JP2002306583A - Deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant which is low in its own odor and exhibits an excellent deodorization effect to the odors of amines, mercaptans and lower fatty acids. SOLUTION: At least one of the compounds selected from pyruvic acids, glyoxylic acids and their salts as well as the deodorant containing water and having a specific pH buffer capacity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant capable of effectively removing odors such as lower fatty acids, amines and mercaptans.

[0002]

2. Description of the Related Art In general, malodors are complex odors of many odorants. Among them, the odors of lower fatty acids such as acetic acid and isovaleric acid, amines such as ammonia and trimethylamine, and mercaptans such as methyl mercaptan are regulated by government ordinance. Specified. Conventionally, a compound having a betaine structure is effective for deodorizing these odors.
Although disclosed in 102,760, its effect is not sufficient. Further, it has been found that pyruvate is effective for deodorizing amines and mercaptans.
No. 822, the pyruvate itself has a unique aroma and its use is limited.

[0003]

An object of the present invention is to provide a deodorant which has a low odor peculiar to the deodorant itself and is highly effective against various malodorous components such as lower fatty acids, amines and mercaptans. To provide.

[0004]

SUMMARY OF THE INVENTION The present invention provides pyruvic acid,
An object of the present invention is to provide a deodorant containing at least one compound selected from glyoxylic acid and salts thereof, and water, and having a pH fluctuation value in the range of ± 0.3 according to the following measurement method. <Measurement of pH fluctuation value> Test in which the total amount of at least one compound selected from deodorants, pyruvic acid, glyoxylic acid and salts thereof is 5 mmol / l and the pH at 25 ° C. is about 7. Prepare a deodorant for use. P at this time
Let H be the initial pH. In 50ml of this test deodorant,
Add 0.05 ml of 0.1N hydrochloric acid aqueous solution or 0.1N sodium hydroxide aqueous solution, measure pH at 25 ° C.,
This pH is used as the final pH. The pH fluctuation value is determined according to the following equation. pH fluctuation value = (initial pH)-(final pH)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, at least one compound selected from pyruvic acid, glyoxylic acid and salts thereof (hereinafter referred to as pyruvic acid, etc.) is used. The content of pyruvic acid or the like varies depending on the concentration of the malodor to be deodorized, but may be 0.001% by weight or more in the deodorant, and is preferably in the range of 0.01 to 10.0% by weight. is there.

[0006] Unique acid odors such as pyruvic acid can be suppressed without impairing the deodorizing effect on amines and mercaptans by keeping the pH substantially neutral.

[0007] The deodorant of the present invention may contain pyruvic acid and the like and have an action of keeping the pH substantially neutral.

That is, the pH fluctuation value by the above-mentioned measuring method is in the range of ± 0.3, furthermore ± 0.1, that is, the pH fluctuation value for acid or alkali is in the range of ± 0.3. Is preferred. Such a pH buffering capacity is determined by using, for example, a Michaelis buffer consisting of dipotassium hydrogen phosphate and disodium hydrogen phosphate or a pine kilbane buffer consisting of disodium hydrogen phosphate and citric acid. Can be achieved by mixing

Further, the deodorant of the present invention preferably contains an organic dibasic acid and / or a salt thereof. For example, a Clarkrabs buffer solution comprising potassium hydrogen phthalate and sodium hydroxide is exemplified. Can be Further, the organic dibasic acid is particularly preferably an organic dibasic acid having a difference between the first acid dissociation index and the second acid dissociation index at 25 ° C. (hereinafter referred to as “index difference”) of 1.7 or more.

[0010] The acid dissociation index can be determined by, for example, The Journal of Phy.
sical Chemistry vol. 68, number 6, page 1560 (1964). More simply, an automatic potentiometric titrator manufactured by Kyoto Electronics Industry Co., Ltd. (for example, AT
310J) can be used. Further, existing data may be used. For example, an organic dibasic acid can be selected from a database (C) such as pKaBASE manufactured by Compudrug. The first acid dissociation index and the second acid dissociation index of the organic dibasic acid are determined by the method (a) to
What is necessary is just to obtain | require by any method of (c). According to the method (c), the specific substance and its first acid dissociation index (p
K ₁ ) and the second acid dissociation index (pK ₂ ) are shown in Table 1.

