Sr, Ba) 2 to 7 mol% and CuO 1 to 13 mol%. A deodorant used in the air, which decomposes malodorous components in the air by the catalytic action of CuO in the glass .

It said glass _composition, B 2 _{O 3} 8 to 18 _{mol%, R 2 O (R =} Li, Na, K) and 15 to 26 mol%, it preferably contains.

According to a third aspect of the invention, a good glassy deodorant sustainability, the SiO ₂ 51 to 55 _mol%, B 2 _{O 3} 12 to 16 mol%, 19 to 22 molar Na ₂ O %, CaO 4.5 to 6.5 mol%, CuO 4 to 13 mol% glass deodorant used in the air, due to the catalytic action of CuO in the glass, in the air It is characterized by decomposing malodorous components .

Claims (5)

The SiO ₂ 46~70 mol%,
B ₂ O ₃ and _R 2 O 15 to 50 mol% in total (R = Li, Na, K ) and,
R′O (R ′ = Mg, Ca, Sr, Ba) 0-10 mol%,
0.1-23 mol% of CuO
A deodorant characterized by comprising glass. The glass is
B ₂ O ₃ 5 to 20 mol%,
_{R 2 O (R = Li,} Na, K) 10 to 30 mol%
The deodorizer according to claim 1, which is contained. The SiO ₂ 50~63 mol%,
B ₂ O ₃ and 23 to 44 _{mol% R 2 O (R = Li} , Na, K) in total,
2 to 7 mol% of R′O (R ′ = Mg, Ca, Sr, Ba),
1-13 mol% of CuO
A deodorant characterized by comprising glass. The glass is
B ₂ O ₃ 8 to 18 mol%,
_{R 2 O (R = Li,} Na, K) and 15 to 26 mol%,
The deodorizer according to claim 3, which is contained. The SiO ₂ 51~55 mol%,
12 to 16 mol% of B ₂ O ₃
Na ₂ O and 19-22 mol%,
4.5-6.5 mol% CaO,
4-13 mol% of CuO
A deodorant characterized by comprising glass.