JPH0564071B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sustained-release fragrance, and more particularly, to a novel sustained-release fragrance that has improved fragrance persistence and reliability.

[Prior Art] Air fresheners used in home living rooms, hotel rooms and lobbies, cars, toilets, etc. can be divided into three types: solid, liquid, and aerosol.
Classified as a species.

Solid fragrances include those processed into plastics by blending fragrances with plasticizers, stabilizers, and porous powders, and the products are considered for use in interior decorations.

Liquid type fragrances maintain their fragrance by sucking up the liquid into a volatilization material such as felt or filter paper inserted into the opening of the container, and adjusting the rate of volatilization using the volatilization material and the opening of the container.

In addition, aerosol type air fresheners are spatial spray systems, and have the characteristic of instantly, effectively, and always giving a constant fragrance. There are two types: (using surfactant).

[Problems to be Solved by the Invention] Among the above-mentioned conventional fragrances, solid fragrances have the disadvantage that they are difficult to process as low-boiling point fragrances because heat is applied during the molding process.

Additionally, liquid fragrances have the disadvantage that the liquid spills when the container topples.

Furthermore, with aerosol-type fragrances, care must be taken not to use fragrance ingredients that may cause chemical changes or corrosion of the can; using such fragrances may change the fragrance or destabilize the emulsion, causing valve clogging. As a result, there was a problem in that the amount of fragrances available was limited.

An object of the present invention is to provide an excellent sustained-release fragrance that overcomes the above-mentioned conventional problems.

[Means for Solving the Problems] The sustained release fragrance of the present invention comprises a fragrance and the below-mentioned ()
It is characterized by containing an inclusion compound with one or more polyphenyl compounds (hereinafter simply referred to as "polyphenyl compounds") selected from the group consisting of the compounds represented by ().

In the present invention, the fragrances include cineole, cypress oil, osmanthus, diasmine, lemon, cinnamon leaf, cassia oil, menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, menthaarvensis, l-α-terpineol, l - One or more liquid fragrances selected from the group consisting of menthone, citronellal, d-pulegone, linalool oxide, cinnamon ceylon, peppermint oil, and l-carabone are preferred.

In addition, as the polyphenyl compound, one or two of the compounds shown in () to () below.
Seeds or more are preferred.

The present invention will be explained in detail below.

The clathrate compound contained in the sustained-release fragrance of the present invention is an clathrate compound in which a fragrance is a guest molecule and a polyphenyl compound is a phossu molecule.

In the present invention, the fragrance may be any aromatic material, such as cineole (1,8-cineole), cypress oil containing hinokiol as a main component, osmanthus, diasmine, lemon, cinnamon leaf, cassia oil, menthol. , rose, rosemary, palmarosa oil, lavender, spearmint oil, menthaarvensis, l-α-terpineol, l-menthone, citronellal, d-pulegone, linalool oxide, cinnamon ceylon, peppermint oil, and l-carvone liquid fragrances. can be mentioned. In addition, menthol and the like can be used as they are as a solid fragrance without being made into a liquid. These fragrances can be used alone or in combination of two or more as needed.

In the present invention, polyphenyl compounds that serve as host molecules that include such fragrances are the following compounds () to ().

() 1,1,6,6-tetraphenyl-2,4
-hexadiyne-1,6,diol () 1,1-di(2,4-dimethylphenyl)
-2-propyn-1-ol () 1,1-bis(4-hydroxyphenyl)
-cyclohexane () N,N′,N″,N,-tetra(cyclohexyl)-1,1′-biphenyl)-2,2′-dicarboxamide () Bis(4-hydroxyphenyl)sulfone () 4,4'-Butylidenebis(6-tert-butyl-3-methylphenol) () 2,2'-methylenebis(6-tert-butyl-4-methylphenol) ()4,4'-thiobis(6-tert-butyl-3
-methylphenol) () 1,1,4,4-tetraphenyl-2-butyne-1,4diol () 1,1′-bi-2-naphthol (XI) 1,1,6,6-tetra(2,4-dimethylphenyl)-2,4-hexadiyne-1,6
-diol (XII) 9,10-di(4-methylphenyl)-9,
10-dihydroanthracene-9,10-diol () 1,1,2,2-tetraphenylethane-1,2-diol In the present invention, fragrance and the above () to ()
In the case of a liquid perfume, the clathrate compound with a polyphenyl compound as shown in is produced by directly bringing the perfume and the above-mentioned polyphenyl compound into contact at a predetermined molar ratio. On the other hand, solid fragrances are manufactured using the following (a) and (b) as raw materials.

(a) A solution in which a polyphenyl compound is dissolved in a solvent selected from solvents such as methanol, ethanol, n-propanol, acetone, benzene, chloroform, esters such as ethyl acetate, and ethers such as dipropyl ether.

