JP5401397B2 - Toilet seat device and method for producing deodorized molded body for toilet seat device - Google Patents

Description

  The present invention relates to a toilet seat apparatus having a deodorized molded body capable of removing odor components such as trimethylamine, ammonia, methyl mercaptan and hydrogen sulfide, and a method for producing a deodorized molded body for toilet seat apparatus.

  The air in the toilet room contains nitrogen-based odor components such as amine-based nitrogen compounds such as trimethylamine and ammonia, and sulfur-based odor components such as sulfur compounds such as hydrogen sulfide and methyl mercaptan. Furthermore, odor components of aldehydes such as acetaldehyde and formaldehyde may be contained. These odor components are uncomfortable for the toilet user.

  For this reason, the porous material carries a first additive composed of one or both of a transition element such as copper or a transition element compound, and a second additive composed of one or more of halogen such as bromine or a halogen compound. A deodorizing material is known (Patent Document 1). Furthermore, a deodorizer formed by supporting an acidic salt of m- and / or p-aromatic amino acid, an acid, iodine and / or iodide on a porous material is known (Patent Document 2). . Furthermore, as a deodorizing agent for removing nitrogen compound-based odor components and sulfur compound-based odor components, a deodorizing agent supporting cuprous oxide and copper trihydroxide nitrate is known (Patent Document 3). .

JP-A-8-281113 JP-A-5-23588 JP 2004-166920 A

  However, the deodorizing material according to Patent Document 1 cannot exhibit a sufficient deodorizing performance in an actual use environment in which a low-concentration odor component is present. The deodorizer according to Patent Document 2 uses a volatile substance such as iodine as its active ingredient. Since such substances are corrosive, when a deodorizer is used together with metal parts or the like, these metal parts may be corroded. Furthermore, since halogens such as iodine may generate dioxins during incineration, it is not preferable from the viewpoint of reducing environmentally hazardous substances. Moreover, although the deodorizing agent which concerns on patent document 3 can remove a nitrogen compound type odor component and a sulfur compound type odor component, it cannot remove the odor of aldehydes.

  The present invention has been made in view of the above circumstances, is highly efficient, can remove odorous components for a long period of time, is safe for the environment, and further has a nitrogen compound type such as trimethylamine or ammonia. Manufacture of toilet seat apparatus and deodorized molded article for toilet seat apparatus having deodorized molded article advantageous for deodorizing odor components, odor components of sulfur compounds such as hydrogen sulfide and methyl mercaptan, and odor components of aldehydes such as acetaldehyde and formaldehyde It is an object to provide a method.

  (1) A toilet seat device according to a first aspect of the present invention is a toilet seat having a base that is mounted on a Western-style toilet, a toilet seat that is swingably provided at the base, and a toilet lid that is swingably provided at the base. The base has a deodorized molded body holding part and a deodorized molded body held by the deodorized molded body holding part, and the deodorized molded body has copper oxide and nitric trinitrate as a porous carrier. It is formed by supporting copper and aminobenzoic acid as active ingredients.

In the porous carrier, copper oxide and copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ) are supported. For this reason, the synergistic effect of copper oxide and copper trihydroxide nitrate effectively removes amine-based nitrogen compound-based odor components such as trimethylamine and ammonia, and sulfur compound-based odor components such as methyl mercaptan and hydrogen sulfide. can do. Aminobenzoic acid supported on the porous carrier removes odor components of aldehydes such as acetaldehyde and formaldehyde. In consideration of deodorizing properties, cuprous oxide (Cu ₂ O) is preferable as the copper oxide, but copper oxide (CuO) may be used in some cases.

  The chemical mechanism of copper oxide and copper trihydroxide nitrate to remove odor components is that for sulfur compound odor components such as methyl mercaptan and hydrogen sulfide, copper oxide and copper trihydroxide nitrate are sulfur compounds. This is thought to be due to the oxidation of the odor components of the system to produce sulfur or metal sulfides. In addition, for nitrogen compound odor components such as trimethylamine and ammonia, it is considered that copper trihydroxide nitrate mainly forms a complex with the amine compound.

  The deodorized molded body has a porous carrier supporting copper oxide such as cuprous oxide and copper trihydroxide. For this reason, a deodorizing molded object has a large contact area with an odor component, and the copper oxide and copper trihydroxide nitrate couple | bonded with the porous support | carrier can deodorize an odor component efficiently. Furthermore, unlike the conventional deodorizing material, the deodorized molded article does not contain halogen such as iodine harmful to the environment. For this reason, the lifetime of a deodorizing performance improves rather than the said conventional deodorizing material, without producing the malfunction that a halogen volatilizes during use and the removal performance of an odor component falls easily. It is also safe for the environment. As described above, according to the first aspect of the present invention, it is possible to provide a deodorized molded body that is highly efficient and that can remove odor components for a long period of time and is safe to the environment.

  (2) A method for producing a deodorized molded article for toilet seat apparatus according to the second aspect of the present invention includes a first impregnation step of impregnating a porous carrier with a metal salt containing copper, and a porous carrier after completion of the first impregnation step Heat treatment step of heating the substrate in an inert gas atmosphere at 400 ° C. to 800 ° C., a second impregnation step of impregnating the porous carrier after completion of the heat treatment step with a metal salt, and a porous carrier after completion of the second impregnation step A drying step of drying the porous carrier after the completion of the third impregnation step, and a third impregnation step of impregnating the aromatic amino acid into the multi-rigid support after completion of the drying step.

