JP6441185B2 - Deodorant plate - Google Patents

Description

  The present invention relates to a deodorant plate having a deodorizing function.

  Conventionally, plate-like bodies made of synthetic resin and rubber have been widely used in various fields such as building materials such as walls and partitions, kitchenware such as cutting boards and food trays, stationery such as underlays and plastic plates for work. Yes. When such a plate-like body is used for a long period of time, dirt and wrinkles are generated, which causes problems of being unsanitary and deterioration of appearance quality. Therefore, the present applicant has developed a powder in which a soluble glass powder containing silver or zinc is held in a plate-like body to improve the antifouling / antifouling effect. Proposed.

Dissolving glass has the advantage that it releases silver and zinc ions gradually when it comes into contact with moisture, and can exhibit antifouling and antifouling effects for a relatively long period of time. However, in many cases, the soluble glass is a fine powder having a particle size of D ₉₆ = 40 μm or less, so that the total content of silver and zinc is small, and the effect depends on the surface exposure. For this reason, it is inevitable that the conventional deodorant plate-like body gradually decreases in antibacterial effect as the release of ions proceeds.

  In addition to the antibacterial effect, silver ions have the effect of preventing malodors produced by bacteria, and also exhibit deodorizing effects against sulfur-based malodors such as hydrogen sulfide and methyl mercaptan by chemisorption and physical adsorption. However, this deodorizing effect also gradually decreases as the release of ions proceeds, and there is a problem that it has poor durability. Moreover, silver ions have no deodorizing effect on malodorous components such as lower fatty acids and body odor components, and there is a problem that these odors cannot be prevented. Recently, in recent years, it has been studied to give a deodorizing effect to indoor partitions in the nursing field, but the main component of the odor is body odor components such as lower fatty acids and aging odors. There was also a problem that it was not suitable.

JP-A-3-75142 JP-A-7-246168 JP-A-5-202227

  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 plate-like body having a function of deodorizing.

The present invention made to solve the above problems is a deodorant plate having a glassy deodorant supported on a plate, the glassy deodorant containing a copper component, alkaline earth - - alkali content was 0 to 5.5 mole% Al ₂ O ₃ containing borosilicate glass or copper component, and the content of _Al 2 _{O 3} 0 to 5.5 mol% It is made of alkali-alkaline earth-silicate glass, and while the copper component is held in the glass , the bad odor component in the air in contact with the plate-like body is obtained by the catalytic action of the copper component held in the glass. It has a function of decomposing.

In addition, as described in claim 2, the content of the vitreous deodorant is preferably 0.1 to 15% by mass, and as described in claim 3, the vitreous deodorant is D ₉₆ = A powder of 40 μm or less is preferable.

  Furthermore, as described in claim 4, the plate-like body may be made of synthetic resin or rubber.

Deodorizing plate-like body of the present invention contains a copper component, an alkali content was from 0 to 5.5 mol% of Al ₂ O ₃ - alkaline earth - borosilicate glass, or the copper component A glassy deodorant made of alkali-alkaline earth-silicate glass containing Al ₂ O _{3 in} a content of 0 to 5.5 mol% is supported and contained in the glass. The malodorous component is decomposed by the catalytic action of the obtained copper component. The vitreous deodorant is preferably carried by being kneaded into the plate-like body so that a part of the glass-like deodorant is exposed, or by being attached to the surface of the plate-like body. When the glassy deodorant is supported on the surface of the plate-like body, the amount of the glassy deodorant used can be reduced, but depending on the application, there is a risk that it will fall off. It is preferable to select by.

  While various deodorants using soluble glass have been developed, conventionally, a “glass agent showing a deodorizing effect by catalytic action” has 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 attention is paid only to the deodorizing amount, a small amount of the glassy deodorant may be added.

  The vitreous deodorant used in the present invention can exhibit an excellent deodorizing effect particularly with respect to methyl mercaptan. That is, this vitreous 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), 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.

