JP2017046746A - Deodorant spray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant spray having excellent persistence of deodorant effect and being provided with a function to deodorize not only sulfur-based malodorous substances such as hydrogen sulfide, methyl mercaptan and the like but also malodorous substances such as lower fatty acids, body odor components and the like.SOLUTION: A deodorant spray comprises a liquid concentrate having a glassy deodorant dispersed and a propellant. The glassy deodorant comprises alkali-alkaline earth-borosilicate glass containing a copper component or alkali-alkaline earth-silicate glass containing a copper component, and possesses a function of decomposing malodorous substances by catalytic action of the copper component retained in the glass. In addition, the glassy deodorant is preferably powder having D=25 μm or less, and may contain a surfactant.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a deodorizing spray containing a glassy deodorant.

  Traditionally, deodorant sprays have been used for toilet deodorization, garbage deodorization, pet dung deodorization, entrance and living room deodorization, shoes and shoebox deodorization, bed and carpet deodorization, underwear and clothing It is used in various places such as deodorizing. Recently, deodorant sprays such as human sweat odor, aging odor, and body odor have also become widespread. Many of these are sprays that contain chemicals that exert a deodorizing effect by chemical adsorption reaction such as neutralization with malodorous components, or adsorbents that physically adsorb malodorous components to exert a deodorizing effect. (For example, Patent Documents 1 and 2).

  Each of the adsorbents described in Patent Documents 1 and 2 chemically adsorbs malodorous components using a silver-containing compound. However, since the amount of chemicals to be sprayed is small, there is a problem that the deodorizing limit is reached in a short time after spraying and the deodorizing effect is not maintained. Similarly, those sprayed with an organic drug have a problem that the deodorizing effect is not long-lasting.

  In addition, silver ions have an antibacterial effect and thus prevent odors produced by bacteria, and also have a deodorizing effect on sulfur-based malodorous substances such as hydrogen sulfide and methyl mercaptan, but malodorous substances such as lower fatty acids and body odor components. There is no deodorizing effect on substances, and there is a problem that these odors are not suitable for use in the nursing field where human odors are mainly used, and for deodorizing human sweat odor, body odor and aging odor. Antibacterial deodorization by silver ions is preferably sprayed before prevention of bad odor, but is not effective after bad odor is generated. However, in practice, since it is common to use a deodorant spray after annoying the smell, there is a problem that antibacterial deodorization is not practical.

Japanese Patent Laid-Open No. 8-3007 JP 2005-237784 A

  Therefore, the object of the present invention is to solve the above-mentioned conventional problems, have excellent deodorizing effect, and not only sulfur-based malodorous substances such as hydrogen sulfide and methyl mercaptan, but also malodorous substances such as lower fatty acids and body odor components. Another object is to provide a deodorizing spray having a function of deodorizing.

The deodorant spray of the present invention made to solve the above problems is a deodorant spray containing a stock solution in which a glassy deodorant is dispersed and a propellant as essential components,
The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component,
It has a function of decomposing malodorous components by the catalytic action of the copper component held in the glass.

The deodorant spray of the present invention is a foam-like deodorant spray containing a stock solution in which a glassy deodorant is dispersed, a surfactant and a propellant as essential components,
The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component,
It has a function of decomposing malodorous components by the catalytic action of the copper component held in the glass.

As described in claim 3, the vitreous deodorant is preferably a powder having a D _{96 of} 25 μm or less. Moreover, as described in claim 4, the content of the vitreous deodorant is preferably 0.1 to 15% by mass with respect to the stock solution.

  The deodorizing spray of the present invention contains a vitreous deodorant composed of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component in a stock solution. Therefore, the malodorous component is effectively decomposed by the catalytic action of the copper component held in the glass of the injected glassy deodorant. Similarly, when injected in the form of foam, the malodorous component is decomposed by the catalytic action of the copper component.

  Conventionally, various deodorizers using soluble glass have been developed, whereas “glass agents showing a deodorizing effect by catalytic action” have not been known. As a result of many years of research, the inventors of the present invention, the copper component contained in the glass of the above composition functions as a catalyst, promotes the decomposition reaction of the sulfur-based malodorous substance, the deodorizing effect of the sulfur-based malodorous substance I found a new finding that "I play".

