JPH0370528B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deodorizing agent that has a good deodorizing effect on malodorous components, particularly sulfur compounds such as hydrogen sulfide and methyl mercaptan.

BACKGROUND ART Conventionally, there have been many sources of bad odors such as garbage and filth in the living environment, and it has been desired to control or deodorize the bad odors. In addition, bad odors generated from large-scale facilities such as sewage treatment plants, fish processing plants, fish meal manufacturing plants, livestock feces or chicken powder drying plants, and pulp factories have become a social problem. In addition, the bad odor 1
One such problem is bad breath, and it is also desired to effectively control or deodorize this bad breath.

Various malodorous components are known to cause such malodors, but sulfur compounds such as hydrogen sulfide and methyl mercaptan are particularly problematic.
Conventional deodorizing methods have been proposed, such as a method using copper chlorophyllin sodium and a method using 1,4-naphthoquinone.

However, copper chlorophyllin sodium has the disadvantage of relatively weak deodorizing power, and 1.
4-naphthoquinone loses its deodorizing power in ethanol, is difficult to preserve in deodorants, and is highly toxic, posing safety problems for the human body.
For this reason, it has a particularly strong effect on sulfur compounds such as hydrogen sulfide and methyl mercaptan as an ingredient for deodorants, and has a low toxicity without losing its deodorizing power when placed in ethanol. Something is requested.

In view of the above circumstances, the present inventors conducted various studies on deodorizing substances that have an excellent deodorizing effect on malodor components, particularly sulfur compounds such as hydrogen sulfide and methyl mercaptan, and found that the following formula (1 ) 5,8-dihydroxy-2-(1-
hydroxy-4-methyl-3-pentenyl)-
1,4-naphthoquinone, the following formula (2) 7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,6a,9,10
(6H)-tetrol and its oxide, and the following formula (3) 7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,4,6a,9,
It has been found that 10(6H)-pentol and its oxides have an excellent deodorizing effect on the above-mentioned sulfur compounds.

That is, the present inventors have found that the above-mentioned compound has a much higher ability to deodorize methyl mercaptan than conventionally known natural deodorants such as sodium copper chlorophyllin, and is inactivated in ethanol. The inventors have now discovered that the above-mentioned compound can be effectively used as an active ingredient of deodorants because it has low toxicity and has low toxicity, leading to the present invention.

The present invention will be explained in more detail below.

The deodorant according to the present invention comprises 5,8-dihydroxy-2-(1-hydroxy-4-methyl-3-pentenyl)-1,4-naphthoquinone of the formula (1),
7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,6a,9,10 of the above formula (2)
(6H)-tetrol and its oxide and the above (3)
7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,4,6a,9,10 (6H)
- One or more selected from pentol and its oxides are used as deodorizing active ingredients.

The deodorant of the present invention comprises one or two of the above-mentioned compounds.
By using the above-mentioned seeds as deodorizing active ingredients, it has a fast-acting and excellent deodorizing power, especially against methyl mercaptan, and effectively suppresses, deodorizes, and prevents the bad odor of methyl mercaptan. Therefore, the deodorizer of the present invention can be used as a deodorizer for preventing and deodorizing sources of bad odors generated in food processing factories, pulp factories, etc., sources of bad odors generated in garbage, toilets, etc., as well as bad breath. It can be effectively used for industrial, household, oral, etc.

The deodorizer of the present invention may be used alone, but it can also be used in combination with other deodorizing active ingredients, and when used as an industrial or household deodorizer, it may be used as an ordinary deodorant if necessary. Ingredients used in deodorants, such as sodium perborate, hypochlorous acid, manganese dioxide, permanganate, benzoquinone,
Oxidizing agents such as naphtoquine, aldehydes such as glyoxal and acrolein, ketones, epoxy compounds such as 1,2-propylene oxide and 1,2-n-butylene oxide, methacrylic acid esters, maleic acid derivatives, etc. Unsaturated compounds, metal salts such as copper sulfate and zinc sulfate, adsorbents such as activated carbon, silica gel, and alumina may be mixed together. The deodorant may be in the form of a solution in which the active deodorizing ingredient of the present invention is dissolved in an appropriate solvent, or may be in the form of powder, granules, blocks, or the like. In this case, the amount of the deodorizing active ingredient of the present invention is not particularly limited.

In addition, when the deodorant of the present invention is used for the purpose of preventing or deodorizing bad breath, it may be used in toothpaste, mouthwash,
Oral compositions such as troches, chewing gums, and candy can be prepared. In this case, the amount of the deodorizing active ingredient of the present invention in the oral composition is
0.00001-50% by weight, more preferably 0.0001-10
It is preferable to set it as weight%.

In this case, the deodorizing active ingredient of the present invention has low toxicity;
Can be safely incorporated into oral compositions. For example 1, 4
- In rats by oral administration of naphthoquinone
The LD ₅₀ of the compound is 190 mg/Kg, which poses a safety problem, whereas the compound of formula (1) has an LD ₅₀ of 1 g/Kg or more, indicating extremely low toxicity.

