JPS63249565A - Deodorant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a deodorant for various malodorous substances. More specifically, it is a completely new deodorant that is made of clay minerals with specific metal ions or metal compounds between its layers, has excellent deodorizing ability against various malodorous substances, and is highly safe and stable. It provides:

[Prior Art] Nowadays, people are placing more importance on the sense of living that seeks comfort, and there is growing social interest in various malodorous substances such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes that are generated in daily life. Various types of deodorants are commercially available and used to remove odor.

These deodorants not only have a strong deodorizing effect on various malodorous substances, but also have a high degree of safety as they are used in daily life, are easy to handle, and have a good appearance such as color tone. It is also desired that

However, a deodorant that satisfies all of these conditions has not yet been developed. For example, activated carbon, which is most commonly used as a deodorant, is excellent against malodorous substances such as mercaptans and amines, but is less effective against hydrogen sulfide and ammonia. It also has the disadvantage that its deodorizing effect decreases when it gets wet with water. Because activated carbon is black in color, it is difficult to use for everyday purposes. Other deodorants that utilize chemical reactions include acidic agents, alkaline agents, and oxidizing agents such as stabilized chlorine dioxide and hydrogen peroxide, but they have safety issues and
Disadvantages include that the amount of malodorous substances that can be deodorized is limited and that it dissolves in water.

[Problems to be Solved by the Invention] In view of the above circumstances, the present inventors have developed a product that 1) has excellent deodorizing ability against a wide range of malodorous substances, 2) is easy to handle, and 2) has good appearance such as color tone. ■ As a result of extensive research to obtain a safe deodorant, clay minerals with specific metal ions or metal compounds between layers have been found to be effective against various malodorous substances such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes. On the other hand, we have discovered that the above objects can be achieved, such as having extremely excellent deodorizing ability, even when the powder itself is wet with water or the like, and based on this knowledge, we have completed the present invention.

Means for solving the problem between
and a deodorant made of a clay mineral, characterized by having metal ions or metal compounds other than calcium between layers.

Hereinafter, the configuration of the present invention will be explained in detail.

The deodorant according to the present invention is made of a clay mineral having metal ions or metal compounds other than sodium, potassium, lithium, and calcium between layers, as described above.

Specifically, metals other than sodium, potassium, lithium, and calcium include magnesium, aluminum, manganese, silver, nickel, iron, zinc, cobalt,
Examples include cadmium and copper. Among these, silver, zinc, cobalt, cadmium, and copper are preferred.

Examples of metal compounds other than sodium, potassium, lithium, and calcium include hydroxides and oxides of the metals mentioned above. In the present invention, these metal compounds may be present alone or in a mixture of two or more kinds between the clay mineral layers.

The deodorant of the present invention may be any deodorant as long as it has the metal ions or compounds mentioned above between the layers, and therefore it does not negate the deodorant having the metal ions or compounds mentioned above on the surface of the clay mineral.

In order to obtain the deodorant according to the present invention, a water-swellable clay mineral is used as a raw material.

Water-swellable clay minerals are layered silicate minerals belonging to the genus smectite, and are generally referred to as montmorillonite, beidellite, nontronite, sabonite, hectorite, and the like. It may be either natural or synthetic. Commercially available products include Kunipia, Smectone (Kunimine Industries), Veegum (Panderbilt), Laponite (Laborte), and Fluorotetrasilicon Mica (Tobi Industries). In carrying out the present invention, one or more types of water-swellable clay minerals are arbitrarily selected from among these water-swellable clay minerals.

Cations such as sodium ions and lithium ions usually exist between the layers of these water-swellable clay minerals, and electrically neutralize the entire water-swellable clay mineral, but these cations are exchangeable. , can be easily replaced by other cations. This cation exchange capacity varies depending on the type of water-swellable clay mineral, but is approximately 60 to 150 milliequivalents per 100 g of clay mineral.

One embodiment of the deodorant according to the present invention, the clay mineral having one or more metal ions other than sodium, potassium, lithium, and calcium between the layers, is a clay mineral having interlayer metal ions ( It can be obtained by replacing part or all of the exchangeable cations with one or more metal ions excluding sodium, potassium, lithium, and calcium.