  In the present invention, as described above, since it has a mechanism for promoting the decomposition reaction of the sulfur-based malodorous substance using the copper component contained in the glass as a catalyst, compared to the conventional technology using chemical adsorption and physical adsorption, The deodorizing capacity can be increased, and the deodorizing effect can be exhibited stably over a long period of time. That is, both conventional chemical adsorption and physical adsorption depend on the surface exposure amount of the adsorbent, and the deodorization limit is determined by the exposure amount. However, in the present invention, since the catalytic reaction is used, the exposure amount is small. Even so, a large total deodorizing amount can be obtained. For this reason, if paying attention only to the deodorizing amount, a small amount of the glassy deodorant may be added, but in order to add the deodorizing speed, as described above, 0.1 to 15% by mass with respect to the stock solution. It is preferable to contain.

  The vitreous deodorant used in the present invention can exhibit an excellent deodorizing effect particularly with respect to methyl mercaptan. That is, this glassy deodorant catalytically oxidatively decomposes methyl mercaptan to produce dimeric dimethyl disulfide. At this time, radicals are generated and oxidatively decomposed. Similarly, similar oxidative decomposition is possible for other gases. This point is also referred to in examples described later. However, the odor that can be deodorized is not limited to sulfur-based odor substances. Specific examples include lower fatty acids, acetic acid known as body odor (sweat, foot odor) and aging odor, isovaleric acid, propionic acid, normal butyric acid, normal valeric acid, medium chain The fatty acids caproic acid, enanthic acid and trans-2-nonenal known as aging odor can also be deodorized. In general, those having 2 to 4 carbon atoms are referred to as short chain fatty acids (lower fatty acids), but in this specification, acetic acid having 1 carbon atom and 5 valeric acids are also treated as lower fatty acids.

  The deodorizing spray of the present invention is suitable for deodorizing toilets, garbage, pet feces, doors, rooms, cars, deodorizing shoes and shoe boxes, and deodorizing beds and carpets. Further, since the glassy deodorant is harmless to the human body, it can be applied to deodorization of underwear and clothes. Furthermore, the present invention is applicable to deodorization of human sweat odor, foot odor, halitosis, aging odor, body odor, tobacco odor and the like. Methyl mercaptan is known as a component of bad breath, and the deodorizing spray of the present invention may be sprayed on a mask that comes into contact with the mouth. Sprays containing metal components cannot be used by those who are allergic to metals, but are safe if vitrified as in the present invention. In addition, when it is necessary to completely contain odors or when odors are removed from toilet toilets or places around water, it is ensured by forming mousse-like bubbles using a foam-like deodorant spray. It can contain bad odors. In addition, it can be used for defecation in mountain hut toilets that are often left unattended, used for portable toilets, diapers, sanitary products, cigarette butts, ashtrays, drains, sludge, etc. It is done.

  There is a growing interest in promoting combustion in a combustion furnace, particularly with respect to garbage bags. Since this agent generates radicals, it is suitable not only for deodorization but also for use in garbage bags as a combustion promoting catalyst. Spraying garbage bags or raw garbage inside them can be expected to promote combustion in a garbage incinerator.

It is explanatory drawing which shows the outline of the deodorizing spray of this invention. 10 is a graph showing the results of Example C.

Embodiments of the present invention will be described below.
FIG. 1 is an explanatory view showing an outline of a deodorizing spray according to the present invention, wherein 1 is a metal container, 2 is a spray button incorporating a valve mechanism, and 3 is a dip tube. The container 1 is filled with a mixture of a propellant and a stock solution, and a gas phase of the propellant is formed in the upper part. When the injection button 2 is pressed, the propellant and stock solution pressurized by the gas phase are ejected from the injection button 2 through the dip tube 3 and sprayed in the form of a mist.

  The deodorizing spray of 1st Embodiment contains the stock solution and the propellant which disperse | distributed the vitreous deodorizing agent as an essential component. The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component, and the copper component held in the glass It has a function of decomposing malodorous components by the catalytic action. Details of the glassy deodorant will be described later.

  A glassy deodorant is dispersed in the stock solution. As the main component of the stock solution, water such as purified water or distilled water, alcohols such as lower alcohols having 1 to 4 carbon atoms and glycols, ketones, esters, etc. are used alone or in combination. Among these, it is preferable to use water, lower alcohols, and glycols. In particular, as lower alcohols, methanol, ethanol, isopropanol, etc., and as glycols, ethylene glycol, propylene glycol, etc. are suitable for use, and derivatives of glycols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc. The ethers are also suitable for use.