In addition, when the deodorizing active ingredient of the present invention is blended into an oral composition, appropriate components depending on the type of composition can be used as the components of the oral composition. For example, in the case of toothpaste, abrasives such as dicalcium phosphate, calcium carbonate, calcium pyrophosphate, insoluble sodium metaphosphate, amorphous silica, crystalline silica, aluminosilicate, aluminum oxide, aluminum hydroxide, resin, etc. (usually 20-60% by weight), binders such as sodium carboxymethyl cellulose, bidroxyethyl cellulose, alginate, carrageenan, gum arabic, polyvinyl alcohol (usually 0.3-5% by weight),
Thickening agents such as polyethylene glycol, sorbitol, glycerin, propylene glycol (usually 10
~70% by weight), sodium lauryl sulfate, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, sodium N-lauroyl sarcosinate, N-acylglutamate, sucrose fatty acid ester, etc. Foaming agents (usually 0.1 to 5% by weight), essential oils such as peppermint and spearmint, fragrance materials such as l-menthol, carvone, eugenol, and anethole, saccharin sodium, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, It is produced by mixing components such as perillartine, a sweetener such as p-methoxycinnamic aldehyde, and a preservative with water and following a conventional method. Furthermore, in mouthwashes and other mouthwashes, ingredients are appropriately blended depending on the properties of the product.

In addition, in these oral compositions, lysozyme chloride, dextranase, lytic enzyme, mutanase, chlorhexidine, sorbic acid, alexidine, hinokitiol, cetylpyridinium chloride, alkylglycine, alkyldiaminoethylglycine salt, allantoin, ε-aminocaproic acid Contains active ingredients such as , tranexamic acid, azulene, vitamin E, sodium monofluorophosphate, sodium fluoride, stannous fluoride, water-soluble mono- or di-phosphates, quaternary ammonium compounds, and sodium chloride. You can also.

Next, examples will be shown to specifically explain the effects of the present invention.

Example 1 The deodorizing power of the compound of formula (1) was investigated by the following deodorizing power test.

For comparison, the deodorizing powers of 1,4-naphthoquinone and sodium copper chlorophyllin were also investigated in the same manner.

Deodorizing power test: Ethanol solution or 80v/v containing various amounts of samples (deodorizing substance) in test tubes with a content capacity of approximately 22 to 23ml.
% ethanol solution (for control, ethanol or 80v/v% ethanol solution only) and 1 ml.
1.5 ml of 0.1M phosphate buffer was added to adjust the pH to 7.5. To this was added 0.5 ml of a 10% by volume ethanol aqueous solution containing 1 ppm of methyl mercaptan, and the mixture was immediately capped with a silicone rubber stopper and stirred vigorously for 1 minute.
Thereafter, the tube was allowed to stand at 37.degree. C. for 6 minutes, and then 5 ml of air was injected into the test tube by piercing the silicone rubber stopper using a gas syringe for gas chromatography.
After stirring vigorously for 30 seconds, 5 ml of the head space was sampled using the same gas syringe and immediately injected into a gas chromatograph to measure the integral count of methyl mercaptan. The gas chromatograph used was Hitachi 163.

The results showed the deodorization rate using the following calculation formula.

Deodorization rate = C-S/C x 100 (%) C: Integral count of control S: Integral count of sample Also, for the compound of formula (1) and 1,4-naphthoquinone, these solutions were heated to 10% at room temperature. Similar tests were conducted after storage for 1 day and 40 days.

In the above test, the compound of formula (1) and 1,4-naphthoquinone were measured using an ethanol solution, and sodium copper chlorophyllin was measured using an 80% ethanol solution.

The results are shown in Figure 1. FIG. 1 shows the relationship between the sample amount and the deodorization rate, with the horizontal axis representing the amount of sample per 500 ng of methyl mercaptan and the vertical axis representing the deodorization rate. In Figure 1, a indicates the solution of the compound of formula (1) immediately after preparation, a' indicates the solution of the compound of formula (1) after storage for 10 days, and a'' indicates the solution of the compound of formula (1) after storage for 40 days. , b is immediately after preparing the 1,4-naphthoquinone solution, b' is 1,4
- After storage of naphthoquinone solution for 10 days, b″ is 1,4-
After storing the naphthoquinone solution for 40 days, c is the result immediately after preparing the sodium copper chlorophyllin solution.

From FIG. 1, it is found that the compound of formula (1) exhibits a strong deodorizing power approximately 40 times that of sodium copper chlorophyllin, and that the deodorant of the present invention has an excellent deodorizing effect on methyl mercaptan. Ta.

In addition, the solution of the compound of formula (1) was stored for 10 days and
There was almost no change in deodorizing power even after storage for 40 days, indicating that the compound of formula (1) was difficult to deactivate in ethanol. On the other hand, immediately after preparation, a 1,4-naphthoquinone solution exhibits extremely strong deodorizing power, about 10 times that of the compound of formula (1), but after storing this solution for 40 days, the deodorizing power is about 1/1 10 (same level as the compound of formula (1)), and it was observed that 1,4-naphthoquinone was deactivated in alcohol.