[0011]

[Table 1]

Further, examples of the compound having a surfactant activity include an alkyl or alkenyl succinic acid having an alkyl or alkenyl chain having 8 to 18 carbon atoms. The first acid dissociation index is around 4.1, and the second acid dissociation index is 6.
It is around 1 (exponential difference 2).

A Diels-Alder reaction product of a diene compound such as isoprene, cyclopentadiene and myrcene and a dienophile compound such as maleic acid and citraconic acid can be easily synthesized with an organic dibasic acid having an index difference of 1.7 or more. . For example, 5-norbornene-2,3-
Dicarboxylic acid (pK ₂ = 6.75, pK ₁ = 4.01; index difference is 2.74). These reactants may be hydrogenated double bonds newly formed in the reaction, for example, 4-methyl-1, hydrogenated Diels-Alder reactant of isoprene and maleic acid.
2-cyclohexanedicarboxylic acid (pK ₂ = 6.74;
pK ₁ = 4.25: the index difference is 2.49).

Other compounds that can be synthesized include alkyl phosphate esters and tartaric acid obtained by acetalization, ketalization, and carbonate esterification with aldehydes, ketones, and phosgene.

Of these, more preferred are those having a second acid dissociation index of 6 to 8, specifically, cis-1,
2-cyclooctanedicarboxylic acid, cis-1,2-cycloheptanedicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-1,2-cyclopentanedicarboxylic acid, cis-1,2-cyclopebutanedicarboxylic acid ,
Cis-1,2-cyclopropanedicarboxylic acid, trans-1,2-cyclooctanedicarboxylic acid, trans-
1,2-cycloheptanedicarboxylic acid, trans-1,
2-cyclohexanedicarboxylic acid, 4-methyl-1,2
-Cyclohexanedicarboxylic acid, an alkyl or alkenyl succinic acid having an alkyl or alkenyl chain having 8 to 18 carbon atoms is selected.

The organic dibasic acid forms a buffer solution as a salt, and the counter salt is selected from alkali metal salts, ammonium salts and the like, and preferably alkali metal salts of potassium and sodium.

The content of the organic dibasic acid and / or its salt varies depending on the content of pyruvic acid and the like, but it is sufficient that the content is 0.001% by weight or more in the deodorant of the present invention. It is in the range of 0.1 to 50.0% by weight.

The pH (25 ° C.) of the deodorant of the present invention is preferably kept almost neutral, and the pH (25 ° C.) = 6 to 8 is more preferable in view of the deodorizing effect. It is preferable to adjust the ratio of pyruvic acid and / or glyoxylic acid, organic dibasic acid and / or a salt thereof, etc., so that the pH falls within this range.

Further, in the present invention, for sterilization and antibacterial,
For the purpose of fiber deodorization, ethanol can be blended in order to facilitate evaporation of the liquid deodorant from the treated fiber product and facilitate drying, and the blending amount is 1 to 15% by weight, and 2 to 15% by weight. ~ 12% by weight is preferred. As ethanol, denatured ethanol can be used, and it is particularly preferable to use 8-acetylated sucrose denatured ethanol or polyoxyethylene alkyl ether sodium sulfate denatured ethanol. Most preferably, the sum of water and ethanol comprises from 90% to 99.5% by weight of the deodorant of the present invention.