In the porous carrier, copper oxide such as cuprous oxide (Cu ₂ O) and copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ) are supported. For this reason, the synergistic effect of cuprous oxide such as cuprous oxide and copper trihydroxide nitrate enables efficient use of amine odor components such as trimethylamine and ammonia, and sulfur compound odor components such as methyl mercaptan and hydrogen sulfide. Can be removed. The aromatic amino acid supported on the porous carrier removes odor components of aldehydes such as acetaldehyde. Aromatic amino acids include aromatic monoamino monocarboxylic acids. Examples of the aromatic monoaminomonocarboxylic acid include paraaminobenzoic acid, metaaminobenzoic acid, and paraaminosalicylic acid.

  According to the manufacturing method of the second aspect of the present invention, the metal salt containing copper is impregnated twice by the first impregnation step and the second impregnation step, and further, the heat treatment step is performed after the first impregnation step, and after the first impregnation step. A drying process is performed. For this reason, in the heat treatment step, a metal salt containing copper is supported on the porous carrier as a metal oxide. In the drying step, the metal salt is supported on the porous carrier in a state as it is or in a state in which hydroxide ions are taken out from water or the like as a solvent used for impregnation and bonded to the hydroxide ions. Therefore, according to the production method of the second invention, the metal salt containing copper is supported on the porous carrier in at least two forms. As a result, the resulting deodorized molded article exhibits an excellent deodorizing effect with respect to nitrogen compound-based odor components and sulfur compound-based odor components. In addition, since the porous carrier does not contain a volatile substance such as halogen, it is safe for the environment, and the active ingredient is volatilized and the deodorizing performance is likely to be lowered like the conventional deodorizing material. There is no problem.

It is a figure which shows typically the state which opened the toilet lid of the toilet seat apparatus attached to the toilet bowl. It is a figure which shows typically the state which closed the toilet lid of the toilet seat apparatus attached to the toilet bowl. It is a figure which concerns on Embodiment 1 and shows the state by which the deodorizing molded object holding part is hold | maintained typically. It is a figure which concerns on Embodiment 2 and shows the state by which the deodorizing molded object holding part is hold | maintained typically. It is a figure which concerns on Embodiment 3 and shows the state by which the deodorizing molded object holding part is hold | maintained typically. It is a figure which concerns on Embodiment 4 and shows the state by which the deodorizing molded object holding | maintenance part is hold | maintained typically. It is a figure which concerns on Embodiment 5 and shows the state by which the deodorizing molded object holding | maintenance part is hold | maintained typically. It is a perspective view which concerns on an Example and shows a deodorizing molded object typically. It is a figure which shows the concept of a measuring device typically. It is a graph which shows the relationship between elapsed time and the removal rate of hydrogen sulfide. It is a graph which shows the relationship between elapsed time and the removal rate of acetaldehyde. It is a graph which shows the relationship between elapsed time and the removal rate of a trimethylamine.

  In toilets, in general, nitrogen compound odor components such as trimethylamine and ammonia, and sulfur compound odor components such as methyl mercaptan and hydrogen sulfide are stronger than odor components of aldehydes such as acetaldehyde. Therefore, preferably, copper oxide such as cuprous oxide and copper trihydroxide nitrate are supported on the upstream region of the porous carrier or the entire porous carrier, and paraaminobenzoic acid is supported on the downstream region of the porous carrier. It is preferable that In this case, the air containing an odor component passes through the portion where the aromatic amino acid is supported after passing through the portion where cuprous oxide and copper trihydroxide nitrate are supported in the porous carrier. That is, air from which nitrogen compound-based odor components such as trimethylamine and ammonia and sulfur compound-based odor components such as methyl mercaptan and hydrogen sulfide have been removed is the downstream region of the porous carrier (region where aminobenzoic acid is supported) ) For this reason, the air in contact with aminobenzoic acid is air from which most of the nitrogen compound odor component and sulfur compound odor component have been removed. For this reason, the advantage which can deodorize effectively the odor component of aldehydes, such as acetaldehyde by paraamino benzoic acid, is acquired. Examples of the aminobenzoic acid include paraaminobenzoic acid, orthoaminobenzoic acid, and metaaminobenzoic acid, and paraaminobenzoic acid is preferable in consideration of deodorizing properties.

A form in which aminobenzoic acid such as paraaminobenzoic acid is not supported can be adopted in a portion of the porous support where copper oxide such as cuprous oxide and copper trihydroxide nitrate are supported. This is because the area occupied by copper oxide and copper trihydroxide nitrate is reduced in the porous carrier. In the porous carrier, a portion in which aminobenzoic acid such as paraaminobenzoic acid is supported can adopt a form in which copper oxide such as cuprous oxide and copper trinitrate nitrate are not supported. The reason is that the area occupied by aminobenzoic acid such as paraaminobenzoic acid in the porous carrier is reduced, and the deodorizing effect by aminobenzoic acid may be reduced. The deodorizing moldings, with respect to 100 parts by weight of porous carrier, cuprous oxide _(Cu 2 O) M1 parts by weight of copper oxide, such as, trihydroxide copper nitrate _{(Cu 2 (OH) 3 NO} 3) M2 parts by mass and aminobenzoic acid M3 parts by mass.