It is desirable that the substitution rate is the same as the cation exchange capacity of the water-swellable clay mineral (that is, substantially 100%), but an excellent deodorizing effect can be obtained even at approximately 50% of the cation exchange capacity.

Specific manufacturing methods include aluminum, manganese,
Water-soluble metal salts such as chlorides, nitrates, sulfates, acetates, etc. of silver, nickel, iron, zinc, cobalt, cadmium, copper, etc. are dissolved in water and/or an organic solvent, and water-swellable clay minerals are dissolved in water and/or an organic solvent. Disperse and separate the precipitated clay minerals,
If necessary, the deodorant of the present invention is obtained by washing) and drying.

As the organic solvent, common solvents such as ethanol, methanol, and acetone are used.

The concentration of the water-swellable clay mineral during production is not particularly limited, but if it exceeds 20 weight, stirring becomes difficult and ion exchange becomes difficult. The amount of metal ions in the dispersion is
It is desirable that the cation exchange capacity is greater than or equal to that of the water-swellable clay mineral. If the cation exchange capacity is less than 50%, the resulting clay mineral will have poor deodorizing effect. The temperature of the dispersion liquid when performing the ion exchange reaction can be set at any temperature.
Usually room temperature is sufficient. The deodorizer of the present invention may be obtained by separating and collecting clay minerals produced as precipitates, but
It may be washed and dried if necessary.

In particular, when used in a system where there is concern that metal ions attached to the surface may have an adverse effect, cleaning is preferable. The drying temperature may be any temperature as long as it is below the decomposition temperature of the clay mineral, but when the interlayer metal ions are cobalt ions, it is particularly preferably 200°C or above. For other ions, the higher the drying temperature for -a, the better the deodorizing effect, but 8
0°C is also sufficient.

These interlayer metal ions have a deodorizing effect on malodorous substances through chemical reactions such as oxidation, and clay minerals themselves have a deodorizing effect due to their adsorption ability, so the deodorant of the present invention has a synergistic deodorizing effect on both. It is an excellent deodorant. Clay minerals that have been replaced by metal ions have weaker water swelling properties and are less likely to gel when in contact with water, but are well dispersed in water and exhibit a strong deodorizing effect even in that state. Furthermore, since these metal ions are bonded between layers through ion exchange reactions, they do not elute into water, and there is no problem in terms of safety.

Another embodiment of the deodorant of the present invention is a clay mineral having interlayer metal compounds other than sodium, potassium, lithium, and calcium, in which the interlayer metal ions of the above-mentioned water-swellable clay mineral are sodium, potassium, lithium,
and one or more metal compounds other than calcium.

Specifically, the manufacturing method is to dissolve a water-soluble metal salt in water and/or an organic solvent, disperse water-swellable clay minerals therein, and remove interlayer metal ions from metals other than sodium, potassium, lithium, and calcium. Replace with ions. An alkaline solution is added dropwise to this dispersion while stirring, and the resulting precipitate is separated and collected to obtain a clay mineral having metal hydroxide between layers. Next, by drying while controlling heating conditions, a clay mineral having metal hydroxide and/or metal oxide between layers can be obtained.

As water-soluble metal salts used at this time, chlorides, nitrates, sulfates, acetates, etc. of aluminum, manganese, silver, nickel, iron, zinc, cobalt, cadmium, copper, etc. can be used.

As the alkaline solution, a solution in which an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved in water and/or an organic solvent is used.

As the organic solvent, common solvents such as ethanol, methanol, and acetone are used.

The concentration of the water-swellable clay mineral during production is not particularly limited, but if it exceeds 20 weight, stirring becomes difficult and exchange with metal ions becomes difficult. The concentration of metal ions in the dispersion is preferably at least twice the cation exchange capacity of the water-swellable clay mineral. If the amount is less than that, the amount of metal hydroxide and/or metal oxide produced with respect to water-swellable clay minerals will be small, resulting in poor deodorizing effect. The amount of the alkaline solution to be dropped is such that the ratio of hydroxide ions to the initially charged metal ions (metal ions/hydroxide ions) is between 0.2 and the valence of the metal ions used, preferably between 0.5 and the metal used. It is preferable to adjust the valence to 273, which is the valence of the ion. If it is less than that, the amount of metal hydroxide and/or metal oxide produced will be small, and the deodorizing effect will be poor. Further, if it exceeds this range, too much metal hydroxide and/or metal oxide will be produced in areas other than between the layers of clay minerals, and the deodorizing effect will be deteriorated, which is not preferable.