  Further, the vitreous deodorant used in the present invention exerts a function of deodorizing not only sulfur-based malodorous substances such as methyl mercaptan but also malodorous substances such as lower fatty acids, body odor components and aging odors over a long period of time. This is preferable. For example, since the main components of the garbage odor are hydrogen sulfide, methyl mercaptan, and propionic acid, the plate-like body of the present invention is suitable for use as a cutting board. Further, as described in Examples and the like, radicals are generated from the vitreous deodorant used in the present invention, which is promoted by moisture. The fact that the deodorizing effect is promoted by moisture as described above is also the reason why the plate-like body of the present invention is suitable for use as a cutting board.

  However, the plate-like body having a deodorizing function of the present invention is not limited to a cutting board, for example, as a building material such as a wall material or a partition, as a kitchen utensil such as a food tray, an underlay or a plastic plate for work. It can be applied to various uses such as a stationery such as a drawing board, a playground equipment such as a drawing board, and a cool mat for pets, a body housing member, and a water tank. The vitreous deodorant is not harmful even if it directly touches the skin, and there is no problem in terms of safety.

It is a typical perspective view showing an embodiment of the present invention. It is typical sectional drawing which shows the deodorizing plate-shaped object of 1st Embodiment. It is typical sectional drawing which shows the deodorizing plate-shaped object of 2nd Embodiment. 10 is a graph showing the results of Example C.

Embodiments of the present invention will be described below.
FIG. 1 is a perspective view showing an embodiment of the present invention, wherein 1 is a plate-like body made of synthetic resin, and 2 is a glassy deodorant 2 dispersed and held on the surface of the plate-like body 1. As shown in FIG. 2, the deodorant plate-like body of the first embodiment is obtained by kneading a glassy deodorant 2 in a resin-made plate-like body 1. The glassy deodorant 2 is composed of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkali earth-silicate glass containing a copper component, and is a powder having a D _{96 of} 40 μm or less. It is desirable to be.

Here, D ₉₆ means a particle size at which the integral value when the particle size distribution measurement is performed and the cumulative distribution is 96%. With D ₉₆ are uniformly dispersed difficulties of the exceeding 40μm resin plate body in order to reduce the catalytic effect specific surface area of the vitreous deodorant 2 is lowered, unfavorably. If the particle size is less than 1 μm, the efficiency of pulverization and classification of the glass is extremely reduced, which is not preferable for production. A particle size of about 1 to 40 μm is practical. The composition of the vitreous deodorant 2 of the present invention will be described below.

(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~} 5.5 mol%, CuO: 0.01 to 23 is a glass containing mol%. _Here, B ₂ O 3: _{5~20 mol%,} R 2 O: can be 10 to 30 mol%.

Preferred compositions the vitreous deodorant _2, SiO 2: 51~63 _{mol%, B 2 O 3 + R} 2 O: 21~39 mol%, R'O: 2 to 7 _mol%, Al _{2 O} 3: 0 to 5.5%, CuO: 1 to 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 deodorant _2, SiO 2: 53-62 _{mol%, B} 2 O 3: _{10~17 mol%,} R 2 O: _13~19 mol%, R'O: 3~ 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 becomes high 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. Increasing the viscosity, since it can affect the redox state of copper ions in the glass by the addition, its content is 5.5% by mole or less, and most preferably 4.5 mol% or less To do.

(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 2. This _glass, SiO 2: 50-70 _mol%, R 2 O: _10~33 mol%, R'O: 0 to 15 _{mol%, Al 2 O 3: 0~} 5.5 mol%, CuO: 0. It is a glass containing 01 to 23 mol%.

The preferred composition of the vitreous deodorants _2, 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.