The deodorant of the present invention has 8 to 2 carbon atoms.
A surfactant such as an anionic surfactant having one or two alkyl or alkenyl groups, a nonionic surfactant, a cationic surfactant or an amphoteric surfactant; Agents or nonionic surfactants are preferred. The anionic surfactant is an anionic surfactant having 8 to 18 carbon atoms in the alkyl or alkenyl group, specifically, an alkylbenzene sulfonate,
Alkyl sulfate, average addition mole number of ethylene oxide (hereinafter referred to as EOp) is 1.0 to 20.0
A polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl ether acetate having an EOp of 1.0 to 20.0, a dialkyl sulfosuccinate or a polyoxyethylene alkyl sulfosuccinate having an EOp of 0 to 8.0, The ionic surfactant is a nonionic surfactant having an alkyl or alkenyl group having 8 to 18 carbon atoms. Specifically, the average degree of sugar condensation is 1.
Alkyl glycosides of 0 to 2.0, EOp of 1.0 to 4
0.0 polyoxyethylene alkyl ether, EOp
Is 1.0 to 40.0 polyoxyethylene glyceride,
Examples include polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters and mono-long chain alkyl type amine oxides. Among these surfactants, when used as a spray deodorant for space, when an alkyl group or alkenyl group having 8 to 18 carbon atoms is added at the 1-position of glucose, a glucose residue It is preferable that the polymerization uses 1.2 to 1.8 alkyl glycosides, because the effect of the perfume described later is improved. When used as a deodorant for textile products, it is preferable to use monoalkyldimethylamine oxide or fatty acid amidopropyldimethylamine oxide having an alkyl group having 8 to 18 carbon atoms.

The content of these surfactants in the deodorant of the present invention is preferably 0.005 to 10% by weight, particularly preferably 5 to 10% by weight.
It is preferably less than 10% by weight, more preferably 0.05 to 3% by weight as the total amount of the anionic surfactant and the nonionic surfactant.

In the present invention, a more suitable deodorizing effect can be obtained by blending the fragrance in an amount of 0.001 to 2% by weight, more preferably 0.005 to 1% by weight, and most preferably 0.01 to 1% by weight. Can be obtained. As the fragrance, a single fragrance may be used, but it is preferable to use a compounded fragrance.
Specific flavor components constituting the flavor include mint-based fragrance components such as 1-carvone, 1-menthone, and 1-menthol, and natural essential oils include peppermint oil, peppermint oil, and spearmint oil. In addition to limonene, citral, dihydromycenol, and the like as flavor components having a citrus aroma, natural essential oils include lemon oil, orange oil, lime oil, grapefruit oil, bergamot oil, lemongrass oil And the like. In addition, in addition to methyl salicylate, thymol, 1,8-cineole, linalool, sitnerol, geraniol, terpineol, camphor and the like as a flavor component having an herbal aroma, natural essential oils include eucalyptus oil, geranium oil, citronella oil and the like. As a flavor component having a woody aroma, in addition to a, b-pinene, natural essential oils include hinoki oil, cedar oil,
Pine oil, Hiba oil and the like are mentioned.

Among these flavor components, 1-carvone,
Geraniol, citral, thymol, 1,8-cineole, peppermint oil, spearmint oil, lemongrass, and hiba oil have an antibacterial effect. It is a particularly preferable fragrance for suppressing the generation of offensive odor due to propagation of bacteria and the like. In the present invention, the flavor component having an antibacterial action preferably accounts for 3 to 100% by weight, particularly 10 to 100% by weight of the total flavor component.

The flavor is at least one selected from 2-methyl-2,4-dihydroxybutane, 2-methyl-2,4-dihydroxypentane, 2,4-dihydroxybutane, dipropylene glycol and tripropylene glycol. It is preferable to incorporate a compound diluted with the compound.

The deodorant of the present invention further comprises, as solubilizers, lower (3 to 4 carbon atoms) alcohols such as isopropanol, ethylene glycol, propylene glycol,
Polyhydric alcohols (2 to 12 carbon atoms) such as glycerin and sorbitol, and aromatic sulfonates such as p-toluenesulfonate and m-xylenesulfonate can be blended. In addition, edible pigments, thickeners and the like may be added as desired, and it is preferable to add an antiseptic / antifungal agent such as methyl paraben, sodium benzoate, or Proxel BDN.

