JP2001137323A - Deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the deodorizing effect of a deodorant having the effect of deodorizing to a wide range of various causatives to a sulfur-based offensive odor, such as that of mercaptan, etc., by improving the deodorizing effect of glyoxylic acid to the offensive odor. SOLUTION: In a deodorant, glyoxylic acid is used by adjusting its pH value to 2.4-9. The pH value of the glyoxylic acid is further adjusted to neutral by jointly using a surface active agent with the glyoxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a deodorant. More specifically, a deodorant containing glyoxylic acid as an active ingredient, which maintains or further improves the deodorizing effect on basic malodor caused by amines such as ammonia and trimethylamine that glyoxylic acid originally has, and In addition, the present invention relates to a deodorant which exhibits an excellent deodorizing effect on sulfur-based odors such as hydrogen sulfide and mercaptan.

[0002]

2. Description of the Related Art Odors emitted from toilets and sewage treatment plants in households, odors emitted from garbage dumps in households and garbage disposal facilities in cities, and odors emitted from waste liquid discharged from various factories and the like. Such odors are always a problem in everyday life. Therefore, it is necessary and indispensable to solve such a problem of odor in order to maintain a sanitary and comfortable living environment.

In general, an odor is not composed of a single odor-causing substance, but is composed of various substances in various combinations. For this reason, a sufficient deodorizing effect cannot be obtained with only a single deodorizing substance. For example, it is known that an alkali agent such as an aqueous solution of caustic soda is effective for deodorizing hydrogen sulfide and lower fatty acids, but has almost no effect on amines such as ammonia and trimethylamine, which are a cause of malodor of basic substances.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a deodorant which exerts a wide range of deodorizing effects on various causative substances constituting a bad odor.

[0005]

The present inventors have studied the deodorizing effect of glyoxylic acid. The glyoxylic acid is relatively excellent against basic malodors such as ammonia and trimethylamine. Although it has a deodorizing effect, it has been found that the deodorizing effect is extremely weak against sulfur-based odors such as hydrogen sulfide and methyl mercaptan. Therefore, the inventors of the present invention repeatedly studied day and night in search of a method for improving and improving the deodorizing effect of glyoxylic acid on such a sulfur-based malodor, and found that the deodorizing effect on the sulfur-based malodor has a deep relationship with the pH of the glyoxylic acid solution. Yes, pH
By adjusting the pH to a weakly acidic to weakly alkaline range with a regulator or the like, an excellent deodorizing effect improved against a sulfur-based odor while maintaining an excellent deodorizing effect against a basic odor. Was found to be effective. In addition, the present inventors have found in further studies that the combined use of glyoxylic acid and a surfactant further improves the deodorizing effect on sulfur-based odors, especially methyl mercaptan, and further shows that the deodorizing effect is moderate. It was confirmed that the deodorant effect was remarkable in the acidic region, and that the combined use of the glyoxylic acid and the surfactant further improved the deodorant effect on basic odors, especially trimethylamine. I was convinced that it was useful as a deodorant that exerts an excellent deodorant effect on malodors widely. The present invention has been developed based on such knowledge.

That is, the present invention provides various deodorants listed in the following (1) to (4): (1) A deodorant containing glyoxylic acid as an active ingredient and having a pH of about 2.4. A deodorant characterized by being in the range of ~ 9. Such a deodorant has a pH adjusted to about 2.4 to 9, thereby maintaining a good deodorizing effect on basic malodors such as ammonia and trimethylamine of glyoxylic acid, while maintaining hydrogen sulfide and methyl sulfide. It exhibits a good deodorizing effect improved against sulfur-based odors such as mercaptan.

(2) A deodorant containing glyoxylic acid and a surfactant as active ingredients, wherein the pH is in the range of about 2.4 to 9. By having a surfactant in addition to glyoxylic acid, such a deodorant exerts an excellent deodorizing effect that is even more improved against sulfur-based odors, particularly methyl mercaptan.

(3) The deodorant according to (2), wherein the surfactant is at least one of a nonionic surfactant and a cationic surfactant. Such a deodorant has an improved deodorizing effect not only on sulfur-based odors such as hydrogen sulfide and methyl mercaptan but also on basic odors such as trimethylamine.

(4) The deodorant according to (2) or (3), which has a pH of 5 to 9, preferably 5 to 8. Such a deodorant can exhibit an excellent deodorizing effect on both basic odor and sulfur-based odor.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An aqueous solution of glyoxylic acid produced industrially is usually a strongly acidic solution having a pH of about 1.
In this pH range, as described above, it has a relatively high deodorizing effect on basic malodors derived from amines such as ammonia and trimethylamine, but deodorizes sulfur-based malodors such as hydrogen sulfide and methyl mercaptan. The effect is weak, especially for methyl mercaptan (see Table 1).