  Here, considering the deodorization of nitrogen compound odor components and sulfur compound odor components, M1> M2 and M1> M3 can be established. M1> M2> M3 or M1> M2 = M3 or M1> M2≈M3. Further, M2> M1> M3. M1 = M2 = M3. M1≈M2≈M3. In consideration of deodorization of odor components of aldehydes, M3> M1 and M3> M2. M3> M1> M2.

  The porous carrier preferably contains at least one selected from activated carbon, hydrous magnesium silicate clay mineral, bentonite, kaolin, cocoon clay, zeolite, silica gel, and activated alumina. In this case, the strength of the deodorized molded body is improved. Moreover, since a porous support | carrier becomes what is excellent in adsorption | suction of an odor component, the removal performance with respect to the odor component of a deodorizing molded object improves.

  Preferably, the porous carrier contains at least activated carbon. This is because activated carbon is excellent in the performance of adsorbing and removing sulfur compound-based odor components such as methyl mercaptan and hydrogen sulfide, and thus the removal performance of the deodorized molded body from sulfur compound-based odor components can be improved. Moreover, it is preferable to contain at least hydrous magnesium silicate clay mineral. The hydrous magnesium silicate clay mineral has a hydroxyl group rich in reactivity on the surface and is excellent in the ability to adsorb and remove amine-based odor components such as trimethylamine and ammonia. It is because the removal performance with respect to a component can be improved.

  Preferably, the porous carrier contains at least activated carbon and hydrous magnesium silicate clay mineral. In this case, it is because the removal performance with respect to the sulfur compound type odor component and amine type odor component of the deodorized molded article can be further improved. The hydrous magnesium silicate clay mineral is a clay mineral mainly composed of magnesium silicate, such as sepiolite and mountain bark.

  In addition, as the porous carrier, one containing activated carbon and hydrous magnesium silicate clay mineral as a main component and further containing at least one selected from bentonite, kaolin, cocoon clay, zeolite, silica gel, and activated alumina is used. be able to. At this time, when it further contains bentonite, kaolin, and Sasame clay, the strength of the deodorized molded article can be further improved. On the other hand, when zeolite, silica gel and activated alumina are further contained, the adsorption performance of odor components can be further improved.

  Further, the porous carrier contains at least activated carbon and hydrous magnesium silicate clay mineral, and when the total content of both is 100 parts by mass, the activated carbon is 30 to 90 parts by mass and 40 to 80 parts by mass. It is preferable that the hydrous magnesium silicate clay mineral is 10 to 70 parts by mass and 20 to 60 parts by mass. If the content of activated carbon is too small, or if the content of hydrous magnesium silicate clay mineral is excessive, the adsorption performance of the deodorized molded body for odor components may be reduced. On the other hand, when the content of activated carbon is excessive, or when the content of hydrous magnesium silicate clay mineral is excessive, the strength of the deodorized molded body may be reduced. The deodorized molded body preferably has a honeycomb shape. In this case, the deodorized molded body has a large surface area and a large contact area with the odor component. Therefore, the deodorized molded body can efficiently come into contact with the odor component, and the deodorization efficiency can be improved. Note that the honeycomb shape includes a cell having a circular cross-sectional shape or a polygonal shape such as a quadrangle and a hexagon.

According to the manufacturing method according to the second aspect of the present invention, examples of the metal salt containing copper include Cu (NO ₃ ) ₂ , CuCl ₂ , and CuSO ₄ . In addition, as a method of impregnating a metal salt containing copper in the first impregnation step and the second impregnation step, there is a method of immersing a porous carrier in an aqueous solution or the like in which the metal salt is dissolved. In addition, a porous carrier can be impregnated with an aqueous solution in which a plurality of metal salts are dissolved. In the heat treatment step, the porous carrier is heated at a temperature of 400 ° C. to 800 ° C. in an inert gas atmosphere. Here, when the heating temperature is excessively low, the metal salt may not be supported on the carrier as an oxide. As a result, the removal performance of the deodorized molded body with respect to the odor component may be deteriorated. On the other hand, when the temperature is excessively high, the metal salt oxide and the porous carrier are sintered (aggregated), and as a result, the removal performance of the deodorized molded body with respect to the odor component may be lowered. In the heat treatment step, the metal salt becomes a metal oxide in which the oxidation number of the metal in the metal salt is changed, and may be bonded to the porous carrier. For example, when copper nitrate (Cu (NO ₃ ) ₂ ) is used as the metal salt containing copper, the copper nitrate is supported on the porous carrier as cuprous oxide (Cu ₂ O) after the heat treatment step. . At this time, the oxidation number of copper changes from + II to + I. On the other hand, in the drying step, the oxidation number of copper in copper nitrate (Cu (NO ₃ ) ₂ ) remains + II and is supported on the porous carrier. As a result, the same metal (copper) atoms having different oxidation numbers can be bonded in two forms.

In the second impregnation step, it is preferable to use the same metal salt as in the first impregnation step. Preferably, in the first impregnation step and the second impregnation step, an aqueous solution containing copper nitrate as a metal salt containing copper may be used. In this case, in the heat treatment step performed after the first impregnation step, copper nitrate as a metal salt becomes cuprous oxide (Cu ₂ O), and in the drying step performed after the second impregnation step, copper nitrate is Copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ) is supported on the porous carrier. As a result, a deodorized molded article having an excellent deodorizing effect due to a synergistic effect of cuprous oxide (Cu ₂ O) and copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ) can be produced.

