JP2553936B2 - Bath fragrance composition - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a bath fragrance composition containing a sulfur spring-like scent component.

[Prior art]

So-called Yunohana has long been known as a bath fragrance that gives a sulfur-like aroma. The nature of this Yunohana is crushed sulfur solid matter deposited in a vat such as a hot spring or mineral spring containing a large amount of sulfur for a long time, and most of its components are sulfur. It contains a small amount of calcium, magnesium or silicic acid. On the other hand, the artificially made Yunohana is, for example, sulfur and lime heated and melted in a kettle, cooled and mechanically crushed, and has large particles and a large amount of lime (if it is small, it is dispersed in water. However, the original acidic sulfur spring is difficult to reproduce. In addition, there is also known a method of improving the dispersibility of sulfur powder by treating sulfur powder with methyl or ethyl alcohol as a medium and treating it in a mixed solution in which a surfactant and glycerin or ethylene glycol are added. Kaisho 52-38
No. 031). In addition, a mildly acidic bathing agent containing a carbonate and an acid is mixed with a rust preventive, and in particular, a compound containing 2-mercaptothiazole as an organic rust preventive is also known (Japanese Patent Laid-Open Publication No. Sho.
60-215612). Further, a sulfur compound is disclosed as a bath component, but the exemplified sulfur compounds are all sulfur and inorganic sulfur compounds such as sodium thiosulfate, but those using mercaptan in an appetite-suppressing fragrance as an aroma agent. It has been disclosed (JP-A-62-270518).

[Problems to be Solved by the Invention]

In recent years, the demand for bath salts at home has increased dramatically, and bath agents using various scents have been marketed along with the diversification of life. However, the conventional sulfur-based bath fragrance uses an inorganic sulfur compound like a flower of a hot spring as a sulfur spring-like scent component,
They have poor wettability with water, they are charged with static electricity and remain floating on the surface of the water, and there is a risk of corroding the copper and stainless steel in the bathtub. There are problems such as deterioration due to aging. Therefore, an object of the present invention is to provide a sulfur spring-like bath fragrance composition that has good dispersibility in water, does not corrode copper and stainless steel in a bathtub, and can avoid deterioration during long-term storage. .

[Means for solving problems]

In order to solve the above problems, the present invention takes a procedure of using an organic sulfur compound instead of an inorganic sulfur compound as a sulfur spring-like scent component. That is, the present invention provides a bath fragrance composition characterized by containing a sulfur spring-like scent component consisting of one or both of an alkylthiol and a methylthioalkanol. In the present invention, the alkylthiol which is a sulfur spring-like scent component preferably has an alkyl component having 3 to 7 carbon atoms, for example, 1-butanethiol, 2-butanethiol,
2-Methyl-2-propanethiol, pentanethiol, synchropentylthiol, 3-methyl-1-butanethiol, 2-pentanethiol, 3-hexanethiol, cyclohexylthiol are used, and particularly preferably 3-methyl-1-. Butanethiol, 2-pentanethiol, 3-pentanethiol, 3-methyl-2-butanethiol are used. On the other hand, methylthioalkanol preferably has an alkanol component having 3 to 8 carbon atoms, for example, 3-methylthiopropanol, 2-methylthiopropanol, and 4
-Methylthiobutanol, 3-methylthiobutanol,
2-methylthiobutanol, 5-methylthiopentanol, 4-methylthiopentanol, 3-methylthiopentanol, 2-methylthiopentanol, 6-methylthiohexanol, 5-methylthiohexanol, 3-methylthiohexanol, 2-methylthiohexanol,
3-Methylthioheptanol and 3-methylthiooctanol are used, and particularly preferably 3-methylthiopropanol, 3-methylthiobutanol, 3-methylthiopentanol and 3-methylthiohexanol are used. It is desirable that the alkyl thiol and methyl thioalkanol be used in a mixture at an arbitrary ratio. In addition, this sulfur spring-like fragrance component, together with the known jasmine-like fragrance, rose-like fragrance, etc., with respect to the entire bath fragrance composition,
It can be used by containing it in a ratio of 1 to 1000 ppm. Since these alkylthiols and methylthioalkanols have a very strong odor, they are usually diluted with a solvent such as dipropylene glycol (DPG), propylene glycol (PG), and hexylene glycol (HG) to prepare a 0.1 to 3% solution. Used.