Further, usual additives such as antioxidants, preservatives, dyes, ultraviolet absorbers and the like can be added. By using the deodorant of the present invention, products having various shapes such as liquid, powder, gel, and granule can be obtained. The deodorant of the present invention can be used in combination with another deodorant.

By filling the spray container with the deodorant of the present invention, a spray deodorant can be obtained. As the spray container, for example, the first container disclosed in JP-A-50-78909 is used.
As shown in FIG. 3, FIG. 3 or FIG. 4, a mist type spray container having a spray amount of about 0.2 ml to 0.5 ml at a time or the first container disclosed in Japanese Utility Model Laid-Open Publication No. 4-37554.
It is preferable to use a pressure-accumulation trigger that is excellent in liquid dripping prevention and spray uniformity as shown in the figure.

The deodorant of the present invention is neutral and highly safe for the human body, and may be sprayed on articles that may come into contact with the body, such as clothes, socks, carpets, sofas, car seats, curtains, and the like. It may be sprayed directly on the body. Further, it may be used by impregnating it in a sheet or paper napkin. Further, the deodorant of the present invention can be used for deodorizing garbage bins, garbage, odors in refrigerators, odors in sewage treatment, odors in garbage disposal sites, odors in livestock buildings, and the like.

[0029]

According to the present invention, the deodorant itself has a low odor peculiar to itself and is highly safe to the human body, and is effective against various malodorous components such as lower fatty acids, amines and mercaptans. A high deodorant can be obtained.

[0030]

EXAMPLES (Measurement of deodorizing effect) As malodorous substances, nitrogen-based malodor ammonia, sulfur-based malodor methyl mercaptan,
The deodorizing effect was measured using isovaleric acid, a lower fatty acid.

First, an odor standard solution was prepared as follows, and the solution was poured into a 100 ml glass bottle using a microsyringe, and the odor concentration in the glass bottle was measured with a gas tech detector tube to obtain a blank. At that time, 1 microliter of ammonia obtained by diluting a commercially available 28% aqueous ammonia three times was injected. The blank ammonia concentration at that time was about 700
ppm. As for methyl mercaptan, 2 μL of commercially available methyl mercaptan ampule (1 μg / 1 μL) was injected. The concentration of methyl mercaptan in the blank at that time was about 5 ppm. As for isovaleric acid, 0.3 μL of a commercially available reagent was directly injected. The concentration of isovaleric acid in the blank at that time was about 100 ppm.

(Preparation of Deodorant) Reference Example 1 (Preparation of Deodorant 1) 15 g of cis-1,2-cyclohexanedicarboxylic acid
(0.087 mol) and 48% aqueous potassium hydroxide solution 17
g was dissolved in 50 g of ion-exchanged water. 4 g (0.044 mol) of glyoxylic acid monohydrate was added to the solution, and p
H (25 ° C) was adjusted to 7, and the whole amount was adjusted to 10 with ion-exchanged water.
It was set to 0 g and evaluated as deodorant 1. P of this deodorant 1
The H fluctuation value was measured by the method described above, and was 0.02 with respect to the addition of the 0.1N hydrochloric acid aqueous solution.

Reference Example 2 (Preparation of deodorant 2) 15 g of cis-1,2-cyclohexanedicarboxylic acid
(0.087 mol) and 48% aqueous potassium hydroxide solution 17
g was dissolved in 50 g of ion-exchanged water. 3.9 g (0.044 mol) of pyruvic acid was added to the solution, and pH (25
° C) was adjusted to 7, the total amount was adjusted to 100 g with ion-exchanged water, and evaluated as deodorant 2. The pH fluctuation value of this deodorant 2 was measured by the method described above, and was 0.02 with respect to the addition of a 0.1N aqueous hydrochloric acid solution.