  The metal salt containing copper is preferably copper nitrate and / or copper chloride. In this case, a compound containing copper is supported on the porous carrier, and a deodorized molded article having an excellent deodorizing action can be produced by utilizing the excellent deodorizing action of the copper atom. It is particularly preferable to use at least copper nitrate as the metal salt containing copper. In this case, as described above, cuprous oxide and copper trihydroxide nitrate are supported on the porous carrier. As a result, the deodorizing action can be further improved by the synergistic effect of cuprous oxide and copper trihydroxide nitrate.

  In the first impregnation step and the second impregnation step, it is preferable to impregnate the metal salt by immersing the porous carrier in an aqueous solution in which the metal salt containing copper is dissolved. In this case, the porous carrier can be easily impregnated with a metal salt containing copper. In this case, in the drying step, the metal salt can be bound to the porous support in a state where hydroxide ions are bound. Thus, since the metal salt which couple | bonded the hydroxide ion becomes easy to form a complex with an amine type compound, the removal performance with respect to the amine type odor component of a deodorizing molded object can be improved. In addition, a metal salt to which hydroxide ions are bonded is likely to be formed when it is supported on a hydrous magnesium silicate clay mineral that is a basic oxide, for example, sepiolite. Therefore, hydrous magnesium silicate clay mineral is suitable as the carrier for supporting the metal salt.

  Next, in the drying step, the porous carrier is preferably dried at 50 ° C to 180 ° C, particularly 90 ° C to 130 ° C. When the drying temperature is excessively low, a solvent such as water that has entered the pores of the porous carrier cannot be sufficiently removed, and the adsorption removal performance for odor components based on physical adsorption of the deodorized molded article may be reduced. is there. Further, when the drying temperature is excessively high, the metal salt loses acid such as nitric acid and decomposes, so that the removal performance of the deodorized molded body with respect to the nitrogen compound odor component may be excessively lowered.

(Embodiment 1)
1 to 3 show the concept of the first embodiment. The toilet seat device includes a base 1 equipped in the Western-style toilet 100, a toilet seat 2 provided on the base 1 so as to be swingable, and a toilet lid 3 provided on the base 1 so as to be swingable. The base 1 has an odor inlet 1c and an odor outlet 1d communicating with the toilet room. It is preferable that the odor inlet 1 c communicates with the excretion space of the toilet bowl of the toilet 100. It is preferable that the base 1 is equipped with a cleaning nozzle for cleaning a local part such as a toilet part of a user seated on the toilet seat 2.

  As shown in FIG. 3, the base 1 has a deodorized molded body holding portion 4 having a storage space 40 and a deodorized molded body 5 held in the storage space 40 of the deodorized molded body holding portion 4. The deodorized molded body 5 is preferably replaceable with respect to the deodorized molded body holding portion 4, but may not be replaceable. The deodorized molded body holding unit 4 includes a wall 41 forming the accommodation space 40, an inlet 42 located upstream in the accommodation space 40, an outlet 43 located downstream in the accommodation space 40, and between the inlet 42 and the outlet 43. And a fan 44 functioning as an air blowing element. The fan 44 is rotated by a motor. The deodorized molded body 5 includes a porous carrier 50, cuprous oxide, copper trihydroxide nitrate, and paraaminobenzoic acid supported as active ingredients in the porous carrier 50.

As can be understood from FIG. 3, for the porous carrier 50, both cuprous oxide and copper trihydroxide nitrate are supported on the upstream region 50 u and the downstream region 50 d of the porous carrier 50. For this reason, the carrying area and carrying amount of cuprous oxide and copper trihydroxide nitrate are secured. In the downstream region 50d of the porous carrier 50, paraaminobenzoic acid is supported as aminobenzoic acid. Here, the deodorized molded body 5 includes 100 parts by mass of the porous carrier 50, M1 part by mass (for example, 2 to 10 parts by mass) of cuprous oxide (Cu ₂ O), and copper trihydroxide nitrate (Cu). ₂ (OH) ₃ NO ₃ ) is supported by M2 parts by mass (for example, 1-6 parts by mass), and paraaminobenzoic acid is supported by M3 parts by mass (for example, 1-6 parts by mass). Examples are M1> M2 = M3, M1> M2≈M3, and M1>M2> M3. However, it is not limited to this.

According to this embodiment, the following manufacturing method is adopted. First, in the first impregnation step, the entire porous carrier 50 which is a honeycomb structure is impregnated with an aqueous copper nitrate solution ((Cu (NO ₃ ) ₂ aqueous solution.) And the porous carrier 50 is pulled up from the aqueous copper nitrate solution. Next, in the first heat treatment step, the porous carrier 50 after the first impregnation step is heated in an inert gas atmosphere (nitrogen gas) at 500 ° C. to 800 ° C. During this heating, the porous carrier 50 is impregnated. The copper nitrate (Cu (NO ₃ ) ₂ ) thus converted into cuprous oxide (Cu ₂ O) Next, in the second impregnation step, the entire porous carrier 50 after the first heat treatment step is treated with copper nitrate. The porous carrier 50 was pulled up from the aqueous copper nitrate solution, and then in the first drying step, the porous carrier 50 after the second impregnation step is dried at 80 to 150 ° C., for example. During this drying, many Copper nitrate impregnated quality carrier _{50 (Cu (NO 3) 2} ) will trihydroxide copper nitrate _{(Cu 2 (OH) 3 NO} 3). Next, then in the third impregnation step, para Using the aqueous benzoic acid solution, only the downstream portion of the porous carrier 50 after the first heat treatment step is impregnated with the aqueous paraaminobenzoic acid solution, and the porous carrier 50 is pulled up from the aqueous paraaminobenzoic acid solution. The paraaminobenzoic acid aqueous solution is not impregnated with the upstream portion of 50. Next, in the second drying step, the porous carrier 50 after the third impregnation step is dried at 80 to 150 ° C. Thus, the porous carrier 50 is dried. In addition, cuprous oxide, copper trihydroxide nitrate and paraaminobenzoic acid can be supported.