  The propellant discharges the stock solution in which the vitreous deodorant is dispersed from the nozzle to the outside of the container by gas pressure. As the propellant, liquefied petroleum gas (LPG), dimethyl ether (DME), fluorinated hydrocarbon, etc. can be used, and compressed carbon dioxide, nitrogen gas, nitrous oxide gas, etc. can also be used. . These propellants can be used alone or in combination of two or more. Note that LPG and DME are flammable, and fluorinated hydrocarbons, carbon dioxide gas, and nitrogen gas are difficult to burn. Therefore, it is preferable to use the propellant properly depending on the application. The blending amount of the propellant is not particularly limited, but from the viewpoint of the internal pressure, the internal pressure is usually 0.2 to 0.8 MPa at 35 ° C., preferably 0.3 to 0.7 MPa. Adjust so that

Next, the foam-like deodorant spray which is the 2nd Embodiment of this invention is demonstrated.
The foam-like deodorant spray contains a stock solution in which a glassy deodorant is dispersed, a surfactant and a propellant as essential components. The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component, and the copper component held in the glass It has a function of decomposing malodorous components by the catalytic action.

About a stock solution and a propellant, the thing similar to 1st Embodiment can be used.
Surfactant is for making the sprayed mist-like liquid foam. Examples of the surfactant include nonionic surfactants, anionic surfactants, and amphoteric surfactants. Among these, it is desirable to use a nonionic surfactant having a high hydrophilicity and an HLB (hydrophile-lipophile balance) value in the range of 13 to 15 and having a relatively high cleaning action. Further, these surfactants can be used alone, but two or more kinds can be mixed and used.
Examples of usable surfactants are shown below.

  Nonionic surfactant: glycerin fatty acid ester, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid amide ester, sucrose Fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and the like.

  Anionic surfactant; fatty acid salt, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkyl sulfonate, N-acyl sulfonate, alkyl phosphate, N-acyl amino acid salt, alkyl ether carboxylate, N-acylmethyl taurate, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl ether phosphate and the like.

  Amphoteric surfactants; betaine-type amphoteric surfactants such as carboxybetaine, sulfobetaine, and betaine acetate; and imidazoline-type amphoteric surfactants.

Next, the glassy deodorant will be described.
The vitreous deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component, and D ₉₆ = 25 μm or less, preferably 10 μm The following powder is desirable. Here, D ₉₆ means a particle size at which the integration point is 96% when the particle size distribution is measured and cumulatively distributed. Easily settle D ₉₆ is more than 25 [mu] m, there is a possibility of clogging the spray nozzles, also the specific surface area decreases. Furthermore, since this vitreous deodorant is a colored glass made of copper, there is a concern that the color may be concerned. If the particle size is less than 0.1 μm, the efficiency of pulverizing and classifying glass is extremely lowered, which is not preferable in production. A particle size of about 0.1 to 25 μm is practical.

  The particle size is preferably selected according to the application. For example, the foot odor is desired to be immediately deodorized and the glass color is not noticeable, so the particle size is reduced. On the other hand, when spraying for food waste, since it is stored for several days, the deodorization rate should be sustained even if it is slow, and there is no need to worry about coloring with glass. There is no problem.

The content of the glassy deodorant is 0.1 to 15% by mass, preferably 0.1 to 10% by mass, based on the stock solution. If the amount is more than 15% by mass, the dispersibility may decrease and precipitate or the nozzle may be blocked. If the amount is less than 0.1% by mass, a sufficient deodorizing effect cannot be obtained. Such a vitreous deodorant can be produced by a method in which the raw material for preparation is melted and rapidly cooled to obtain a pre-molded product, and then pulverized. For the pulverization, a generally known pulverizer (for example, a ball mill, a bead mill, a jet mill, a CF mill, etc.) can be used, and it may be dry or wet.
Next, the composition of the vitreous deodorant will be described.

(Alkali-alkaline earth-borosilicate glass)
The alkali-alkaline earth-borosilicate glass containing the above-described copper component is SiO ₂ : 46 to 70 mol%, B ₂ O ₃ + R ₂ O (R: alkali metal): 15 to 50 mol%, R′O. (R ′: alkaline earth metal): 0 to 10 mol%, Al ₂ O ₃ : 0 to 6%, CuO: 0.01 to 23 mol%. _Here, B ₂ O 3: _{5~20 mol%,} R 2 O: can be 10 to 30 mol%.

A preferred composition of the vitreous _deodorants, SiO 2: 51 to 63 _{mol%, B 2 O 3 + R} 2 O: 21~39 mol%, R'O: 2 to 7 _mol%, Al _{2 O} 3: 0 -5.5%, CuO: 1-13 mol%. _Here, B ₂ O 3: _{8~17 mol%,} R 2 O: can be 13 to 22 mol%.