  As shown in FIG. 1, the vitreous deodorant 2 comprising an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component is a resin. It is kneaded into the plate 1 made of rubber or rubber. The type of resin is not particularly limited. Polyethylene (PE), polypropylene (PP), chlorinated polypropylene, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polytetrafluoroethylene, polystyrene, polyvinyl fluoride , Polyvinylidene fluoride, polyimide, polybutadiene, polychloroprene, polyester elastomer, polysulfone, silicone resin, eval resin, alkyd resin, polyvinyl acetate, vinyl acetate nylon, polyester, polyvinyl alcohol, acrylic resin, vinyl chloride / vinyl acetate copolymer resin , Styrene resin, epoxy resin, polymethylpentene, polymethyl methacrylate, polymethylmethacrylate (PMMA), polyvinyl butyral, ionomer, polyurethane And synthetic resins such as fine cellulose derivatives, can be any resin. Of course, resins that can be kneaded and multilayered may be combined. In addition to the above, the plate-like body 1 includes general-purpose engineering plastics such as polyethylene terephthalate (PET), polycarbonate (PC), and polyamide (PA), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), and modified polyphenylene ether (m -PPE), polyetherimide (PEI), polyethersulfone (PES), polyarylate (PAR), heat-resistant polyamide (nylon 6, nylon 6T, nylon 66, nylon 12, nylon 9T, nylon 46T), polybutylene terephthalate ( Heat-resistant resins such as PBT), polyacetal (POM), polyetheretherketone (PEEK), liquid crystal polymer (LCP), and thermosetting resin can also be used. These various resins may be kneaded or multilayered by one kind or two or more kinds. In addition, you may comprise a part of plate state with such resin, and even if it crystallizes, there is no problem in the deodorizing effect.

  As rubber, natural rubber, synthetic natural rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, butyl rubber, nitrile rubber, ethylene propylene rubber, acrylic rubber, urethane rubber, silicone rubber, fluorine rubber, polysulfide rubber, etc. Rubber can be used. One or more of these rubbers may be kneaded and multilayered. You may comprise a part of plate state with such rubber | gum.

  The content of the glassy deodorant 2 in the plate-like body 1 is preferably 0.1 to 15% by mass. If it is less than this range, the deodorizing effect is insufficient. In the present invention, since the vitreous deodorant 2 exhibits a deodorizing function due to a catalytic effect, the deodorizing amount does not depend on the exposed amount of the vitreous deodorant 2. For this reason, in the long term, it is sufficient that a small amount is exposed on the plate-like surface, and even if the content exceeds 15%, an increase in deodorizing amount cannot be expected. A more preferable content rate is 1 to 5% by mass.

  In the first embodiment described above, the glassy deodorant 2 is uniformly kneaded into the plate-like body 1, but only in the surface layer portion of the plate-like body 1 as in the second embodiment shown in FIG. A glassy deodorant 2 may be supported. In this case, for example, the glassy deodorant 2 may be dispersed in the binder 3 and then coated on the surface of the plate-like body 1.

  Since such a deodorizing plate-like body can reduce the vitreous deodorant 2 which is buried in the plate-like body 1 and does not contribute to deodorization, the deodorizing effect can be further enhanced. Examples of binders include acrylic resin, phenol resin, urethane resin, polyvinyl alcohol, epoxy, vinyl acetate, polyvinyl acetate, nitrile rubber, styrene butadiene rubber, chloroprene rubber, and silicone rubber binder. It can be used and attached to the surface of the plate-like body 1 by an appropriate method such as spraying, dipping or roll coating.

  The deodorant plate-like body 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 2. 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. However, the vitreous deodorant 2 in the present invention has a deodorizing effect on malodorous substances such as lower fatty acids and body odor components. Have.

  The deodorant plate-like body of the present invention is, for example, a building material such as a wall material or a partition, a kitchen article such as a cutting board or a food tray, a stationery such as an underlay or a working plastic board, and a drawing board. It is used for various uses as a playground equipment such as, and is processed into a plate-like material having a predetermined size and thickness according to each use.

  In the above-described embodiment, the glassy deodorant 2 is used alone, but it can also be used in combination 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 of patent document 1,2. Such combined use makes it possible to aim at effects such as speeding up the deodorization speed, expanding target gas, and reducing costs.

  Examples of the present invention are shown below. In the table, n.d. 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 vitreous deodorant was blended in the base resin under the conditions shown in Table 2, and a 15 cm square and 0.3 cm thick deodorant plate was molded using an injection molding machine. Using this deodorant plate, a deodorization effect confirmation test was conducted.

