JPH114878A - Deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remarkably improve deodorizing capacity and a deodorizing speed to various offensive smells particularly under the existence of moisture by including a metallic complex and/or a transition metal ion having at least oxidation/reduction capacity in a water absorptive resin gelatinized by absorbing moisture. SOLUTION: A deodorant is prepared by including a metallic complex and/or a transition metal ion having at least oxidation/reduction capacity in a water absorptive resin gelatinized by absorbing moisture. The metallic complex and/or the transition metal ion having oxidation/reduction capacity can remarkably improve deodorizing capacity and a deodorizing speed to various offensive smells under the existence of moisture, and particularly extremely effective in a water soluble offensive smell. A metallic phthalocyanine carboxylic acid and a metallic phthalocyanine sulfonic acid are desirable as the metallic complex having oxidation/reduction capacity to be used. The metallic complex and/or the transition metal ion having oxidation/reduction capacity is contained by 0.01 to 5.0 wt.% to the water absorptive resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant, and more particularly to a gel deodorant excellent in deodorizing ability and deodorizing speed.

[0002]

2. Description of the Related Art Conventionally, adsorbents utilizing the physical properties of inorganic porous substances such as activated carbon and deodorants utilizing the chemical properties of metal ion complex formation have been known as substances having a deodorizing effect. Have been. Utilizing these, for example,
Japanese Patent Application Laid-open No. Sho 59-82559, which contains a metal complex having a redox ability and a paraffinic hydrocarbon.
JP-A-189855 discloses a water-absorbent resin impregnated with a stabilized chlorine dioxide solution.
No. 837 discloses a fired product of a mixture of cordierite and a metal oxide catalyst dispersed in a water-absorbent resin.

[0003]

However, these deodorants have the following problems. For example, JP-A-4-
Japanese Patent No. 82559 discloses that by using paraffinic hydrocarbons, it is possible to deodorize odors such as disulfides, sulfites and aromatic compounds, but there is a limit in increasing the deodorizing ability and deodorizing speed. is there. In JP-A-59-189855, chlorine dioxide is liberated at room temperature, evaporates into the air, and deodorizes by utilizing the sublimation phenomenon, and its volatilization rate and deodorizing power are adjusted. Therefore, it is impregnated in a gel-like water-absorbing resin, and if the air is at a high temperature or in a dry state, the volatilization rate and deodorizing power cannot be adjusted, which may cause a significant decrease in deodorizing capacity. is there. Furthermore, Japanese Patent Application Laid-Open No. 7-59837 also discloses that a malodorous component adsorbed by cordierite is changed to an odorless component by a metal oxide catalyst, but the adsorbent generally has a reduced adsorbing function in the presence of moisture. Therefore,
The fact is that a deodorant having both the deodorizing ability and the deodorizing speed has not yet been obtained. The present invention has been made in view of such circumstances, and provides a gel deodorant excellent in deodorizing ability and deodorizing speed.

[0004]

Means for Solving the Problems The deodorant of the present invention is characterized in that a water-absorbent resin that has absorbed water and gelled contains at least a metal complex and / or a transition metal ion having a redox ability. And With this configuration, the deodorizing ability and the deodorizing rate of the metal complex and / or transition metal ion having a redox ability are remarkably improved in the presence of moisture.

The metal complex having a redox activity of the present invention is
It is desirably at least one selected from metal phthalocyanine carboxylic acids and metal phthalocyanine sulfonic acids. By using such a metal complex, excellent deodorizing ability and deodorizing speed can be realized.

[0006] The metal complex and / or transition metal ion having an oxidation-reduction ability is added to the water-absorbent resin in an amount of from 0.01 to 0.01%.
It is desirable to contain 5.0% by weight. With such a content, excellent deodorizing ability and deodorizing speed can be realized.

The water content of the gelled water-absorbent resin of the present invention is desirably 2000% or more based on the weight of the water-absorbent resin. By adjusting the water content to such a value, the metal complex and / or transition metal ion having a redox ability can have excellent deodorizing ability and deodorizing speed, and can have an appropriate viscosity and can be easily handled.