The most preferred composition of this vitreous _deodorants, SiO 2: 53-62 _{mol%, B} 2 O 3: _{10~17 mol%,} R 2 O: _13~19 mol%, R'O: 3 to 6 _{mol%, Al 2 O 3: 0~4.5} %, CuO: 4~13 are mole%. Below, each glass composition is demonstrated in detail.

(SiO ₂ )
SiO ₂ is a main component that forms the structural skeleton of glass, and its content is 46 to 70 mol%, preferably 51 to 63 mol%, and more preferably 53 to 62 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. Its _content, in consideration of the volatilization amount of B 2 _{O 3,} 5 to 20 mol%, preferably 8 to 17 mol%, further preferably 10 to 17 mol%. 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 ₂ O (R = Li, Na, K) breaks the bond between Si and O in the glass structure skeleton to form non-crosslinked oxygen, resulting in a decrease in glass viscosity, moldability and solubility. And a flux similar to B ₂ O ₃ . The content of one or more of R ₂ O is 10 to 30 mol% in total, preferably 13 to 22 mol%, more preferably 13 to 19 mol%, considering the content ratio with multiple components. And When it exceeds 30 mol%, the chemical durability of the glass becomes insufficient. Specifically, a whitening phenomenon called bloom is caused by a reaction between the glass agent and moisture in the atmosphere. The occurrence of bloom is undesirable because it reduces the contact area with malodorous gas.

(B ₂ O ₃ + R ₂ O)
As mentioned above, both B ₂ O ₃ and R ₂ O are used as fluxing agents. The range in which the total content of B ₂ O ₃ and R ₂ O is 15 to 50 mol%, preferably 21 to 39 mol%, is a region that 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 50 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 catalysis. 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′O (R ′ = Mg, Ca, Sr, Ba) is a component that improves the chemical durability of the glass. The content is one or two or more of R′O (R ′ = Mg, Ca, Sr, Ba) in a total of 0 to 10 mol%, preferably 2 to 7 mol%, more preferably 3 to 6 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. Note that R′O is not an essential component in the deodorant of the invention, and its content may be 0 mol%, but is preferably 2 mol% or more.

(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 the viscosity and the addition may affect the redox state of copper ions in the glass, its content is 6 mol% or less, preferably 5.5 mol% or less, most preferably 4 .5 mol% or less.

(CuO)
CuO functions as a catalyst, accelerates the decomposition reaction of the sulfurous malodorous substance, and exhibits the deodorizing effect of the sulfurous malodorous substance. The content is 0.01 to 23 mol%, preferably 1 to 13 mol%, more preferably 4 to 13 mol%. If it exceeds 23 mol%, undissolved material tends to remain, and metal copper tends to precipitate during rapid cooling or processing, which is not preferable. Since the glass is discolored with the deposition of metallic copper, it is not suitable for applications where discoloration of the glass is a problem. Moreover, when it precipitates as metallic copper, poisoning will advance. On the other hand, if CuO is included as a glass component, poisoning does not proceed easily, and the catalytic function can be stably exhibited over a long period of time.

(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.

(Alkali-alkaline earth-silicate glass)
In the present invention, an alkali-alkaline earth-silicate glass containing a copper component can also be used as the vitreous deodorant. This _glass, SiO 2: 50-70 _mol%, R 2 O: _10~33 mol%, R'O: 0 to 15 _{mol%, Al 2 O 3: 0~6} %, CuO: 0.01~23 It is a glass containing mol%.

A preferred composition of the vitreous _deodorants, SiO 2: 55 to 70 _mol%, R 2 O: _12~24 mol%, R'O: 2 to 10 _{mol%, Al} 2 O 3: _0~5.5 %, CuO: 1 to 20 mol%. The most preferred composition of this vitreous deodorant _2, SiO 2: 55 to 65 _mol%, R 2 O: _12~20 mol%, R'O: 3 to 7 _mol%, Al ₂ O 3: _0~ 5%, CuO: 4 to 13 mol%.

Unlike the alkali-alkaline earth-borosilicate glass described above, the alkali-alkaline earth-silicate glass does not contain B ₂ O ₃ , so the numerical range of the composition is slightly changed. Is the same as alkali-alkaline earth-borosilicate glass.

  A vitreous deodorant comprising an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component is dispersed in a stock solution and is usually added together with a propellant. Fill the spray container according to the method.