(b) Flavoring agent: (a) and (b) are brought into contact and reacted. As a result, the clathrate compound is precipitated by evaporating the solvent or leaving it for a while after the reaction, if necessary. This precipitate is filtered and separated by a conventional method to obtain the desired clathrate compound.

In the case of a solid perfume, the perfume may be dissolved in advance in the solvent described in (a) above, and the polyphenyl compound may be added therein and reacted.

The sustained release fragrance of the present invention can be produced not only by a liquid-liquid reaction or a solid-liquid reaction, but also by a solid-solid reaction between a solid fragrance and a solid polyphenyl compound.

In the present invention, the sustained-release fragrance may contain a clathrate compound of a fragrance and any one of polyphenyl compounds, or may contain two or more of each clathrate compound. It's okay if it's hot. The sustained release fragrance of the present invention obtained in this way is
It is usually a powdered solid and can be easily molded.
Further, by changing the particle size of the powder, the shape of the molded body, etc., the contact area with the atmosphere can be adjusted, and the degree of sustained release of the aroma can be easily adjusted.

The sustained release fragrance of the present invention is used in various embodiments as shown below.

Use the powdered drug in a container with holes.

This drug is molded into an appropriate shape and used.

Mix with paint, other resins, etc. and apply to parts, etc.

It is attached to the surface of an object by an appropriate method.

[Function] Since the fragrance is a clathrate compound with a polyphenyl compound, the sustained-release fragrance of the present invention is in a solid state. For this reason, for example, liquid fragrances have the disadvantage that the liquid spills if the container falls over, but the fragrance of the present invention eliminates such concerns and is easy to handle.

Furthermore, by clathrating the aroma component, the aroma component is gradually volatilized from the clathrate compound and the volatilization rate is reduced, thereby increasing the persistence of the aroma. By changing the particle size of this clathrate, the surface area in contact with the atmosphere can be adjusted, and the volatilization rate of aroma components can be adjusted. (If the particle size of the clathrate is increased, the sustained release of the aroma becomes more pronounced.) Furthermore, since the clathrate (powder form) can be formed into various shapes, it can be applied to the following uses.

Aromatic interior and car interior decorations Aromatic building materials, flooring materials Aromatic furniture Aromatic bedding Toiletries (cosmetics, bath additives, detergents,
(Toothbrushing, etc.) Aromatic toys Aromatic accessories Aromatic accessories Aromatic stationery, office supplies Aromatic sanitary products In the sustained-release fragrance of the present invention, once the fragrance has finished volatilizing, the host compound remains, so the fragrance can be reused. The host compound can also be reused by contacting with the host compound.

In the present invention, in particular, cineole, cypress oil, osmanthus, diasmine,
Lemon, cinnamon leaf, cassia oil, menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, mentha arvensis, l-α-terpineol, l-menthon, citronellal, d-bregon, linalool oxide, cinnamon ceylon, peppermint. When one or more selected from the liquid fragrance group consisting of oil and l-carvone is used, and one or more of the compounds shown in () to () above are used as the polyphenyl compound, Excellent effects are produced.

[Examples] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 5 g of 1,1-bis(4-hydroxyphenyl)-cyclohexane was placed in a 30 ml Erlenmeyer flask,
9.6 ml of 1,8-cineole (C ₁₀ H ₁₈ O, Mwt, 154, colorless liquid with a characteristic cephalic odor)
(Amount that gives a molar ratio of 3 times that of the host compound)
was added. The reaction system became a suspension of the host compound and the guest compound, but the reaction proceeded after stirring for several minutes and solidified instantly after several minutes. The solidified material was finely ground, taken into a Buchner funnel, washed with 5 ml of benzene, and filtered with suction using an aspirator for about 1 hour. The solid after suction filtration gave off a brain-like aroma characteristic of cineole. Further, as a result of observation using an electron microscope, it was confirmed that this solid substance was a crystalline substance. Furthermore, the results of NMR analysis,
The molar ratio of 1,1-bis(4-hydroxyphenyl)-cyclohexane and cineole is approximately 1:
It was confirmed that the content was 2.5 (weight% = 40.9:59.1).

The resulting solidified material was finely ground, and 4 g of a sample with a particle size of about 1 mm or less was taken into a 80 mm diameter shear dish, and the rate of volatilization of aroma components was measured by measuring the change in weight of the sample at room temperature and atmospheric pressure. By measuring,
I asked for it. That is, the ratio W ₁ /W ₀ ×100 (%) of the weight W ₁ after aging to the initial weight W ₀ of the sample was determined. The higher the volatilization rate, the greater the amount of weight decrease, and the greater the rate of decrease in weight change rate with respect to elapsed time.

The results are shown in Figure 1. As is clear from Figure 1, the volatilization of the aroma components of this drug continued for more than 40 days.

