JP2690835B2 - Deodorants - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant for odors of thiols (mercaptans) among malodors and offensive odors in daily life.

[0002]

2. Description of the Related Art Generally, smoke and waste liquid from factories, cigarettes and raw sewage, kitchen garbage, and the like are sources of offensive odors and offensive odors, and there are various types thereof. At home, odors from toilets, kitchens, pets, cigarettes, etc. cause discomfort, frustration, headaches, and the like. In particular, when the air conditioner is operated, it is often kept in a closed room, so countermeasures against these malodors and offensive odors are a big problem.

Examples of such substances that cause offensive odors and unpleasant odors in daily life include amines such as trimethylamine, which is a perishable odor of fish and meat, ammonia of toilet odor,
Examples thereof include hydrogen sulfide which is a rotten odor of eggs and milk, rotten odor of vegetables and garbage, manure odor, sewage odor, socks odor, and thiols such as methanethiol which is a pickle odor, and disulfides.

Conventionally, as the deodorant, for example, a deodorant solid composed of a gas adsorbing substance capable of deodorizing by physically adsorbing an odor substance such as a porous body of activated carbon or ceramics. is there. There are also chemically reactive deodorant solids. For example, Fe, Mn, Cr, Ni, Z
Pores having a skeleton made of a three-dimensional mesh-like sintered body of a metal such as n, Al, or Cu, and the surface of the skeleton covered with a reaction product (complex) of the metal and oxypolybasic acid. There is a deodorant solid composed of a body (hereinafter, this may be referred to as "metal-oxy polybasic acid type porous body"). This deodorant solid can be deodorized and removed by subjecting odorous substances to chemical reactions such as oxidation, reduction and neutralization.

[0005]

However, the deodorant solid composed of the above-mentioned metal-oxypolybasic acid type porous body is not suitable for odor substances having high chemical reactivity such as amines, ammonia and hydrogen sulfide. Although it exhibits an excellent deodorizing effect, there is a problem that the deodorizing effect is not sufficient for a sulfur-based odorous substance such as thiols having poor chemical reactivity. For example, among sulfur-based odorous substances, hydrogen sulfide is weakly acidic, so it is possible to neutralize and deodorize it with a deodorant solid carrying a basic substance, but thiols are almost neutral. Therefore, it cannot be expected to use the neutralization reaction to deodorize.

Further, even with the above-mentioned conventional deodorant solids composed of gas adsorbents, there is a problem that it is often difficult to deodorize sulfur odors such as thiols. In view of such circumstances, it is an object of the present invention to provide a deodorant having an excellent deodorizing effect particularly on thiol-based odors among odors in daily life.

[0007]

Means for Solving the Problems In order to solve the above problems, the inventors have made various studies. As a result, the present invention was completed by confirming the following by experiments. That is, the thiols (R-SH) are thiol radicals (R-S.) In the presence of a base, as described later in detail.
Generate.

Radicals are generally highly reactive substances, and when other radicals are present, they react significantly with them. Therefore, if a radical is allowed to exist on the surface of the deodorant solid carrying the basic substance, the basic substance carried on the deodorant solid reacts with the thiol to generate a thiol radical. Later, this thiol radical
By reacting with the radicals present on the surface of the deodorant solid, the substance is changed into a substance that is no longer in a gaseous state. As a result, the odor of thiols is deodorized.

Therefore, the deodorant according to the present invention is
A deodorant for a thiol-based odor, which is characterized by comprising a deodorant solid carrying a basic substance and having radicals on its surface. The deodorant solid used in the present invention is not particularly limited, but for example, the above-mentioned activated carbon, a gas adsorbing material made of a porous material such as ceramics or a porous material such as a metal-oxy polybasic acid porous material. Etc. These may be used alone or in combination of two or more.

The basic substance supported by the deodorant solid is not particularly limited, but a solid without deliquescent is preferable. The basic substance is not particularly limited, but examples thereof include alkaline earth metal basic salts, specifically, slaked lime (calcium hydroxide). The amount of the basic substance supported on the deodorant solid is not particularly limited, but in order to efficiently generate a thiol radical by the above-described reaction of the basic substance and the thiols, the deodorant solid is preferably added to the deodorant solid. 0.01 to 10 basic substances
% By weight (in this specification, "to" means "greater than or equal to")
It is preferred that If less than 0.01% by weight,
The thiol radical formation reaction is less likely to occur, and 10
This is because if it exceeds the weight%, the deodorizing performance of the deodorant solid itself may be impaired.