[Action]

The sulfur-fountain-like scent component according to the present invention exhibits an aroma similar to the scent of a sulfur spring even in a slight amount of concentration in ordinary warm water, and has little effect on metals (copper and iron).

【Example】

The alkylthiol and methylthioalkanol used in the present invention can be produced by known synthetic methods, or commercially available products may be used. As a synthesizing method, in the case of an alkyl thiol, for example, thioacetic acid is added to a double bond of an olefin by a radical reaction to form a thioacetic acid ester, which is then hydrolyzed with an alkali to synthesize. Specifically, 0.2% by weight of benzoyl peroxide was added to 2-pentene as a catalyst, and the reaction temperature was maintained at 30 to 35 ° C. while flowing dry air in the reaction vessel to obtain a predetermined amount of thioacetic acid. Is added dropwise. The addition reaction is completed within a short time after this addition. The product is not purified at this stage and is hydrolyzed by heating with a hydroalcoholic solution of caustic potash or caustic soda to give the mercaptan. Thus from 2-pentene an equal mixture of 2-pentanethiol and 3-pentanethiol (boiling point, 112
~ 115 ° C / 760 mmHg) is obtained with a yield of 61%. Similarly, from 3-methyl-2-butene, only 3-methyl-2-butanethiol (boiling point, 108 to 110 ° C./760 mmHg) can be obtained with a yield of 84%. Methylthioalkanol is generally prepared by adding methylmercaptan to α, β-unsaturated aldehyde or α, β-unsaturated carboxylic acid ester to give a 3-methylthio derivative, which is then reduced to synthesize the corresponding methylthioalkanol. You can For example, 3-methylthio-1-butanol can use crotonaldehyde as a starting material, and 3-methylthio-1-hexanol can use trans-2-hexenal as a starting material. In the case of 3-methylthio-1-pentanol, trans- when the corresponding trans-2-pentenal is not available
2-Pentenoic acid ethyl ester was synthesized, methyl mercaptan was added thereto, and the ester group was further reduced with lithium aluminum hydride to give 3-methylthio-1-
It can be pentanol (boiling point, 88.5 to 90 ° C / 5.5 mmHg). Addition of methyl mercaptan to α, β-unsaturated aldehyde or carboxylic acid ester can accelerate the reaction by using a basic compound as a catalyst as is known. For example, methyl mercaptan is added to crotonaldehyde (trans-2-butenal) and trans-2-hexenal using triethylamine as a catalyst to give 3-
Methylthiobutanal and 3-methylthiohexanal are obtained, which are reduced with sodium borohydride. For example, an equivalent solution of 3-methylthiobutanal (0.3 mol) and ethanol is added with 50 ml of sodium hydride (0.15 mol).
% Water-containing ethanol solution at 10 ° C. or lower, the reaction is maintained for 10 hours, neutralized with dilute hydrochloric acid, and extracted sufficiently with ether to give 3-methylthio-1-butanol (96% yield). Boiling point, 83 ℃ / 7.5mmHg) is obtained. Hereinafter, specific formulation examples will be described in detail, but the numerical value indicating the mixing ratio means parts by weight. [Example-1] (Preparation example in which jasmine-like aroma and sulfur spring-like aroma are harmonized) Musk ketone (fragrance) 40.0 Methylnaphthyl ketone (fragrance) 5.0 2-Methyl-4- (2,2,3-trimethyl-3-) Cyclopentene) -2-Putenol (fragrance) 20.0 4- (4-Hydroxy-4-methylpentyl) -3-cyclohexenecarbaldehyde (fragrance) 100.0 Carbanam oil (fragrance) 2.0 Patchouli oil (fragrance) 50.0 Grapefruit oil (fragrance) 200.0 Synthetic Jasmine (fragrance) 500.0 3-Methyl-1-butanethiol (1%) 5.0 3-Methylthio-1-pentanol (1%) 2.0 3-Methylthio-1-butanol (1%) 3.0 Dipropylene glycol (solvent) 73.0 1000.0 [Example-2] (Mixing example in which rose-like aroma and sulfur spring-like aroma are in harmony) Musk ketone (fragrance) 40.0 Isobo Nylcyclohexanol (fragrance) 20.0 Methylionone (fragrance) 80.0 Patchouli oil (fragrance) 5.0 Grapefruit oil (fragrance) 200.0 Lemon oil (fragrance) 100.0 Synthetic rose oil (fragrance) 500.0 3-Pentanethiol (1%) 3.0 2-Methyl- 2-Butanethiol (1%) 5.0 3-Methylthio-1-propanol (1%) 2.0 Dipropylene glycol (solvent) 45.0 1000.0 [Example-3] (Preparation example in which muguet-like aroma and sulfur spring-like aroma are harmonized) 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran (Galaxolide)
(50%) (fragrance) 50.0 Musk ketone (fragrance) 10.0 Coumarin (fragrance) 15.0 Methylionone (fragrance) 100.0 Jasmine oil (fragrance) 80.0 Grapefruit oil (fragrance) 200.0 Synthetic muguet (fragrance) 500.0 2-Pentanethiol (1%) 3.0 3-Methylthio-1-hexanol (1%) 2.0 Dipropylene glycol (solvent) 40.0 1000.0 In the formulation examples shown in Examples 1 to 3 above, alkyl thiol and methylthioalkanol were each 1 g.