[0011] The deodorant of the present invention, even with such glyoxylic acid, changes the liquidity from a strong acid range to a weakly acidic, and thus from neutral to neutral.
It has been developed based on the finding that the deodorizing effect on sulfur-based malodors such as methyl mercaptan and hydrogen sulfide is remarkably increased by adjusting to a weakly alkaline region.

The glyoxylic acid solution used in the present invention is:
Usually, the pH is about 2.4 to 9, preferably about 2.4 to 8, more preferably about 4 to 8, and even more preferably p.
It has a pH of H5-8.

The method of adjusting the deodorant of the present invention to such a pH range is not particularly limited, but generally includes a method of blending a pH adjuster. There are no particular restrictions on the pH adjuster, but caustic soda, sodium carbonate, malic acid,
Alkaline agents such as alkali metal salts of organic acids such as succinic acid, maleic acid or citric acid (eg, sodium salt, potassium salt), tris (hydroxymethyl) amine methane or alkanolamine (eg, triethanolamine, etc.); and glyoxyl Examples thereof include a buffering agent that can adjust the pH to the above range by being added to an acid.
Here, as a buffer, a mixed solution of potassium dihydrogen phosphate and disodium hydrogen phosphate, a mixed solution of potassium dihydrogen phosphate and caustic soda, a mixed solution of citric acid and caustic soda, a mixed solution of acetic acid and caustic soda, Examples include a mixed solution of succinic acid and caustic soda, a mixed solution of maleic acid and caustic soda, and a mixed solution of citric acid and disodium hydrogen phosphate.

The glyoxylic acid used in the present invention can be produced and obtained by an oxidation reaction of glyoxal or a reduction reaction of oxalic acid or the like, but a commercially available one can be used simply. Glyoxylic acid does not necessarily have to be pure, and may be crude glyoxylic acid.

The deodorant of the present invention can be prepared, for example, by adjusting a glyoxylic acid solution obtained by dissolving glyoxylic acid in water or a mixed solvent of water and an organic solvent to the above-mentioned pH. The concentration of the acid is not particularly limited, but may be usually 1 to 40% by weight, preferably 2 to 10% by weight.

Further, the deodorant of the present invention may contain a surfactant in addition to glyoxylic acid.

Here, as the surfactant, any surfactant can be used as long as the effect of the present invention is exhibited, and there is no particular limitation. For example, higher fatty acid salts, higher alkyl dicarboxylates, higher alcohol sulfates, alkyl sulfonates, higher alkyl phosphates, higher fatty acid esters sulfates, higher fatty acid esters sulfonates, higher alcohol ethers Sulfates, sulfonates of higher alcohols and ethers, alkyl sulfonates of higher fatty acid amides,
Anionic surfactants such as alkylbenzene sulfonates and alkylphenol sulfonates; glycine-type amphoteric surfactants (eg, sodium alkyldiaminoethylglycine, alkylpolyaminoethylglycine hydrochloride, etc.), alanine-type amphoteric surfactants, betaine-type amphoteric surfactants Amphoteric surfactants such as surfactants (eg, lauryl dimethylaminoacetate betaine), amidobetaine type amphoteric surfactants (eg, coconut oil fatty acid amidopropyl betaine) and sulfobetaine type amphoteric surfactant; glycerin of fatty acid Fatty acid ester nonionic surfactants of polyols such as esters, glycol esters of fatty acids, sucrose esters of fatty acids, sorbitan esters of fatty acids, mannitan esters of fatty acids, higher alcohol condensates, higher fatty acid condensates, higher fatty acids Nonionic surfactants such as a polyethylene oxide condensed nonionic surfactant such as a killamine condensate, a higher fatty acid amide condensate, a higher alkylmercaptan condensate, an alkylphenol condensate, and a polypropylene oxide condensate; an aliphatic alkylamine condensate; Higher alkylamine salt-type cationic surfactants containing aliphatic amine derivatives, tertiary amine salts, alkylolamide, fatty acid amines or fatty acid amine esters as main components, alkyl quaternary ammonium salts (for example, didecyldimethylammonium) Chloride, cetyltrimethylammonium chloride, etc.), alkyl quaternary ammonium salts having an element other than carbon, alkylbenzyl quaternary ammonium salts (eg, alkyldimethylbenzylammonium chloride, etc.) Quaternary ammonium salt type cationic surfactants such as cationic surfactants such as quaternary ammonium salt containing a nitrogen ring can be exemplified.