The form of the deodorant of the present invention includes, for example, tablets, granules, powders, blocks, plates and the like, and is not particularly limited. Further, the size and particle size of the deodorant are not particularly limited. The basic substance is
It is preferable that the deodorant solid is locally supported and unevenly distributed, rather than being entirely supported on the deodorant solid.

Examples of the method of supporting the basic substance on the deodorant solid include, but are not limited to, a method of treating the deodorant solid with a treatment liquid containing a basic substance, which will be described later. However, other methods may be used. Other methods include, for example, a method of applying an adhesive or the like on a part of the surface of the deodorant solid, and then directly adding a basic substance to adhere the deodorant solid.

A method for supporting a basic substance on a deodorant solid by treating the deodorant solid with a treatment liquid containing a basic substance will be described below. The solvent used for incorporating the basic substance into the treatment liquid is not particularly limited, and examples thereof include water. Regarding the concentration of basic substances in the treatment liquid and the method of preparing the treatment liquid,
There is no particular limitation.

The method of treating the deodorant solid with the treatment liquid containing a basic substance is not particularly limited, but the treatment liquid is attached to the deodorant solid by, for example, a dipping method or a spray method. After that, a method of drying and the like can be mentioned. Conditions such as temperature and time of treatment are not particularly limited. The method for causing radicals to be present on the surface of the deodorant solid carrying the basic substance is not particularly limited, and for example, a method of treating the deodorant solid carrying the basic substance with a radical-generating treatment agent, etc. Can be mentioned.

A method of treating a deodorant solid carrying a basic substance with a radical-generating treatment agent will be described below. The radical generating agent used is not particularly limited, but examples thereof include an aqueous solution containing Fe ²⁺ and / or Ti ³⁺ , and hydrogen peroxide water. For example, when a deodorant solid is treated with an aqueous solution containing Fe ²⁺ and hydrogen peroxide as a radical-generating treatment agent, the reaction as shown in the following chemical formula 1 progresses, thereby deodorizing Radicals can be generated on the surface of a crystalline solid.

[0016]

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(In the formula, M represents a deodorant solid.) As shown in Formula 1, first, Fe ²⁺ is reacted with hydrogen peroxide (H ₂ O ₂ ) to generate a hydroxy radical (. O
H) is produced, and this hydroxy radical is reacted with a deodorant solid (M-OH ⁻ ) carrying a basic substance to give a deodorant solid (M-OH ⁻ ) having a radical on the surface.
O ₂ ^- ·) it is possible to obtain.

The concentrations of both the treating agent containing the aqueous solution containing Fe ²⁺ and / or Ti ³⁺ and the hydrogen peroxide solution are not particularly limited, but in order to sufficiently generate radicals on the surface of the deodorant solid, Fe is required. It is preferable that the concentration of one of ²⁺ or Ti ³⁺ (the total concentration of these ions when used together) and hydrogen peroxide is 0.5 mol / liter or more. The source of Fe ²⁺ is not particularly limited,
For example, iron (II) salts such as FeSO ₄ and FeCl ₂ may be mentioned. The supply source of Ti ³⁺ is not particularly limited, but examples thereof include titanium (III) salts such as TiCl _{3 and the} like.

The method of performing the treatment using the radical generation treatment agent is not particularly limited, and examples thereof include a method of dropping the radical generation treatment agent on a deodorant solid carrying a basic substance. When an aqueous solution containing Fe ²⁺ and / or Ti ³⁺ and a hydrogen peroxide solution are used as the radical generation treatment agent, it is necessary to use both treatment agents in a separated form. If an aqueous solution containing Fe ²⁺ and / or Ti ³⁺ and a hydrogen peroxide solution are used in a mixed form, the hydroxy produced by the reaction of Fe ²⁺ and / or Ti ³⁺ with hydrogen peroxide is used. This is because radicals are instantly generated and disappeared when the two liquids are mixed, so that it becomes impossible to generate radicals on the surface of the deodorant solid by reacting the hydroxy radical with the deodorant solid. .

The aqueous solution containing Fe ²⁺ and / or Ti ³⁺ and the hydrogen peroxide solution may be added at the same time or separately as long as they are used in separate forms. When the treatment agents are separately dropped, the order of dropping these treatment agents is not particularly limited, but it is preferable to drop the aqueous solution containing Fe ²⁺ and / or Ti ³⁺ and then drop the hydrogen peroxide solution. The dropping time is not particularly limited, but a few minutes is sufficient. The treatment temperature is also not particularly limited, but it is preferable to perform the treatment at room temperature using a treatment agent at room temperature.

[0021]

The thiols (R-SH) are thiol radicals (R-S) in the presence of a base, as shown in the following chemical formula 2.
・) Is generated.