Reference Example 3 (Preparation of Deodorant 3) Instead of 15 g of cis-1,2-cyclohexanedicarboxylic acid of Reference Example 1, 4-methylcyclohexane-1,2-
Deodorant 3 was prepared and evaluated in the same manner as in Reference Example 1 except that 16.2 g (0.082 mol) of dicarboxylic acid was used. When the pH fluctuation value of this deodorant 3 was measured by the above-mentioned method, it was found that the pH value was 0.1%.
0.03 for the addition of 1N aqueous hydrochloric acid.

Reference Example 4 (Preparation of Deodorant 4) Instead of 15 g of the cis-1,2-cyclohexanedicarboxylic acid of Reference Example 1, 8 g (0.082 mol) of phosphoric acid was used. Deodorant 4 was prepared and evaluated in the same manner as in Reference Example 1 except that a 48% aqueous sodium hydroxide solution was used instead. The pH fluctuation value of this deodorant 4 was measured by the method described above, and was 0.03 with respect to the addition of a 0.1N aqueous hydrochloric acid solution.

Examples 1 to 4 50 mg of each of the deodorants 1 to 4 prepared in the reference example was added to 100 m
1 liter of the glass bottle, the same amount of the odor standard solution as the amount of the blank was added, and the mixture was shaken with a shaker at room temperature for 20 minutes (120 times / minute). The concentration of offensive odor in the glass bottle was measured with a gas tech detector tube, and the deodorizing rate was determined according to the following equation. Deodorization rate (%) = [(concentration of blank−concentration remaining in sample) / concentration of blank] × 100.

As Comparative Example 1, glyoxylic acid 3.
50 mg of a 3% by weight aqueous solution, 50 mg of a 3.9% by weight aqueous solution of pyruvic acid as Comparative Example 2, and cis-
The deodorizing effect was compared in the same manner as in the Example using 50 mg of a neutral aqueous solution in which 15 g of 1,2-cyclohexanedicarboxylic acid and 17 g of a 48% aqueous potassium hydroxide solution were dissolved in ion-exchanged water to make the total amount 100 g. In addition, when the pH fluctuation value of the aqueous solution (deodorant) of Comparative Examples 1 and 2 was measured by the above-mentioned method,
0.4.

Further, in order to check the smell of the deodorant itself, 1 g of the deodorant was sprayed on a 10 cm square cotton cloth, and five skilled panelists checked whether or not there was an acid odor. 1;
The evaluation was made in four steps of slightly acid odor and 0; no odor, and the average value was obtained. The results are summarized in Table 2.

[0039]

[Table 2]

As shown in Table 2, the deodorant of the present invention has almost no odor in the deodorant itself,
High deodorizing effect was recognized against all types of malodors such as isovaleric acid and methyl mercaptan.

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Claims (4)

[Claims] Claims: 1. A composition comprising at least one compound selected from pyruvic acid, glyoxylic acid and salts thereof, and water, and having a pH fluctuation value of ±
Deodorant in the range of 0.3. <Measurement of pH fluctuation value> Test in which the total amount of at least one compound selected from deodorants, pyruvic acid, glyoxylic acid and salts thereof is 5 mmol / l and the pH at 25 ° C. is about 7. Prepare a deodorant for use. P at this time
Let H be the initial pH. In 50ml of this test deodorant,
Add 0.05 ml of 0.1N hydrochloric acid aqueous solution or 0.1N sodium hydroxide aqueous solution, measure pH at 25 ° C.,
This pH is used as the final pH. The pH fluctuation value is determined according to the following equation. pH fluctuation value = (initial pH)-(final pH) 2. The deodorant according to claim 1, comprising an organic dibasic acid and / or a salt thereof. 3. The deodorant according to claim 2, wherein the difference between the first acid dissociation index and the second acid dissociation index of the organic dibasic acid at 25 ° C. is 1.7 or more. 4. The deodorant according to claim 2, wherein the second acid dissociation index of the organic dibasic acid at 25 ° C. is 6 to 8.