  In the present embodiment, when the toilet lid 3 is opened as shown in FIG. 1, when the fan 44 rotates, the air in the toilet room and the air containing the odor in the excretion space inside the toilet are sucked from the odor inlet 1c. The deodorized molded body holding part 4 flows into the housing chamber 40 from the inlet 42, passes through the inside of the deodorized molded body 5, flows out from the outlet 43, and is further discharged from the odor outlet 1d to the toilet room. Thus, air is deodorized when passing through the inside of the porous deodorized molded body 5. The deodorized and clean air is discharged from the outlet 1d to the toilet room.

  When the toilet lid 3 is closed as shown in FIG. 2, a gap 2c between the toilet bowl and the leg 2a of the toilet seat 2 is formed. Therefore, when the fan 44 rotates, the air in the toilet room is sucked into the toilet from the gap 2c, and further sucked into the odor inlet 1c together with the air in the excretion space inside the toilet, and accommodated from the inlet 42 of the deodorized molded body holding unit 4. It flows into the chamber 40, passes through the inside of the deodorized molded body 5, and is discharged from the odor outlet 1d to the toilet room. In this way, the air is deodorized when passing through the deodorized molded body 5. The deodorized and clean air is discharged from the outlet 1d to the toilet room.

  Here, for sulfur compound odor components such as methyl mercaptan and hydrogen sulfide, cuprous oxide and copper trihydroxide nitrate oxidize sulfur compound odor components to produce sulfur or metal sulfides. It is thought that. In addition, for nitrogen compound odor components such as trimethylamine and ammonia, it is considered that copper trihydroxide nitrate mainly forms a complex with the amine compound. Since both the cuprous oxide and the copper trihydroxide nitrate are supported on the entire porous carrier 50, that is, the upstream region 50u and the downstream region 50d, the supported amount and the supported area are ensured, and the sulfur compound system The odor component and nitrogen compound odor component can be deodorized satisfactorily.

  Furthermore, although paraaminobenzoic acid is supported only in the downstream region 50d of the porous carrier 50, it is not supported in the upstream region 50u. For this reason, paraaminobenzoic acid exerts a deodorizing effect on air from which sulfur compound-based odor components and nitrogen compound-based odor components have been removed. Therefore, even if there is a small amount of paraaminobenzoic acid, it can be deodorized by paraaminobenzoic acid. Good effect is ensured.

  According to the present embodiment, since the porous carrier 50 is formed of a honeycomb structure which is a single structure, the operability is good, each impregnation step and the heat treatment step are simplified, and the assembly property is further improved. Is also convenient. According to the present embodiment, the upstream region 50u and the downstream region 50d in the porous carrier 50 have an apparent volume of the upstream region 50u: an apparent volume of the downstream region 50d = 100 when the total apparent volume of the porous carrier 50 is 100. 50:50. However, not limited to this, it may be 60:40, 70:30, 80:20, or 40:60.

(Embodiment 2)
FIG. 4 shows a second embodiment. Since this embodiment basically has the same configuration and the same operation and effect as those of the first embodiment, FIGS. 1 and 2 are applied mutatis mutandis. Regarding the porous carrier 50, both cuprous oxide and copper trihydroxide nitrate are supported in the upstream region 50 u of the porous carrier 50. In the downstream region 50d of the porous carrier 50, paraaminobenzoic acid is supported. In the downstream region 50d of the porous carrier 50, neither cuprous oxide nor copper trihydroxide nitrate is supported. This is advantageous in increasing the carrying area and carrying amount of paraaminobenzoic acid carried on the downstream region 50d of the porous carrier 50. In this case, it is advantageous for deodorizing odor components of aldehydes such as acetaldehyde.

(Embodiment 3)
FIG. 5 shows a third embodiment. Since this embodiment basically has the same configuration and the same operation and effect as those of the first embodiment, FIGS. 1 and 2 are applied mutatis mutandis. Three components of cuprous oxide, copper trihydroxide nitrate and paraaminobenzoic acid are supported almost uniformly on the entire porous carrier 50 as active components.