The deodorant of the present invention contains an antibacterial agent in an amount of from 0.01 to 0.01%.
It is desirable to contain 1.0% by weight. With this configuration, it is possible to prevent the rot of the gelled water-absorbent resin. Hereinafter, the contents of the present invention will be specifically described.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The deodorant of the present invention contains at least a metal complex having a redox ability and / or a transition metal ion in a water-absorbent resin which has absorbed water and has been gelled. The metal complex and / or transition metal ion having a reducing ability has a deodorizing ability and a deodorizing rate against various malodors in the presence of moisture as compared with a metal complex and / or a transition metal ion supporting resin having a normal redox ability. It is extremely effective especially for water-soluble odor. Although the mechanism of the deodorant is not clear, among the malodorous substances, water-soluble substances such as ammonia, hydrogen sulfide, and acetic acid easily dissolve in water in the gelled water-absorbing resin, and the Since a metal complex and / or transition metal ion having a redox ability is supported on the surface, the surface area of the reaction field can be effectively used, or oxygen in bubbles taken in the gel has a redox ability It is presumed that the reaction of the metal complex against malodor is accelerated.

The metal complex having a redox ability used in the present invention includes metal porphyrin, metal porphyrazine and derivatives thereof having a redox ability. Among them, metal phthalocyanine monocarboxylic acid and metal phthalocyanine polycarboxylic acid are exemplified. Preference is given to the metal phthalocyanine carboxylic acids, metal phthalocyanine monosulfonic acids and metal phthalocyanine polysulfonic acids of the acids. The transition metal ions used for this are Fe, Co, Mn, Ti, V, Ni, C
u, Zn, Mo, W, etc., among which Fe and Co are preferred from the viewpoint of deodorizing effect. Specific examples of metal complexes having an oxidation-reduction ability include cobalt phthalocyanine octacarboxylic acid, cobalt phthalocyanine tetracarboxylic acid,
Examples include iron phthalocyanine octacarboxylic acid, iron phthalocyanine tetracarboxylic acid, cobalt phthalocyanine octasulfonic acid, cobalt phthalocyanine tetrasulfonic acid, iron phthalocyanine octasulfonic acid, and iron phthalocyanine tetrasulfonic acid. These metal complexes are used alone or in combination of two or more.

The transition metal ions used in the present invention are preferably Fe, Co, Ni, Cu, Zn and the like.
Substances that provide these transition metal ions include salts of these metals, such as carbonates, sulfates, and acetates, and metal oxides. These transition metal ions are used alone or in combination of two or more. The transition metal ion is preferably used because it has an antibacterial effect in addition to the deodorizing effect.

The metal complex and / or transition metal ion having a redox activity with respect to the water-absorbing resin is 0.0
The content is preferably 1 to 5.0% by weight. More preferably, it is 0.1 to 2.0% by weight. If the amount is less than 0.01% by weight, excellent deodorizing ability cannot be obtained. If the amount is more than 5.0% by weight, the deodorizing ability is improved, but the cost is high.

In the deodorant of the present invention, in order to bring out the excellent deodorizing ability and deodorizing rate of the metal complex and / or transition metal ion having the redox ability, it is necessary to support the metal complex in the presence of a large amount of water. It is an essential requirement, and it is a particularly preferred form to use a water-absorbing resin that has absorbed water and has been gelled, especially in consideration of handleability and the like. As the water-absorbing resin used in the present invention, cellulose, natural polymers such as starch, polyvinyl alcohol, polyacrylic acid,
Synthetic polymer substances such as polymethacrylic acid and metal salts or alkyl esters thereof, and polymethacrylamide.

The water absorbed when the water-absorbent resin is gelled is preferably at least 2,000% in water content with respect to the water-absorbent resin. More preferably, it is 3000-8000%. The gelled water-absorbent resin can be easily obtained by forcibly applying a large amount of water of 2000% or more to the water-absorbent resin. The water content of a normal metal complex having a redox ability and / or a transition metal ion-carrying water-absorbent resin is about 15 to 20%, and absorbs moisture in the air when left in air for a long time. The amount is also less than 100% moisture content, and if the moisture content is less than 100%, the effect of the excellent deodorizing ability and deodorizing speed against various malodors in the presence of moisture as described above is hardly obtained. If the moisture content is less than 2000%, it depends on the purpose of use and the place of installation. However, because the evaporation rate of water is too fast, the deodorizing performance remains sufficiently.
The replacement time comes soon, which makes it impractical. If the water content is more than 8000%, the water-absorbent resin becomes liquid, and the handling property becomes inconvenient. For example, when the container containing the deodorant is tilted, it spills out. This is because there is a possibility that it will have an effect.