Example 2 The deodorizing power of the compound of formula (2) and the compound of formula (3) was investigated by the deodorizing power test shown in Example 1.

Further, for comparison, the deodorizing power of sodium copper chlorophyllin was also investigated in the same manner.

In the above test, the compounds of formulas (2) and (3) were measured using an ethanol solution, and sodium copper chlorophyllin was measured using an 80% ethanol solution.

The results are shown in Figure 2. In FIG. 2, the vertical and horizontal axes are the same as in FIG. 1. Note that d in Figure 2 is
Immediately after preparing the solution of the compound of formula (2), e is the result immediately after preparing the solution of the compound of formula (3), and f is the result immediately after preparing the sodium copper chlorophyllin solution.

Figure 2 shows that the compound of formula (2) and the compound of formula (3) have a strong deodorizing power about 40 times that of sodium copper chlorophyllin, and the deodorant of the present invention is superior to methyl mercaptan. It was found that it has an effect.

In addition, when the deodorizing power of the compound of formula (2) and the oxide (red substance) of the compound of formula (3) was investigated in a similar deodorizing power test, it was found that the deodorizing power was equivalent to that of the non-oxidized compound. It was observed that the deodorizing power of the compounds of formulas (2) and (3) did not change even when oxidized.

Examples of the deodorant of the present invention are shown below. In addition, in the following examples, all percentages are percentages by weight.

Example 1 Deodorant spray ethanol 50% Dichlorodifluoromethane 49.5 Compound of formula (2) 0.5 100.0% Example 2 Liquid deodorant ethanol 99.4% Fragrance 0.1 Compound of formula (3) 0.5 100.0% Example 3 Candy sugar 50% Water candy 33 Organic acid 2 Flavor 0.2 Compound of formula (1) 0.1 Water Remaining 100.0% Example 4 Candy sugar 50% Water candy 33 Organic acid 2 Flavor 0.2 Compound of formula (1) 0.1 Formula (2) Compound of 0.1 water Remaining 100.0% Example 5 Toothpaste calcium carbonate 50.0% Glycerin 20.0 Carrageenan 0.5 Carboxymethyl cellulose 1.0 Lauryl diethanolamide 1.0 Sucrose monolaurate 2.0 Flavor 1.0 Satucalin 0.1 Compound of formula (1) 0.1 Compound of formula (2) Compound 0.05 Chlorhexidine 0.01 Dextranase 0.01 Water Balance 100.0% Example 6 Toothpaste dicalcium phosphate dihydrate 50.0% Glycerin 20.0 Carboxymethyl cellulose 2.0 Sodium lauryl sulfate 2.0 Flavor 1.0 Satucalin 0.1 Compound of formula (1) 0.1 Compound of formula (3) 0.1 Chlorhexidine 0.01 Water Balance 100.0% Example 7 Chewing gum gum base 20% Sugar 53 Glucose 10 Water Candy 16.4 Flavor 0.5 Compound of formula (1) 0.1 100.0% Example 8 Chewing gum gum base 20 % Sugar 55 Corn syrup 12 Water Candy 9.3 Flavor 0.5 Compound of formula (2) 0.2 100.0% Example 9 Liquid toothpaste sodium polyacrylate 50.0% Glycerin 30.0 Flavor 0.9 Satucalin 0.1 Compound of formula (3) 0.1 Ethanol 3.0 Chlorhexidine 0.0 1 Linoleic acid 0.04 water remaining 100.0% Example 10 Mouthwash ethanol 20.0% Fragrance 1.0 Satucalin 0.05 Compound of formula (1) 0.1 Compound of formula (3) 0.1 Sodium monofluorophosphate 0.1 Chlorhexidine 0.01 Lauryl diethanolamide 0.3 Water remaining 100.0 % Example 11 Gargle tablet Sodium bicarbonate 54.0% Sodium diphosphate 10.0 Polyethylene glycol 3.0 Citric acid 17.0 Anhydrous sodium sulfate 13.25 Fragrance 2.0 Compound of formula (1) 0.5 Oleic acid 0.1 Sodium monofluorophosphate 0.1 Chlorhexidine 0.05 100.0 %

[Brief explanation of drawings]

FIGS. 1 and 2 are graphs showing the relationship between the amount of various deodorizing active ingredients used for methyl mercaptan and the methyl mercaptan deodorizing rate.

Claims (1)

[Claims] 1 5,8-dihydroxy-2-(1-hydroxy-4-methyl-3-pentenyl)-1,4
-naphthoquinone, 7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,6a,
9,10(6H)-tetrol and its oxide and 7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,4,6a,9,10(6H)
- A deodorant comprising one or more selected from pentol and its oxides as an effective deodorizing ingredient.