(Embodiment 4)
FIG. 6 shows a fourth embodiment. Since this embodiment basically has the same configuration and the same operation and effect as those of the first embodiment, FIGS. 1 and 2 are applied mutatis mutandis. The deodorized molded body 5 is divided into an upstream portion and a downstream portion. The porous carrier 50u forming the upstream portion carries both cuprous oxide and copper trihydroxide nitrate, but does not carry paraaminobenzoic acid. The porous carrier 50d forming the downstream portion carries paraaminobenzoic acid although neither cuprous oxide nor copper trihydroxide nitrate is supported. Since both the cuprous oxide and the copper trihydroxide nitrate are not supported on the porous carrier 50d forming the downstream portion, it is possible to increase the supporting area and the supporting amount of paraaminobenzoic acid supported on the downstream region 50d. It will be advantageous. In this case, it is advantageous for deodorizing odor components of aldehydes such as acetaldehyde. As a result, the apparent volume of the porous carrier 50d that forms the downstream portion is smaller than that of the porous carrier 50u that forms the upstream portion.

(Embodiment 5)
FIG. 7 shows a fifth embodiment. Since this embodiment basically has the same configuration and the same operation and effect as those of the first embodiment, FIGS. 1 and 2 are applied mutatis mutandis. The deodorized molded body 5 is divided into an upstream portion and a downstream portion, and has a diffusion space 50x interposed between the upstream portion and the downstream portion. The porous carrier 50u forming the upstream portion carries both cuprous oxide and copper trihydroxide nitrate, but does not carry paraaminobenzoic acid. The porous carrier 50d forming the downstream portion carries paraaminobenzoic acid although neither cuprous oxide nor copper trihydroxide nitrate is supported. Since both the cuprous oxide and the copper trihydroxide nitrate are not supported on the porous carrier 50d, it is advantageous for increasing the amount of paraaminobenzoic acid supported on the downstream region 50d. In this case, it is advantageous for deodorizing odor components of aldehydes such as acetaldehyde. As a result, the volume of the porous carrier 50d that forms the downstream portion is reduced. The air that has passed through the upstream porous carrier 50u can be diffused in the diffusion space 50x before entering the downstream porous carrier 50d. It is advantageous in reducing deodorization unevenness. Note that cuprous oxide and copper trihydroxide nitrate may be supported on the porous carrier 50d.

  Next, an embodiment of the present invention will be described with reference to FIGS. The reference numerals common to the embodiment are used, but are not necessarily limited to the same structure. The deodorized molded body 5 of the present embodiment is formed by supporting a cuprous oxide, copper trihydroxide nitrate and paraaminobenzoic acid on a porous carrier 50. The porous carrier 50 contains 70 parts by mass of activated carbon and 30 parts by mass of sepiolite, and has a honeycomb structure having a plurality of cells 52 forming a passage having a substantially square cross section. The dimensions of the porous carrier 50 are a = 9.5 mm, b = 9.5 mm, and c = 35 mm in FIG.

That is, the deodorized molded body 5 carries cuprous oxide (Cu ₂ O), copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ), and paraaminobenzoic acid on the entire surface of the porous carrier 50. Yes. The deodorized molded body 5 includes 5 parts by mass of cuprous oxide (Cu ₂ O) and 3 parts by mass of copper trihydroxide (Cu ₂ (OH) ₃ NO ₃ ) with respect to 100 parts by mass of the porous carrier 50. Part, 3 parts by mass of paraaminobenzoic acid is supported.

  A method for manufacturing the porous carrier 50 of this embodiment will be described. First, the porous carrier 50 was prepared. In this case, 70 parts by mass of activated carbon and 30 parts by mass of sepiolite were mixed to obtain a mixture. To 100 parts by mass of this mixture, 140 parts by mass of water and 10 parts by mass of methylcellulose as a binder were added and kneaded sufficiently with a kneader to obtain a kneaded product. This kneaded product was extruded into a honeycomb shape using a vacuum extruder to produce a green compact of a honeycomb formed body. Next, this green compact was dried at room temperature, and then further dried with hot air. Subsequently, the dried green compact was placed in a firing furnace, and the atmosphere in the firing furnace was changed to a nitrogen gas atmosphere, followed by firing at a temperature of 750 ° C. for 3 hours. The dimensions of the porous carrier 50 and the shape of the cell 52 are as described above.

Next, a method for manufacturing the deodorized molded body 5 will be described. The method for manufacturing the deodorized molded body 5 of this example includes a first impregnation step, a first heat treatment step, a second impregnation step, a first drying step, a third impregnation step, and a second drying step. In the first impregnation step, the entire porous carrier 50 was impregnated with a copper nitrate aqueous solution ((Cu (NO ₃ ) ₂ aqueous solution, concentration: 5 mass%) for a predetermined time (5 minutes). Next, in the first heat treatment step, the porous carrier 50 after the first impregnation step was heated in an inert gas atmosphere (nitrogen gas) at 500 ° C. for 3 hours. Instead, argon gas may be used, and during this heating, the copper nitrate (Cu (NO ₃ ) ₂ ) impregnated in the porous support 50 becomes cuprous oxide (Cu ₂ O), and as a result, the porous support 50 Cuprous oxide (Cu ₂ O) is supported on the entire inner wall 53 of the 50 cells 52 and the entire outer surface 54 of the porous carrier 50.

Next, in the second impregnation step, the entire porous carrier 50 after the first heat treatment step was impregnated with an aqueous copper nitrate solution (concentration: 1% by mass) for a predetermined time (5 minutes). And the porous support | carrier 50 was pulled up out of the copper nitrate aqueous solution. Next, in the first drying step, the porous carrier 50 after the second impregnation step was dried at 80 ° C. At the time of drying, the copper nitrate (Cu (NO ₃ ) ₂ ) impregnated in the porous carrier 50 becomes copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ). Thus, copper trihydroxide nitrate is supported on the entire inner wall 53 of the cell 52 of the porous carrier 50 and the entire outer surface 54 of the porous carrier 50.