In the deodorant of the present invention, the gelled water-absorbent resin is easily decomposed by bacteria and microorganisms.
It is preferable to contain 1.0% by weight. The antibacterial agent used in the present invention is not particularly limited, and may be appropriately selected from known materials, and examples thereof include a cationic compound such as “Marcaside” manufactured by Osaka Kasei Co., Ltd. If these antibacterial agents are less than 0.01% by weight, it is not possible to prevent decay of the water-absorbing resin. This is because it is inferior in biodegradability.

The deodorant of the present invention may be used in combination with a substance other than the above substances, for example, a deodorant or a stabilizer having another deodorant function. Absent.
For example, carbon atoms having 5 to 7 carbon atoms which are excellent in deodorizing function against malodor such as disulfide, sulfites and aromatic compounds.
It is possible to add a substance that deodorizes a malodorous component that is not a water-soluble substance in nature, such as a paraffinic hydrocarbon of 0.

The deodorant of the present invention can be roughly obtained by the following two production methods. (1) A metal complex having a redox ability by adding an aqueous solution such as water or an aqueous sodium hydroxide solution in which a granular or powdered substance of a transition metal ion and / or a transition metal ion is dissolved to a water-absorbing resin. And / or a water-absorbing resin supporting transition metal ions is prepared in advance. Then, the obtained water-absorbent resin is gradually added to a predetermined amount of water while being stirred, dispersed, and gelled. (2) First, a granular or powdery metal complex and / or transition metal ion having a redox ability is added to a predetermined amount of water, and a water-absorbent resin is gradually added thereto while stirring the water. And then dispersed and gelled. In the gelled deodorant thus obtained, a metal complex having a redox ability and / or a transition metal ion is uniformly dispersed in the gelled water-absorbent resin, and a stable deodorant performance is obtained. Can be The deodorant of the present invention is filled in, for example, a plastic container or a paper container having an inner surface coated with aluminum, and is used as a deodorant for general household use, in-car use, and the like.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described with reference to embodiments. The gas removal amount was measured as described below.

(Amount of gas removed) 1 g of a deodorant was placed in a gas analysis bag (volume: 5 liters) made of vinylidene fluoride film, and an odorous gas having an initial concentration of 250 ppm was sealed therein. Is measured, and the difference between the initial concentration and the gas concentration every time is determined. The gas removal amount (mg / g) was calculated by calculating the weight (mg) of the removed gas per 1 g of the absolute dry weight of the deodorant by the following formula.

[0020]

(Equation 1)

Example 1 As a metal complex having a redox ability, cobalt phthalocyanine tetrasulfonic acid 0.1.
5 g, and 5 g of copper sulfate pentahydrate as a transition metal ion
Is dissolved in 20 g of deionized water, and a polyacrylic acid-based water-absorbent resin (product name "Alabsorb", manufactured by Arakawa Chemical Industries, Ltd.)
Spraying was added to 100 g to produce a metal complex and a transition metal ion-supporting water-absorbing resin. Then, 15 g of a product name "Marcaside" (manufactured by Osaka Kasei Co., Ltd.) as an antibacterial agent
The above metal complex and the transition metal ion-supporting water-absorbent resin are gradually added to 3 liters of water to which water is added, and dispersed. Then, a gel-like deodorant in which appropriate bubbles were taken into the gel by the stirring action was obtained. The water content of the obtained gel deodorant was 3000%.

Example 2 An antibacterial agent containing 15 g of "Marcaside" (manufactured by Osaka Kasei Co., Ltd.) was added.
1 g of sodium hydroxide is added to 1 liter of deionized water, and 0.1 g of iron phthalocyanine octacarboxylic acid as a metal complex having a redox ability is uniformly dissolved and neutralized with acetic acid. After adding and dissolving 1 g of zinc sulfate heptahydrate as a transition metal ion, a polyacrylic acid-based water-absorbing resin (product name “Alabsorb”, manufactured by Arakawa Chemical Industry Co., Ltd.) 10
0 g is added slowly with stirring and dispersed. Then, a gel-like deodorant in which appropriate bubbles were taken into the gel by the stirring action was obtained. The water content of the obtained gel deodorant was 3000%.