Preferred are nonionic surfactants and cationic surfactants, and more preferred are cationic surfactants. In addition, as a nonionic surfactant,
Specifically, polyoxyethylene alkyl ethers, alkylene oxide adducts of higher alcohols, and the like can be used, and specific examples of the cationic surfactant include alkyldimethylbenzylammonium chloride and cetyltrimethylammonium chloride.

The proportion of the surfactant to be added to the deodorant depends on the type of the surfactant used and cannot be specified unconditionally, but is usually 0.0 per 100% by weight of the deodorant.
1 to 40% by weight (effective ingredient equivalent), preferably 0.1
A range of from 10 to 10% by weight can be exemplified. The ratio of glyoxylic acid used when a surfactant is used in combination is, for example, in the range of 1 to 40% by weight, preferably 2 to 10% by weight, per 100% by weight of the deodorant.

The deodorant of the present invention containing glyoxylic acid and a surfactant as active ingredients has a pH of about 5 to 9, preferably about 5 to 8, more preferably about 6 to 8, and still more preferably about 7 to 8. It is desirable to be adjusted to have Adjustment to such a pH range can be performed, for example, by using the above-mentioned pH adjuster.

Further, the deodorant of the present invention includes, for example, a coloring agent, a clarifying agent, a flavoring agent, a viscosity modifier, a preservative, a bactericidal antibacterial agent, a plant extract, an essential oil and the like within a range not to impair the effects of the present invention. Can be blended.

The deodorant of the present invention can be prepared in any form such as liquid, powder / granular, solid, etc., depending on the form, such as toilet, washroom, bathroom, kitchen, sink,
Exhaust outlets, drains, drains, garbage disposal sites, garbage (garbage,
The deodorant of the present invention can be used in any form such as being directly scattered on a odor generating source such as filth) and sludge, or arranging the deodorant of the present invention in an atmosphere in which these odors can be generated.
In the latter use mode, the deodorant of the present invention can be used in a solid or semi-solid state by being encapsulated in a capsule or gel base material.

The deodorant of the present invention is excellent in deodorizing not only basic odors such as ammonia and amines, but also acidic to neutral odors represented by sulfur odors such as hydrogen sulfide and mercaptan. The odor effect can be exerted. Therefore, the deodorant of the present invention is not limited to the type of malodor source,
Fish odor, animal odor, sweat odor, mold odor, garbage odor, foot odor, armpit odor,
It can be widely applied to deodorization of bad smells such as manure.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. Example 1 A 400 mL conical beaker was charged with a 10 mL beaker containing various malodorous liquids (ammonia, trimethylamine, hydrogen sulfide, and methyl mercaptan) and a 10 mL beaker containing a deodorant sample (see Table 1). The upper part of the beaker was sealed with a paraffin film and aluminum foil, and left at 25 ° C. and 60% humidity. The deodorant sample (test sample) was prepared from a 4% aqueous glyoxylic acid solution (pH 1.6) using a triethanolamine aqueous solution so that the pH was in the range of about 2 to 8. As a control test, 4% glyoxylic acid aqueous solution (pH 1.6)
An experiment was similarly performed for

After one hour, the concentration of various odors (ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan) was measured with a detector tube manufactured by Gastech, and the deodorizing rate with respect to the blank concentration was calculated. The blank concentration is a malodor concentration measured after one hour by putting each malodorous liquid in a conical beaker without putting a deodorant sample and sealing it.

[0026]

(Equation 1)

The results are shown in Table 1.

[0028]

[Table 1]

From Table 1, it can be seen that increasing the pH of the glyoxylic acid solution to near neutral or weakly alkaline pH increases the deodorizing effect of mercaptan and hydrogen sulfide on sulfur-based malodors. Specifically, the pH is about 2. 0 against the malodor of methyl mercaptan and hydrogen sulfide.
The effect was expected to increase in the range of 4 or more, specifically, in the range of about 2.4 to 9, and a remarkable increase in the effect was observed in the range of pH of about 4 to 7.6. From these facts, the glyoxylic acid solution has a deodorizing effect that glyoxylic acid originally has against malodors such as ammonia and trimethylamine when the pH is in the range of about 2.4 to 9, preferably about 4 to 8. While improving the deodorizing effect against trimethylamine odor, while exhibiting a significantly improved deodorizing effect against sulfur-based odors such as mercaptan and hydrogen sulfide, which had a weak deodorizing effect. Is determined.

Example 2 Trimethylamine, hydrogen sulfide and methyl mercaptan were used as malodorous liquids, and gluoxylic acid (0 g or 4 g) and various surfactants (1 g or 10 g) listed below were added to water as a deodorant sample. The deodorization rate (%) was measured in the same manner as in Example 1 using an aqueous solution (total amount: 100 g) adjusted to pH 3.5 to 9 with triethanolamine, and deodorized against basic odor and sulfur-based odor. The odor effect was evaluated.