Example 2 Powder prepared in Example 1 (sustained release fragrance)
and 1,8-cineole, the volatilization rates of aroma components were compared under reduced pressure conditions of 40°C and 50mmH0. As a result, 65% by weight of the total amount of 1,8-cineole was volatilized in 1 hour. On the other hand, the powder prepared in Example 1 contained 18
% by weight was volatilized in 1 hour, and it took 8 hours for 65% by weight of the total amount to be volatilized.

Example 3 Regarding cypress oil containing hinokitiol as the main component, solidified granular inclusion bodies (1,1-bis(4-hydroxyphenyl)-
Weight ratio of cyclohexane and cypress oil = 50:
50) was prepared. Regarding the obtained granules, the volatilization rate of the cypress scent at room temperature and atmospheric pressure was investigated from the amount of weight change, and compared with the case of cypress oil alone. The results are shown in Figure 2.

As is clear from Figure 2, in the case of cypress oil alone, 52% of the total weight was volatilized in 24 hours. On the other hand, in the case of solidified granular clathrates, the amount of volatilization in 24 hours is 24% of the weight of the cypress oil contained.
It was hot.

Example 4 15g of 1,1-bis(4-hydroxyphenyl)-cyclohexane (abbreviated as “C”) to 100ml
10 ml of Osmanthus fragrant liquid was added to the conical beaker, and the mixture was rapidly stirred with a glass rod. The suspension solidified after a few minutes. From the IR spectrum of the solidified product, it was confirmed that the solidified product was an inclusion compound. The solidified material also gave off an osmanthus odor.

This solidified material was finely ground, and 4 g of a sample with a particle size of about 1 mm or less was taken into an 80 mm diameter shear dish, and the rate of volatilization of aroma components was measured at room temperature and atmospheric pressure by measuring the amount of change in weight of the sample. I asked for it. The results are shown in Figure 3.

As is clear from FIG. 3, the weight after 134 hours was 90.8% of the initial weight, and the weight reduction was 9.2%. This is 26% of the weight of the aroma components contained, meaning that 74% of the flavor remains.

Example 5 Instead of the osmanthus fragrance liquid in Example 4,
Using 10ml of Jasmin fragrance liquid,
A clathrate compound was prepared under the same conditions as in Example 4 except for the following conditions. From the IR spectrum of the solidified product, it was confirmed that the solidified product was an inclusion compound. The solidified product also gave off a fragrance of diasmine.

Regarding this solidified product, the volatilization rate of the aroma component was measured under the same conditions as in Example 4, and the results were
Also shown in the figure.

As is clear from FIG. 3, the weight after 134 hours was 96.3% of the initial weight, which was a 9.7% decrease in the weight of the aroma components contained, and 90.3% remained.

Example 6 Instead of the osmanthus fragrance liquid of Example 4,
A clathrate compound was prepared under the same conditions as in Example 4 except for using 10 ml of a lemon-scented perfume liquid. From the IR spectrum of the solidified product, it was confirmed that the solidified product was an inclusion compound. In addition, the solidified product gave off a lemon scent.

Regarding this solidified product, in the same manner as in Example 4,
The volatilization rate of aroma components was measured and the results were reported in the third
Also shown in the figure.

As is clear from Figure 3, the weight after 134 hours is 78.7% of the initial weight, which is a 49.0% decrease in the weight of the aroma components contained, and 51.0% remains. Become.

Example 7 Instead of the osmanthus fragrance liquid of Example 4,
A clathrate compound was prepared using 10 ml of 1,8-cineole under the same conditions as in Example 4 except for the following. From the IR spectrum of solidification, it was confirmed that the solidified product was an inclusion compound. In addition, the solidified product gave off a brain-like aroma of cineole.

Regarding this solidified product, the volatilization rate of aroma components was measured in the same manner as in Example 4, and the results are also shown in FIG.

As is clear from Figure 3, the weight after 134 hours is 85.7% of the initial weight, which is a 26.5% decrease in the weight of the aroma components contained, and 73.5% remains. .

Example 8 0.206 g of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol was placed in a 10 ml Erlenmeyer flask, and 0.41 ml of 1,8-cineol was added.
(an amount equivalent to a molar ratio of 5 times that of the host compound) and left to stand at room temperature and pressure for 2 weeks,
A precipitate was obtained. The precipitate gave off a brain-like aroma characteristic of cineole. Furthermore, the IR spectrum of the precipitate confirmed that it was an clathrate compound.

Example 9 1,1-di(2,4-dimethylphenyl)-2
-Pour 0.197 g of propyne-1ol into a 10 ml Erlenmeyer flask, add 0.65 ml of 1,8-cineole (an amount that gives a molar ratio of 5 times the amount of the host compound), and leave it standing at room temperature and pressure for 2 weeks. A precipitate was obtained. The precipitate gave off a brain-like aroma characteristic of cineole. Furthermore, it was confirmed from the IR spectrum of the precipitate that it was an clathrate compound.