The temperature of the dispersion during production may be any temperature, and room temperature is usually sufficient. The drying temperature may be any temperature as long as it is below the decomposition temperature of the clay mineral, but the metal compound obtained differs depending on the drying temperature. Taking the case of using zinc as an example, it is thought that zinc hydroxide is produced below about 100°C, zinc oxide is produced above about 150°C, and both coexist in between.

These metal compounds have a deodorizing effect on malodorous substances through chemical reactions, and clay minerals themselves have a deodorizing effect due to their adsorption ability.The deodorant of the present invention has an excellent deodorizing effect in which both of them synergistically exhibit a deodorizing effect. It is a deodorant. Clay minerals complexed with such metal compounds have weak water swelling properties, do not form a gel when in contact with water, and are well dispersed in water, and exhibit excellent deodorizing effects even in that state. Moreover, these metal compounds do not dissolve into water, and there is no problem in terms of safety.

For the deodorant according to the present invention obtained as described above, the slurry-like precipitate obtained at the final stage of the manufacturing process can be used as it is, or it can be washed, dried, and pulverized to form a powdery deodorant. It can also be used as a deodorant by dispersing it in water and/or an organic solvent. Furthermore, it can also be used as a deodorant by subjecting it to hydrophilic treatment such as silica treatment and lipophilic treatment using fatty acid soap, silicone compound, etc. In addition, these deodorant powders and nylon,
It can also be used in the form of a composite powder with organic powders such as polyethylene, acrylic resin, polyester, and various inorganic powders.

[Example] The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto.

The test method is as follows.

(Deodorizing test method) 20 mg of powder for dry method, 5 mg of powder for wet method
Weigh out 0 mg and 1 m of water, put them in a 100 m (L) Erlenmeyer flask, and after sealing with a silicone stopper, inject 8500 ppm of a malodorous substance or a solution of the malodorous substance into the Erlenmeyer flask from a microsyringe. A sample of 1 ml of the air was taken, and the concentration of malodorous substances was measured using a gas chromatograph to determine the residual rate.

Example 1 24.16g of copper nitrate (trihydrate) in 31g of ion-exchanged water
Dissolve and thoroughly disperse 100g of Laponite XLG therein. Thereafter, the precipitate was filtered, washed, dried at 80°C, and crushed to obtain a light blue deodorizer.

Example 2 Cobalt sulfate (heptahydrate) 21.0 in 2 L of ion-exchanged water
8 g and well dispersed therein 100 g of Kunibia F. After that, filter and wash the sediment at 200℃.
A pale red deodorant was obtained by drying and pulverizing.

Example 3 29.75 g of zinc nitrate (hexahydrate) in 3 L of ethanol
and 100 g of Smectone SA are well dispersed therein. Thereafter, the precipitate was filtered, washed, dried at 80°C, and ground to obtain a white deodorant.

Example 4 Cadmium chloride (2,5 hydrate') in 5 ion-exchanged water
Dissolve 22.83g and add Veegum S-619 to it.
Disperse 100g of Step 4 well. Then filter the sediment.
A pale brown deodorant was obtained by washing, drying at 80°C and pulverizing.

Example 5 33.97 g of silver nitrate was dissolved in 3 L of ion-exchanged water, and 100 g of Laponite XLG was dispersed therein.

Thereafter, the precipitate was filtered, washed, dried at 150°C, and crushed to obtain a light brown deodorant.

The deodorants of Examples 1 to 5 were examined for their deodorizing effects on malodorous substances such as hydrogen sulfide, ammonia, mercaptans, and amines. The results are shown in Table-1.