  Next, in the third impregnation step, a paraaminobenzoic acid aqueous solution (concentration: 3 mass%) is used, and only the downstream portion of the porous carrier 50 after the first heat treatment step is kept in the paraaminobenzoic acid aqueous solution for a predetermined time ( For 10 minutes). The porous carrier 50 was pulled up from the paraaminobenzoic acid aqueous solution. In this case, the upstream portion of the porous carrier 50 is not impregnated with the paraaminobenzoic acid aqueous solution. Next, in the second drying step, the porous carrier 50 after the third impregnation step was dried at 80 ° C.

  In this way, the deodorized molded body 5 formed by supporting the cuprous oxide, copper trihydroxide nitrate and paraaminobenzoic acid on the porous carrier 50 was produced. This is used as a sample. As shown in FIG. 1, the sample is loaded with cuprous oxide, copper trihydroxide nitrate, and paraaminobenzoic acid on the inner wall 53 of the cell 52 of the porous carrier 50 and the outer surface 54 of the porous carrier 50. This is a deodorized molded article in which paraaminobenzoic acid is supported only on the part of the porous carrier 50 (a part of the apparent volume corresponding to the downstream half of the porous carrier 50).

In the present embodiment, first, cuprous oxide (Cu ₂ O) that requires high-temperature heat treatment is preferentially supported on the porous carrier 50, and then copper trihydroxide nitrate that does not require high-temperature heat treatment ( Since Cu ₂ (OH) ₃ NO ₃ ) is supported on the porous carrier 50, both cuprous oxide (Cu ₂ O) and copper trihydroxide nitrate (Cu ₂ (OH) ₃ NO ₃ ) are well porous. It can be carried on a quality carrier 50. Furthermore, since paraaminobenzoic acid is finally supported on the porous carrier 50 among the three types of deodorizing components, the deterioration of paraaminobenzoic acid due to high-temperature heat treatment is suppressed. Furthermore, even if the amount of paraaminobenzoic acid is small enough to be supported only in the downstream region of the porous carrier 50, the paraaminobenzoic acid is suppressed from being covered with the copper-based deodorizing substance. The effect can be exhibited well.

(Comparative example)
Next, in order to clarify the excellent effect of the deodorized molded article 5 produced in Example 1, deodorized molded articles according to Comparative Examples 1 and 2 were produced. First, Comparative Example 1 is a deodorized molded article obtained by supporting 5 parts by mass of cuprous oxide and 1 part by mass of copper trihydroxide nitrate over 100 parts by mass of the porous carrier. is there. Comparative Example 2 is a deodorized molded article obtained by supporting 3 parts by mass of paraaminobenzoic acid over the entire porous carrier with respect to 100 parts by mass of the porous carrier. The size of the deodorized molded body 5 according to Comparative Examples 1 and 2 is the same as that of the example.

(Deodorization test)
Next, the deodorizing performance of the deodorized molded bodies 5 produced in Examples and Comparative Examples 1 and 2 was comparatively evaluated. In the evaluation of the deodorizing performance, the measuring device shown in FIG. 9 was used. As shown in FIG. 9, this measuring apparatus includes three containers 10 each containing three kinds of odor components such as trimethylamine (T), hydrogen sulfide (S), and acetaldehyde (A), and a gas containing each odor component. For installing a flow meter 11 for measuring the flow rate, a mixer 12 for mixing odor components to form a mixed odor gas, a flow meter 13 for measuring the flow rate of the mixed odor gas, and a deodorized molded body 5 And three columns 14. Thus, in the examples, mixed odor gas in which three kinds of trimethylamine (T), hydrogen sulfide (S), and acetaldehyde (A) were mixed was used as the odor component. As shown in FIG. 9, these odor components are individually stored in each of the three containers 10, and are mixed by a mixer 12 connected to each container 10 to form a mixed odor gas. . In the mixed odor gas, the odor components of trimethylamine (T), hydrogen sulfide (S), and acetaldehyde (A) were each 1 ppm. Air was used as the carrier gas. In the measurement, the deodorized molded body 5 was placed on the column 14 in the measuring apparatus. Next, mixed odor gas in which three kinds of odor components were mixed was circulated through each column 14. And the density | concentration of each odor component in the inlet side A and the outlet side B of the column 14 was measured with time. Hydrogen sulfide and acetaldehyde were measured with a gas chromatograph (see Table 1), and trimethylamine was measured with a gas detector tube. The removal rate was determined based on the following equation. Removal rate = {1− (measured concentration ÷ initial concentration)} × 100 (%)

  10 to 12, the horizontal axis represents time, and the vertical axis represents the removal rate (%). About 20 hours is considered to correspond to an odor load for 6 to 9 years in an actual toilet. □ indicates an example. ○ indicates Comparative Example 1. Δ indicates Comparative Example 2. As can be understood from FIGS. 10 to 12, the deodorized molded body 5 according to the present example exhibited comprehensively superior deodorizing performance as compared with the deodorized molded bodies according to Comparative Examples 1 and 2. As shown in FIG. 10, Comparative Example 2 is not very effective for removing hydrogen sulfide, but Example and Comparative Example 1 are almost equivalent, and the deodorizing effect is good over a long period of 5 years or more or 7 years or more. Can demonstrate. As shown in FIG. 12, the example was more effective than the comparative example 1 in removing trimethylamine. As can be understood from FIGS. 10 to 12, in this experimental example, excellent removal performance is obtained for any odor components such as hydrogen sulfide, trimethylamine, and further acetaldehyde which are main odor components of toilets as odor components. In order to show, it can utilize as a deodorizing agent, a deodorizing apparatus, etc. which are installed in a toilet.