The surfactants used are as follows: amphoteric surfactant: Levon LD-36 (Sanyo Chemical Industries, Ltd.)
(About 36% aqueous solution of heptane lauryl methylaminoacetate, pH about 7) ・ Anionic surfactant: Marpomerse PT (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) (about 70% aqueous solution of dioctyl sulfosuccinate / Na, pH 6) ・ Nonionic surfactant: Sannonic SS-90 (manufactured by Sanyo Chemical Industries, Ltd.) (polyoxyethylene alkyl ether (RO (CH ₂ CH ₂ O) ₉ H) about 100%, pH about
6.5) Cationic surfactant: Cation G-50 (manufactured by Sanyo Chemical Industry Co., Ltd.) (Alkyl methyl methylbenzene ammonium chloride, about 50% aqueous solution, pH about 8.
5) The results are shown in Tables 2 and 3.

[0032]

[Table 2]

[0033]

[Table 3]

From these results, the deodorant effect on the odor of trimethylamine, hydrogen sulfide and methyl mercaptan is hardly observed in the surfactant itself, but is enhanced by the combined use of glyoxylic acid, and the pH is further increased.
It can be seen that the improvement is further improved by adjusting the amount in the range of 3.5 to 9.

In comparison with the results of Example 1, the deodorization of trimethylamine and hydrogen sulfide was carried out particularly using glyoxylic acid and a nonionic surfactant or a cationic surfactant in a pH of about 5 to 8, preferably about 5 to 8. It can be seen that a higher deodorizing effect can be obtained than by using glyoxylic acid alone by adjusting to a neutral range. Regarding the deodorization of methyl mercaptan, regardless of the type of surfactant, the combined use of glyoxylic acid and a surfactant can provide a higher deodorant effect than the use of glyoxylic acid alone. ~ 8, preferably pH
It turns out that it is remarkable around 7.5.

Example 3 Based on the results of Example 2, the deodorizing effect of hydrogen sulfide and methyl mercaptan when glyoxylic acid and various surfactants were used in combination at pH 7.5 was examined. Specifically, gluoxylic acid 4 was added to water as a deodorant sample.
g and various surfactants shown in Table 4 were mixed and adjusted to pH 7.5 with triethanolamine (total amount: 100).
Using g), a deodorizing experiment was performed in accordance with Example 1 or 2, and the deodorizing rate (%) was determined. As a control experiment, 4 g of gluoxylic acid was dissolved in water, and the pH was adjusted with triethanolamine.
Aqueous solution adjusted to 7.5 (no surfactant added, total 100
The experiment was similarly performed using g). The surfactants used are as follows. <Amphoteric surfactant> Levon LD-36 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) (Lauryl thimethylaminoacetate betaine about 36% aqueous solution, pH about 7) <Anionic surfactant> Marpomerse PT (Matsumoto Yushi Pharmaceutical Co., Ltd.) (Manufactured by Sanyo Kasei Kogyo Co., Ltd.) (Approx. 70% aqueous solution of dioctyl sulfosuccinate / Na, pH approx. 6) <Nonionic surfactant> Sannonic SS-90 (manufactured by Sanyo Chemical Industries, Ltd.) (Polyoxyethylene alkyl ether) 100%, pH approx. 6.5) NAROACTY N-50 (manufactured by Sanyo Chemical Industries, Ltd.) (alkylene oxyto of higher alcohol adduct, pH approx. 7) Emanone CH-80 (manufactured by Kao Corporation) (polyoxy) Ethylene hydrogenated castor oil, pH about 7) <Cationic surfactant> Cation G-50 (manufactured by Sanyo Chemical Industry Co., Ltd.) (Aqueous 50% aqueous solution of alkylmethylmethylperammonium chlorite), pH about 8.
5) Cation DDC-50 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) (Citrusil methylammonium chlorite: about 50% aqueous ethanol, pH approx. 6) Levon TM-16 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) (cetyltrimethylammonium) Chlorite (about 30% aqueous solution, pH about 5.5) The results are shown in Table 4.

[0037]

[Table 4]

From these results, it can be seen that glyoxylic acid exhibits an excellent deodorizing effect at pH 7.5 when used in combination with an optional surfactant against sulfur-based malodors such as hydrogen sulfide and methyl mercaptan.

Claims (4)

[Claims] 1. A deodorant containing glyoxylic acid as an active ingredient, wherein the pH is 2.4 to 9. 2. The deodorant according to claim 1, further comprising a surfactant. 3. The surfactant is at least one of a nonionic surfactant and a cationic surfactant.
The deodorant according to claim 2. 4. The deodorant according to claim 2, which has a pH of 5 to 8.