Was weighed into a 100-ml volumetric flask, and a 1% solution made up to 100 ml with dipropylene glycol was used, and was mixed with the other fragrances listed. [Example-4] (Formulation example in which Yuzu-like aroma and sulfur spring aroma were harmonized) Musk ketone 40.0 α-hexylcinnamic aldehyde 120.0 Citral 40.0 Nonanal 5.0 2-methyl-4- (2,2,3-trimethyl-3- Cyclopentene) -2-butenol 5.0 Yuzu juice oil 400.0 Mandarin oil 250.0 Pettigrene oil 20.0 3-Pentanethiol (in 1% DPG) 0.1 Triethyl citrate 119.9 1000.0 DPG is dipropylene glycol. same as below. [Example-5] (Formulation example in which Yuzu-like odor and faint sulfur spring odor were harmonized) Musk ketone 40.0 α-hexylcinnamic aldehyde 120.0 Citral 40.0 Nonanal 5.0 2-Methyl-4- (2,2,3-trimethyl- 3-Cyclopentene) -2-butenol 5.0 Yuzu juice oil 400.0 Mandarin oil 250.0 Pettigrene oil 20.0 3-Pentanethiol (in 0.1% DPG) 0.1 Triethyl citrate 119.9 [Example-6] (Forest bath aroma and sulfur spring aroma are harmonized) Preparation example) Musk ketone 50.0 Cederwood oil 50.0 Patchouli oil 20.0 Avies oil 300.0 Lavandin oil 130.0 Bergamot oil (synthetic) 40.0 Isobornyl acetate 350.0 2-Methylundecanaal 5.0 Linalool 35.0 3-Methylthio-1-hexanol (in 1% DPG) 0.1 triethyl citrate 19.9 1000.0 [Example-7] (Example of blending fragrance for forest bath and faint sulfur aroma) Musk ketone 50.0 Cedarwood oil 50.0 Patchouli oil 20.0 Avies oil 300.0 Lavandin oil 130.0 Bergamot oil (synthetic) 40.0 Isobornyl acetate 350.0 2 -Methylundecanal 5.0 Linalool 35.0 3-Methylthio-1-hexanol (in 1% DPG) 0.1 Triethyl citrate 19.9 1000.0 In the formulation examples shown in Examples 1 to 7 above, alkyl thiol and methylthioalkanol were each 1 g.
Was weighed and placed in a 100 ml volumetric flask, and a 1% solution made up to 100 ml with dipropylene glycol and a 0.1% solution diluted 10 times with dipropylene glycol were used together with other aromas listed. . [Example 1 of use] 1 part by weight of the mixed flavors obtained in Examples 1 to 7 was mixed with 65 parts by weight of sodium bicarbonate and 34 parts by weight of anhydrous sodium sulfate, and
Dissolve 20 g in 200 l of warm water at 40 ° C in a bath and
Females aged 30 to 30) conducted a preference survey and image survey. The results are shown in Table 1 below. As is clear from this result, it was confirmed that the sulfur spring-like scent component according to the present invention was preferred as a hot spring-like scent by the majority of panelists. From the results of Examples 5 and 7, it was shown that the sulfur spring-like scent component according to the present invention contained 1 ppm or more in the prepared fragrance, which brought about preferable results. [Use Example 2] Various organic sulfur compounds shown in Table 2 below were prepared and diluted with dipropylene glycol to prepare a 1% solution. Using this diluted solution, anhydrous sodium sulfate containing 1% of this diluted solution was prepared, and 0.2 g of the diluted solution was dissolved in warm water 21 at 40 ° C. to give sulfur spring aroma at various concentrations shown in Table 3 to 20 people. Tested by panelists (25-30 year old women). The results are also shown in Table 3. [Use Example 3] The influence of the sulfur spring-like scent component according to the present invention on copper was examined according to the example of JP-A-59-70609. That is, 0.4 g of copper powder and 0.5 g and 0.25 g of anhydrous sodium sulfate containing 2% by weight of each organic compound in a glass stopper bottle.
g, 0.05 g was added, and the amount was adjusted to 100 g with anhydrous ion water to prepare a suspension containing 100 ppm, 50 ppm, 10 ppm as an organic compound. These were stirred at 80 ° C. for 24 hours, and the amount of copper ions eluted in the aqueous solution was measured by atomic absorption spectrometry. The results are shown in Table 4 below. [Use Example 4] The effect of the sulfur spring-like scent component according to the present invention on stainless steel and enamel was examined in accordance with the example of JP-A-59-70609. That is, 2 cm square stainless steel (thickness 1 mm) and enamel (thickness 2 mm) pieces were dipped in 100 ppm of an organic sulfur compound prepared in the same manner as in the above-mentioned Use Example 3, and kept at 80 ° C. for 48 hours.
The mixture was stirred in a sealed state, and the change of metal pieces was observed with the naked eye. The results are shown in Table 5 below.