  In particular, both Example and Comparative Example 2 carry the same amount (3 parts by mass) of paraaminobenzoic acid. As shown in FIG. 11, up to 5 hours from the start of the test, Comparative Example 2 (marked with Δ) carrying only paraaminobenzoic acid was cuprous oxide, copper trihydroxide nitrate, paraaminobenzoic acid, The removal rate of acetaldehyde is higher than the example (□ mark) supporting the above three. However, as shown in FIG. 11, when the elapsed time from the start of the test was 5 hours or more, the results of Example (□) were higher in the acetaldehyde removal rate than Comparative Example 2 (Δ). In particular, when the elapsed time is 8 hours or more, the difference between the □ mark and the Δ mark increases. Therefore, in the example (□ mark), when the period of use of the deodorized molded body 5 is extended, a result in which the removal rate of acetaldehyde is higher than that of Comparative Example 2 (Δ mark) is obtained.

  The reason is considered as follows. In the embodiment, paraaminobenzoic acid is not supported on the upstream side of the porous carrier 50 and is supported only on the downstream side. That is, only cuprous oxide and copper trihydroxide nitrate are supported on the upstream side of the porous carrier 50, and paraaminobenzoic acid is supported on the downstream side of this region. For this reason, in the embodiment, hydrogen sulfide and trimethylamine contained in the gas are preferentially removed by cuprous oxide and copper trihydroxide nitrate on the upstream side of the porous carrier 50. Thereafter, the gas from which most of hydrogen sulfide and trimethylamine have been removed comes into contact with the paraaminobenzoic acid supported on the relatively downstream side of the porous carrier 50, so that the effect of removing acetaldehyde by the paraaminobenzoic acid is obtained. It is considered to be effective. In Comparative Example 2, although the same amount of paraaminobenzoic acid as in Example 1 is supported, hydrogen sulfide and trimethylamine contained in the gas are in direct contact with paraaminobenzoic acid, so the deodorizing effect of paraaminobenzoic acid is reduced. It is thought to do.

  (Others) The present invention is not limited to the embodiment described above and shown in the drawings, and can be implemented with appropriate modifications within a range not departing from the gist. The porous carrier is not limited to the honeycomb structure, and may be an aggregate of pellets. In this case, a pellet carrying cuprous oxide and copper trihydroxide nitrate may be provided upstream, and a pellet carrying paraaminobenzoic acid may be provided downstream.

1 is a base part, 2 is a toilet seat, 3 is a toilet lid, 4 is a deodorizing molded body holding part, 40 is a storage space, 5 is a deodorizing molded body, and 50 is a porous body.

Claims (4)

A toilet seat device having a base equipped in a Western-style toilet, a toilet seat provided swingably on the base, and a toilet lid provided swingably on the base,
The base has a deodorized molded body holding section and a deodorized molded body held by the deodorized molded body holding section, and the deodorized molded body has copper oxide and copper trihydroxide nitrate as a porous carrier. A toilet seat device formed by carrying an aromatic amino acid as an active ingredient. In Claim 1, copper oxide and copper trihydroxide nitrate are carry | supported in the upstream area | region in the said porous support | carrier, or the whole said porous support | carrier, and the aromatic amino acid is carry | supported in the downstream area | region in the said porous support | carrier. ,
The toilet seat device in which air containing a deodorizing component passes through a portion where an aromatic amino acid is supported after passing through a portion where copper oxide and copper trihydroxide nitrate are supported in the porous carrier.   3. The deodorized molded body according to claim 1, wherein the deodorized molded body includes a first impregnation step of impregnating a porous carrier with a metal salt containing copper, and the porous carrier after completion of the first impregnation step in an inert gas atmosphere. A heat treatment step of heating at 400 ° C. to 800 ° C., a second impregnation step of impregnating the porous carrier after completion of the heat treatment step with a metal salt containing copper, and the porous after completion of the second impregnation step A first drying step of drying the porous carrier, a third impregnation step of impregnating the multi-rigid carrier with an aromatic amino acid after completion of the first drying step, and drying the porous carrier after completion of the third impregnation step A toilet seat device formed by a process including a second drying process.   A first impregnation step of impregnating a porous carrier with a metal salt containing copper, and a heat treatment step of heating the porous carrier after completion of the first impregnation step at 400 ° C. to 800 ° C. in an inert gas atmosphere; A second impregnation step of impregnating the porous carrier after completion of the heat treatment step with a metal salt containing copper, a drying step of drying the porous carrier after completion of the second impregnation step, and the drying step A method for producing a deodorized molded article for a toilet seat device, comprising: a third impregnation step for impregnating the aromatic carrier with the aromatic hard amino acid after completion; and a drying step for drying the porous carrier after completion of the third impregnation step.

Images