Comparative Example 1 As a metal complex having a redox ability, cobalt phthalocyanine tetrasulfonic acid 0.1.
5 g, and 5 g of copper sulfate pentahydrate as a transition metal ion
Is dissolved in 20 g of deionized water, and a polyacrylic acid-based water-absorbent resin (product name "Alabsorb", manufactured by Arakawa Chemical Industries, Ltd.)
Spray was added to 100 g to give a particulate deodorant.
The water content of the obtained deodorant was 20%. Example 1
Table 1 shows the change of the gas removal amount with respect to the elapsed time of Comparative Example 2 and Comparative Example 1.

[0024]

[Table 1]

With respect to the amount of ammonia removed in the examples and comparative examples, a difference of more than 20 times in the amount of deodorant removed per absolute dry weight after 24 hours is seen. On the other hand, with respect to the hydrogen sulfide removal amount as well, in Examples 1 and 2, a difference in the removal amount by 8 times or more is seen after 24 hours as compared with Comparative Example 1. Therefore, the deodorant of the embodiment of the present invention has a capacity of 300
The presence of a large amount of 0% water greatly improves the deodorizing performance and the deodorizing speed, so that the content of the redox-active metal complex having the deodorizing function and the transition metal ion is reduced. This is advantageous in terms of cost. Further, the deodorants of Examples 1 and 2 are sufficiently gelled, and are cylindrical with an inner diameter of 7.5 cm and a height of 5.5 cm.
When 150 g of the gel deodorant was filled into a paper container having a mesh-shaped upper lid attached to a paper container whose inner surface was coated with aluminum, and the container was inclined at 45 degrees, the gel deodorant inside did not spill. Further, when the deodorant filled in the container was left in the toilet for one month, the gel deodorant retained the gel state although about one third of the volume had evaporated. And the deodorizing performance did not change. No odor or discoloration due to decay of the water-absorbing resin was observed.

[0026]

The deodorant of the present invention is capable of reducing various odors by containing at least a metal complex having a redox ability and / or a transition metal ion in a water-absorbing resin which has been gelled by absorbing water. The deodorizing ability (gas removal amount) and the deodorizing rate are dramatically improved as compared with ordinary non-gelled redox-capable metal complexes and / or transition metal ion-carrying resins. It is extremely effective. Conventional gel-like deodorants have volatile deodorizing components, so if the air is at a high temperature or in a dry state, the volatilization rate and deodorizing power cannot be adjusted, which may cause a significant decrease in deodorizing capacity. However, since the deodorant component of the deodorant of the present invention is non-volatile, and the malodor is dissolved in the gelled water-absorbent resin to deodorize the deodorant, the deodorant ability under severe conditions in the air is low. It does not change. In addition, since the form of the deodorant of the present invention is a gel, it is easy to handle, and the deodorant component is non-volatile, but water evaporates constantly, so that the volume of the gel is reduced by evaporation of water. Therefore, since the replacement time can be clearly determined, it is suitable for use as a deodorant for general household use, in-vehicle use and the like, for example, filled in a container or the like.

Claims (5)

[Claims] 1. A deodorant characterized in that a water absorbing resin gelled by absorbing water contains at least a metal complex having a redox ability and / or a transition metal ion. 2. The deodorant according to claim 1, wherein the metal complex having a redox ability is at least one selected from metal phthalocyanine carboxylic acids and metal phthalocyanine sulfonic acids. 3. The method according to claim 1, wherein the metal complex having a redox ability and / or a transition metal ion is present in an amount of 0.01 to 0.01 with respect to the water absorbing resin.
3. The deodorant according to claim 1, which contains 5.0% by weight. 4. The deodorant according to claim 1, wherein the water content of the gelled water-absorbent resin is 2,000% or more based on the weight of the water-absorbent resin. 5. The deodorant according to claim 1, wherein the gelled water-absorbent resin contains 0.01 to 1.0% by weight of an antibacterial agent.