【The invention's effect】

As described above in detail, according to the present invention, a sulfur hot spring-like scent can be obtained from an organic sulfur compound without using an inorganic sulfur compound, and a conventional inorganic sulfur compound, for example, sulfur, sodium thiosulfate, calcium thiosulfate, Potassium thiosulfate, calcium sulfide, potassium sulfide, sodium sulfide,
Ammonium sulfide, barium sulfide, zinc sulfide, tin sulfide,
Corrosion of bathtubs made of copper, stainless steel or enamel when using acidic baths or alkaline baths, such as deterioration and deterioration of fragrances that occur when using iron sulfide, carbon disulfide, phosphorus sulfide, etc. It is possible to avoid the problem of dispersibility of the fragrance as described above, and further, since the sulfur hot spring-like fragrance is a fragrance component in terms of formulation, various other fragrances such as jasmine-like, Rose,
Any combination with fragrance components such as muguet is possible, and a new image of hot spring incense can be created.

Claims (3)

(57) [Claims] 1. A bath fragrance composition comprising a sulfur spring-like scent component comprising one or both of an alkylthiol and a methylthioalkanol. 2. The alkylthiol is selected from 3-methyl-1-butanethiol, 2-pentanethiol, 3-pentanethiol and 3-methyl-2-butanethiol, and methylthioalkanol is 3-methylthio-1- The perfume composition for bath according to claim 1, which is one or more selected from propanol, 3-methylthio-1-butanol, 3-methylthio-1-pentanol, and 3-methylthio-1-hexanol. 3. The bath fragrance composition according to claim 1, which contains 1 to 1000 ppm of a sulfur spring-like scent component.