[0022]

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Radicals are generally highly reactive substances, and when other radicals are present, they will react significantly with them. Therefore, when a basic substance is supported on the deodorant solid and radicals are allowed to exist on the surface of the deodorant solid, the basic substance and the thiols supported on the deodorant solid are represented by the above formula. After reacting in accordance with 2 to generate a thiol radical, the thiol radical reacts with a radical existing on the surface of the deodorant solid to be changed into a substance which is no longer in a gaseous state. As a result, it becomes possible to eliminate the odor of thiols.

[0024]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. -Example 1-Slaked lime was added to water and mixed to precipitate an excess of slaked lime that was not dissolved in water, and the supernatant was taken out to obtain a saturated aqueous solution of slaked lime.

To a saturated aqueous solution of this slaked lime (room temperature), 10
A deodorant solid consisting of a block-shaped metal-oxypolybasic acid type porous body (commercially available product) with a size of 10 cm x 10 cm x 1 cm is immersed so that the whole is immersed, and after 5 minutes, it is pulled up and lightly shaken to drain. I went. Then, it was dried at 70 ° C. for about 5 hours using a dryer to obtain a metal-oxypolybasic acid type porous body supporting slaked lime. In this porous body,
The amount of slaked lime supported was 1% by weight based on the weight of the porous body before being supported.

Next, to the obtained metal-oxypolybasic acid type porous material supporting slaked lime, a TiCl ₃ aqueous solution (room temperature) having a concentration of 1 mol / liter was dropped for 5 minutes, and then a concentration of 1
Mol / liter hydrogen peroxide solution (room temperature) was added dropwise for 5 minutes. Then, the porous body was air-dried at room temperature to obtain a deodorant. - In Examples 2-3 and Comparative Example 1 Example 1, in the same manner as in Example 1 was changed to as shown the concentration of TiCl ₃ solution and the hydrogen peroxide solution in the following Table 1, deodorants Got

Example 4 In Example 1, TiCl _{3 having} a concentration of 1 mol / liter was used.
A deodorant was obtained in the same manner as in Example 1 except that an FeCl ₂ aqueous solution having the same concentration was used instead of the aqueous solution. -Example 5-Example 1 except that as the deodorant solid, granular activated carbon (commercially available) having a diameter of 2 to 3 mm was used instead of the metal-oxypolybasic acid type porous body. In the same manner, a deodorant was obtained.

-Comparative Example 2-The deodorant solid consisting of the metal-oxy polybasic acid type porous material used in Example 1 was used as it was as a deodorant without treatment. -Comparative Example 3-The activated carbon (commercially available product) used in Example 5 was used as a deodorant without treatment.

The deodorizing performance of each of the deodorants obtained in the above Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated by the following method using the apparatus shown in FIG. As shown in the figure, first, the upper and lower two-stage mesh 2 containing the deodorant 1 was placed in the acrylic resin chamber 3 having a volume of 40 liters, and methanethiol was injected as a malodorous gas. In order to make the concentration of methanethiol in the chamber 3 uniform, the initial concentration (C ₀ ) of methanethiol was measured by the gas detection tube 5 after being blown and stirred by the circulation fan 4 in the direction of arrow A for several minutes. It was 100 ppm.

Next, the fan 6 for blowing air in the direction of arrow B was actuated to accelerate the odor to the deodorant 1 and left for about 30 minutes. After that, the concentration (C ₁ ) of methanethiol was measured by the gas detection tube 5, and the gas residual ratio of methanethiol [= C ₁ / C ₀ × 10
0 (%)] was calculated. The results are shown in Table 1 below.

[0031]

[Table 1]

The annotations in Table 1 are as follows. * 1: Amount supported on deodorant solids. As shown in Table 1,
It was confirmed that the deodorants of Examples 1 to 5 were significantly superior in deodorizing power to methanethiol as compared with the deodorants of Comparative Examples 2 and 3 which were composed of only deodorant solids. Also,
From the comparison between Examples 1 to 5 and Comparative Example 1, it was confirmed that if the concentration of the radical-generating treatment agent was too low, the deodorizing power was lowered.

[0033]

INDUSTRIAL APPLICABILITY The deodorant according to the present invention has an excellent deodorizing effect particularly on thiol-based odors among odors in daily life.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an apparatus used for evaluating deodorizing performance of a deodorant in Examples and Comparative Examples.

[Explanation of symbols]

 1 deodorant

Claims (1)

(57) [Claims] 1. A deodorant for a thiol-based odor, comprising a deodorant solid carrying a basic substance and having radicals on the surface thereof.