  The deodorizing spray of the present invention has a function of decomposing malodorous components by the catalytic action of the copper component held in the glass of the vitreous deodorant. Unlike the soluble glass, the copper component decomposes the malodorous component by the catalytic action while being retained in the glass, so that the deodorizing effect is maintained over a long period of time and the durability is excellent. Further, since the soluble glass is an acidic glass, it does not have a deodorizing effect on lower fatty acids that are acidic malodors, but the vitreous deodorant in the present invention has a deodorizing effect on malodorous substances such as lower fatty acids and body odor components. .

  In the above-described embodiment, the vitreous deodorant is used alone, but it can be combined with an inorganic deodorant such as general-purpose silica gel, zeolite, activated carbon, clay mineral, photocatalyst (titanium dioxide). Moreover, it can also be used with the phosphate glass containing silver. Such combined use makes it possible to aim at effects such as speeding up the deodorization speed and cost reduction.

Further, for the purpose of promoting uniform dispersion of the vitreous deodorant in the stock solution, a dispersion aid for a silane compound such as alkoxysilane or chlorosilane can be blended, or various fragrances can be blended.
Examples of the present invention are shown below. In the table, nd means not detected.

  Glass raw materials were prepared so as to have the composition shown in Table 1, and melted, molded, and pulverized by a melt quenching method to produce a glassy deodorant. The obtained glassy deodorant was filled in a spray container together with the stock solution and the propellant under the conditions shown in Table 2 to form a deodorant spray. The deodorizing effect of this deodorant spray was confirmed. Moreover, in order to compare with the agent which shows the deodorizing by the chemical adsorption reaction by silver ion and copper ion, and an antibacterial deodorizing, it compared with the conventional soluble glass.

  In the first embodiment in Table 2, methanol was used as the stock solution and LPG was used as the propellant, and the respective mass ratios were 50 parts: 50 parts. The content of the deodorant is a value of deodorant / (deodorant + stock solution). For example, when the content of the deodorant is 10%, 45 parts by mass of methanol, 5% of the deodorant Part, LPG50 part.

  In the second embodiment in Table 2, water is used as a stock solution, LPG is used as a propellant, and glycerin fatty acid ester, which is a nonionic surfactant, is used as a foaming surfactant. 45 parts and 5 parts. The content of the deodorant is the same as described above. For example, when the content of the deodorant is 10%, 45 parts by weight of water, 5 parts of the deodorant, 45 parts of LPG, and 5 parts of glycerin fatty acid ester are added. means.

(Example A: Deodorizing effect against various bad odors)
The sprays of Experimental Examples 1 to 18 in Table 2 were sprayed into a 1 L Tedlar bag enclosing a malodor component, and the malodor concentration in the bag with the elapsed time was measured at room temperature. The spray amount was 10 g. As a comparison, a vitreous deodorant composed of the soluble glasses 1 to 3 shown in Table 3 was produced and pulverized to D ₉₆ = 25 μm or less, and the content rate was 0.1 mass as in the first embodiment of the experimental example. The spray was prepared so as to be%. In addition, Experimental example 3 using the glass which does not contain a copper component corresponds to a blank. As a result, as shown in Table 4, it was confirmed that any offensive odors showed a deodorizing effect. Moreover, it was confirmed that the soluble glass does not show a deodorizing effect on lower fatty acids and aging odors.

(Example B: Sustainability to chemical adsorbent)
The sprays of Experimental Examples 1, 2, 5, and 6 in Table 2 were sprayed into a 1 L Tedlar bag enclosing a malodor component, and the malodor concentration in the bag with the elapsed time was measured at room temperature. The spray amount was 10 g. As a comparison, a vitreous deodorant composed of the soluble glasses 2 to 4 shown in Table 3 was produced and pulverized to D ₉₆ = 25 μm or less, and the content rate was 0.1 mass as in the first embodiment of the experimental example. The spray was prepared so as to be%. As a result, as shown in Table 5, it was confirmed that the soluble glass reached the deodorization limit, whereas the glass agent of the present invention had a large total deodorization amount. Considering the content of silver and copper components, soluble glass may be deodorized, but it is deodorized by chemical adsorption (sulfurization reaction), so the surface is covered with reaction deposits. It is also conceivable that the specific surface area was not sufficiently obtained due to aggregation by moisture. On the other hand, since the glass agent of the present invention exhibits a catalytic action, the total amount of deodorization can be expected even if the surface area is not sufficiently obtained due to some problem. However, the glass changes continuously depending on the composition, and the effect also changes continuously from the catalytic reaction to the adsorption reaction of the soluble glass. Since Experimental Example 5 had a composition with reduced durability (composition approaching soluble glass), it was confirmed that the tendency of the adsorption reaction became strong like the soluble glass and reached the deodorizing limit.