(Example A: Deodorizing effect against various bad odors)
One plate-like body of Experimental Examples 1 to 30 in Table 2 was sealed with a malodorous component in a 1 L Tedlar bag, and the malodor concentration in the bag with the elapsed time was measured at room temperature. For comparison, a glassy deodorant composed of the soluble glasses 1 to 3 shown in Table 3 was produced, pulverized to D ₉₆ = 40 μm or less, and blended in high-density polyethylene so that the content was 0.1% by mass. In the same manner, a plate-like body was formed. In addition, the blank which does not contain a copper component corresponds to Experimental Example 3. Hydrogen sulfide and methyl mercaptan were measured with a gas chromatograph, lower fatty acids were measured with a gas detector tube, and aging odor was measured with a high performance liquid chromatograph. As a result, as shown in Table 4, it was confirmed that there was a deodorizing effect against any offensive odors except for the blank. Moreover, it turns out that soluble glass has no deodorizing effect with respect to propionic acid, isovaleric acid, and trans-2-nonenal.

(Example B: Sustainability to soluble glass)
One plate-like body of Experimental Examples 1, 2, 5, 6, and 22 in Table 2 was sealed with a malodorous component in a 1 L Tedlar bag, and the malodor concentration in the bag with the elapsed time was measured at room temperature with a gas chromatograph. As a comparison, a glassy deodorant composed of the soluble glasses 2 to 4 shown in Table 3 was produced, pulverized to D ₉₆ = 40 μm or less, and blended in high-density polyethylene so that the content was 0.1% by mass. In the same manner, a plate-like body was formed. Nylon 6 has water permeability, and in order to confirm the effect in the presence of moisture, 1 mL of distilled water was put together in a Tedlar bag and sealed, and brought into contact with the plate-like body. As a result, as shown in Table 5, it was confirmed that the soluble glass reached the deodorizing limit and converged. On the other hand, it was confirmed that Experimental Examples 1, 2, 6, and 22 have a large deodorizing total amount. In the case of soluble glass, the deodorization limit is determined according to the exposure amount, whereas the experimental example shows a catalytic action, so that even if a small amount is exposed, the total amount of deodorization can be expected. 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 (because it was a composition approaching soluble glass), it was confirmed that the tendency of the adsorption reaction was the same as that of soluble glass and reached the deodorization limit. Moreover, since nylon 6 has water permeability as conventionally known, the internal soluble glass can also exhibit the effect. Although the glassy deodorant of the present invention has a deodorizing mechanism different from that of the soluble glass, the deodorizing effect is promoted by moisture as a result of Experimental Example 22 (water addition). This is because, as shown in Example D, since radicals are generated, the amount of radicals generated is improved by moisture.

(Example C: Basic characteristics and decomposition action of glassy deodorant)
1 g of glass consisting of composition number 6 in Table 1 pulverized to D ₅₀ = 4.2 μm 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 as a blank, without a glassy deodorant. In addition, it was confirmed in advance by a gas chromatograph mass spectrometer that the gas components present in the bag were only these two components. As a result, as shown in FIG. 4, it was confirmed that the vitreous deodorant of the present invention has an action of decomposing methyl mercaptan and generating dimethyl disulfide. Even if it mixes with resin, the basic characteristic of a glassy deodorant is naturally hold | maintained.

(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 composition numbers 6 and 9 and table 3 of Table 1 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 detected value is a peak area value ratio (area single / area manganese, S / M) with respect to the reference material Mn ²⁺ . 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. Even if it mixes with resin, the basic characteristic of a glassy deodorant is naturally hold | maintained.

1 Plate 2 Glassy Deodorant 3 Binder

Claims (4)

A deodorant plate having a glassy deodorant carried on a plate,
This glassy deodorant contains a copper component, and contains an alkali-alkaline earth-borosilicate glass in which the content of Al ₂ O ₃ is 0 to 5.5 mol% , or a copper component, and Al ₂ O ₃ consisting of an alkali-alkaline earth-silicate glass with a content of 0 to 5.5 mol%, and the catalytic action of the copper component held in the glass while holding the copper component in the glass. A deodorant plate having a function of decomposing malodorous components in the air in contact with the plate.   2. The deodorant plate according to claim 1, wherein the content of the glassy deodorant is 0.1 to 15% by mass. The deodorizing plate-like body according to claim 1 or 2, wherein the glassy deodorant is a powder having a D _{96 of} 40 µm or less.   The deodorant plate according to any one of claims 1 to 3, wherein the plate is made of synthetic resin or rubber.