As a comparative example, Laponite XLG (Comparative Example 1)
, commercially available activated carbon (Comparative Example 2) was used.

As is clear from Table 1, it can be seen that the deodorant of the present invention is an excellent deodorant with a lower residual rate of various malodors than the comparative example.

Example 6 44.6 g of zinc nitrate (hexahydrate) in 3 ion-exchanged water
was dissolved and 100 g of Laponite XLG was well dispersed therein. While stirring this dispersion, 150 n+i of IN sodium hydroxide was added dropwise. Thereafter, the laundry was filtered and washed, dried at 80°C, and crushed to obtain a white deodorant.

Example 68.1 g of zinc chloride is dissolved in 2 L of ion-exchanged water, and 100 g of Kunivier F is well dispersed therein. Add this dispersion (while stirring) 111 potassium hydroxide 50
Drop 0rrt. After that, the precipitate is filtered and washed, and 2
A pale brown deodorant was obtained by drying at oO<0>C and pulverization. When this material was measured by X-ray diffraction, the interlayer distance was approximately 3
It was found that the virus had spread to humans, and that zinc oxide had formed between the layers.

Example 8 62.4 g of copper sulfate (pentahydrate) is dissolved in 3 L of ion-exchanged water, and 100 g of Smectone S A is well dispersed therein. While stirring this dispersion, 500 d of IH sodium hydroxide is added dropwise. Thereafter, the precipitate was filtered, washed, dried at 400°C, and crushed to obtain a light brown deodorant.

Example 9 Cobalt nitrate (hexahydrate) 43.6% in 5L of ion-exchanged water
Dissolve g and add 100 g of Veegum S-6194 to it.
Disperse g well. While stirring this dispersion,
100 d of sodium hydroxide is added dropwise. Thereafter, the precipitate was filtered and washed, dried at 200°C, and crushed to obtain a light brown deodorant.

Comparative Example 3 44.6 g of zinc nitrate (hexahydrate) in 3 L of ion-exchanged water
was dissolved, and 150 rnt of IN sodium hydroxide was added dropwise thereto while stirring. Thereafter, the precipitate was filtered and washed, dried at 80°C, and ground to obtain a white powder.

The deodorizing effects of the deodorants of Examples 6 to 9 on malodorous substances such as hydrogen sulfide, ammonia, mercaptan, and amine were investigated. The results are shown in Table-2.

As a comparative example, the powder obtained in Comparative Example 3, Laponite XLG (Comparative Example 4), was used.

The results are shown in Table-2.

As is clear from Table 2, it can be seen that Examples 6 to 9, which are deodorants according to the present invention, have superior deodorizing effects on various malodorous substances compared to the comparative examples.

[Effects of the Invention] The deodorant according to the present invention is highly safe because it is made of clay minerals, and has extremely strong deodorizing ability against various malodorous substances such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes. Not only can it be used as a powder indoors, in cars, or in refrigerators, but it is a fine powder that can be easily supported on paper or sheets, and it is thermally stable up to about 500°C, so it can be used as a material for mixing into plastics. It also has excellent processability and can be used as a deodorant in industrial applications. In addition, the deodorant of the present invention has a beautiful color tone in which interlayer metal ions are pale blue for copper, pale red for cobalt, white for zinc and cadmium, and light brown or white for metal compounds, so the antiperspirant is It can be used for a variety of purposes, such as cosmetics, cosmetic tools such as sponges, and deodorants for sanitary products and disposable diapers.

Claims (4)

[Claims] (1) A deodorant made of a clay mineral, characterized by having one or more metal ions other than sodium, potassium, lithium, and calcium, or one or more metal compounds between layers. (2) The deodorant according to claim 1, wherein the metal ions other than sodium, potassium, lithium, and calcium are copper ions, cobalt ions, cadmium ions, silver ions, or zinc ions. (3) The deodorant according to claim 1, wherein the metal compound other than sodium, potassium, lithium, and calcium is a metal hydroxide or a metal oxide. (4) The metal hydroxide or metal oxide is copper, cobalt,
The deodorant according to claim 3, which is a hydroxide or oxide of cadmium, silver, or zinc.