(Example C: Basic characteristics and decomposition action of glassy deodorant)
D ₅₀ = 4.2 μm ground glass 1g composed of composition number 6 in Table 2 and methyl mercaptan were sealed in a 5 L Tedlar bag, and methyl mercaptan and dimethyl disulfide in the bag over time were measured with a gas chromatograph at room temperature. did. Moreover, the same operation was performed using the bag of the same capacity | capacity formed with the film which does not contain a glassy deodorant as a blank. It was confirmed in advance using a gas chromatograph mass spectrometer that the gas components present in the bag were these two components. As a result, as shown in FIG. 2, it was confirmed that the vitreous deodorant of the present invention has an action of decomposing methyl mercaptan and generating dimethyl disulfide. The basic characteristics of a glassy deodorant are naturally maintained even when kneaded into a film or the like.

(Example D: Basic characteristics of glassy deodorant / radical generation)
D ₅₀ = 0.1 mol·L ⁻¹ phosphate buffer solution of pH = 7.4 with respect to 200 mg of the glass composed of the soluble glass 1 of Table 2, composition numbers 6, 9 and Table 3 ground to 5.0 μm 200 μL was added. Thereto, 10 μL of 9.2 mol·L ⁻¹ DMPO (manufactured by LABOTEC, LM-2110) was added and shaken. Shake was stopped 10 seconds, 1 minute, and 5 minutes after DMPO addition, and only the solution was collected with a hematocrit tube, and ESR (manufactured by JEOL Ltd., FR-30, X band) measurement was performed. Moreover, the thing except glass was made into the blank. All were performed at room temperature under fluorescent light. This technique corresponds to the spin trap method, which is a general technique for measuring radicals, and spin adducts are generated when DMPO captures radicals. This product (DMPO-OH) was detected by ESR. The unit of the detection value is a peak area value ratio (area single / area manganese, S / M) with respect to the reference material Mn2 +. The results are shown in Table 6. The composition No. 6 glass was confirmed to produce DMPO-OH, whereas the composition No. 9 and the soluble glass 1 only showed a background value as in the blank. It was confirmed that the vitreous deodorant of the present invention has a high possibility of generating radicals.

(Example E: Basic characteristics of glassy deodorant and suppression of catalyst deterioration)
D ₅₀ = 4.2 μm crushed glass of composition number 6 in Table 2 0.1 g and CuO reagent (average particle size 4 μm) 0.1 g each was sealed in a 1 L Tedlar bag at room temperature with time The methyl mercaptan concentration in the bag was measured with a gas chromatograph. The initial concentration of methyl mercaptan was 55 ppm and repeated up to 10 times. Moreover, the same operation was performed without glass as a blank. As a result, as shown in Table 7, the deodorizing effect of the CuO reagent is reduced with repetition. This is a generally known catalyst deterioration (sulfur adsorption) of CuO. On the other hand, it was confirmed that the glass maintained the deodorizing effect and was highly sustainable. Although elucidation of this mechanism remains, it has been confirmed that catalyst degradation is suppressed by vitrification. When the glass surface at this time was analyzed by XPS (manufactured by ULVAC-PHI Co., Ltd., PHI 5000 VersaProbe), as shown in Table 8, it was confirmed that there was certainly no sulfur adsorption after deodorization. The basic characteristics of a glassy deodorant are naturally maintained even when kneaded into a film or the like.

1 container 2 nozzle 3 dip tube

Claims (4)

A deodorizing spray containing a stock solution in which a glassy deodorant is dispersed and a propellant,
The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component,
A deodorizing spray characterized by having a function of decomposing malodorous components by the catalytic action of a copper component held in glass. A deodorizing spray containing a stock solution in which a glassy deodorant is dispersed, a propellant, and a foaming surfactant,
The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component,
A deodorizing spray characterized by having a function of decomposing malodorous components by the catalytic action of a copper component held in glass. The deodorizing spray according to claim 1 or 2, wherein the glassy deodorant is a powder having a D _{96 of} 25 µm or less.   The deodorizing spray according to any one of claims 1 to 3, wherein the content of the glassy deodorant is 0.1 to 15% by mass relative to the stock solution.