Example 10 N,N,N',N'-tetra(cyclohexyl)-
Add 0.198 g of (1,1'biphenyl)-2,2'-dicarboxamide to a 10 ml Erlenmeyer flask, and add 1,8
- 0.30 ml of cineol (an amount giving a molar ratio of 5 times the amount of the host compound) was added, and the mixture was allowed to stand at room temperature and under normal pressure for 2 weeks to obtain a precipitate. The precipitate gave off a brain-like aroma characteristic of cineole. Also,
The IR spectrum of the precipitate confirmed that it was an clathrate compound.

Example 11 Bis(4-hydroxyphenyl)sulfone 1.6
A mixture of 1.0 g of Cineol and 1.0 g of Cineol was stirred at room temperature. The reaction was completed in about 2 hours, and a white solid was precipitated. The IR spectrum of the precipitate confirmed that it was a cineol clathrate compound (cineol content: 38% by weight) (abbreviated as "cineol/(D)").

Example 12 4,4'-butylidene bis(6-tert-butyl-
3-methylphenol) 2.48g and cineole
1.0 g of the mixture was stirred at room temperature. The reaction proceeded rapidly and a white solid was precipitated. of precipitates
The IR spectrum revealed that the silol clathrate compound (cineol content 35% by weight) ("cineol/(E)")
It is abbreviated as ).

Example 13 2,2'-methylenebis(6-tert-butyl-4
- methylphenol) 1.7g and cineol 1.04
The mixture of g was stirred at room temperature. The reaction proceeded rapidly and a white solid was precipitated. The IR spectrum of the precipitate confirmed that it was a cineol clathrate compound (cineol content: 38% by weight) (abbreviated as "cineol/(F)").

Example 14 A mixture of 1.8 g of 4,4'-thiobis(6-tert-butyl-3-methylphenol) and 1.53 g of cineole was stirred at room temperature. The reaction is gradual, 1
A white solid precipitated out after being left for ~2 days. The IR spectrum of the precipitate revealed a cineole clathrate compound (cineole content 46% by weight) ("cineole/(G)").
It is abbreviated as ).

Example 15 The clathrate compounds prepared in Examples 11 to 14, cineole/(D) to cineole/(G), were each placed in a shear dish, and the weight loss was measured over time in an open system at 25°C.
Comparison was made with the case of cineole only. The results are shown in Figure 4.

From FIG. 4, it was found that the inclusion compounds obtained in Examples 11 to 14 clearly had sustained release properties of cineol compared to those containing only cineol by including the guest molecule cineol. It was done.

[Effects of the Invention] As detailed above, the sustained release fragrance of the present invention has the following effects:
It is a clathrate compound of the fragrance component, which is a polyphenyl compound, and the aroma component gradually evaporates into the atmosphere, allowing the aromatic property to be maintained for a long period of time.

Because it is in solid form, it is easy to handle.
It can also be easily molded.

By changing the particle size of the clathrate compound, the rate of volatilization of the aroma component can be easily controlled, and any sustained release properties can be obtained.

Excellent effects such as these can be achieved.

In the present invention, in particular, cineole, cypress oil, osmanthus, diasmine,
Lemon, cinnamon leaf, cassia oil, menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, mentha arvensis, l-α-terpineol, l-menthon, citronellal, d-bregon, linalool oxide, cinnamon ceylon, peppermint. When one or more selected from the liquid fragrance group consisting of oil and l-carvone is used, and one or more of the compounds shown in () to () above are used as the polyphenyl compound-based compound, has excellent effects.

[Brief explanation of the drawing]

Fig. 1 is a graph showing the measurement results in Example 1, Fig. 2 is a graph showing the measurement results in Example 3, Fig. 3 is a graph showing the measurement results in Examples 4 to 7, and Fig. 4 is a graph showing the measurement results in Example 3. 15 is a graph showing the measurement results at No. 15.

Claims (1)

[Scope of Claims] 1. A sustained-release fragrance characterized by containing an inclusion compound of a fragrance and one or more polyphenyl compounds selected from the group consisting of () to () below. 2 Fragrances include cineole, cypress oil, osmanthus, diasmine, lemon, cinnamon leaf, cassia oil, menthol, rose, rosemary, palmarosa oil, lavender, spearmint oil, mentha arvensis, l-α-terpineol, l-menthone, citronellal ,d
- The sustained-release fragrance according to claim 1, which is one or more selected from the liquid fragrance group consisting of pulegone, linalool oxide, cinnamon ceylon, peppermint oil, and l-carvone. agent. 3 The polyphenyl compound is the above () to ()
Claim 1 or 2 is characterized in that one or more types selected from the group consisting of
The sustained release fragrance described in Section 1.