Low-alcohol perfume compositions

Abstract: A low-alcohol perfume composition comprises at least 10% by weight of a single or mixed solvent of a lower glycol and/or a lower alcohol having at least 4 carbon atoms in its principal chain, not more than 40% by weight of water, and not more than 20% by weight of a perfume component. Due to the hydration characteristic of the lower glycol and the dual solvent affinity of the lower alcohol, the perfume can be dissolved. Accordingly, the amount of ethyl alcohol can be reduced without deteriorating the usability of the composition.

Description: BACKGROUND OF THE INVENTION Field of the Invention This invention relates to low-alcohol perfume compositions and, in particular, an improvement in their solvent compositions. Description of the Prior Art In general, perfumes are seldom used in alone. Before use, they are usually diluted with a solvent for perfumes which is mainly composed of ethyl alcohol. As environmental problems have recently become a matter of much concern, restrictions on volatile organic compounds are expected in the United States. Ethyl alcohol, which is an organic solvent, is listed as one of such volatile organic compounds. In near future, it will become necessary for alcoholic perfume compositions with a perfume content of 20% by weight or less to gradually reduce the amount of the volatile organic compound to 75% by weight or less. However, in the case of a product with a perfume content of 15% by weight or less and an ethyl alcohol content of 75% by weight or less, for example, 10% by weight or more of the remnants should be substituted by other solvents. Such solvents have to dissolve ethyl alcohol, perfume, and other components. Also, since these solvents are used, for example, as being applied to skin, they have to be nontoxic, less sticky, and easy to dry. Accordingly, it has been very difficult to find organic solvents with a low volatility which comply the above-mentioned restrictions on the volatile organic solvents. For example, a perfume composition containing a perfume component, alcohol(s), moisture component(s) and oil ingredient(s) is disclosed in Shiseido, Co., Ltd, JP-A-05-279237 (1993). On the other hand, it has been quite difficult for a prescription to include 10% by weight or more of a compound with no flash point, such as water, without using a surface active agent. SUMMARY OF THE INVENTION In view of the foregoing problems of the prior art, the object of the present invention is to provide a low-alcohol perfume composition which contains a reduced amount of alcohol while maintaining the solubility and usability of the perfume composition. As the result of industrious studies, the inventors have found that, in a low-alcohol perfume composition containing 20% by weight or less of perfume and 75% by weight or less of ethyl alcohol, its usability can be maintained when the main ingredient of the remaining solvent component for perfume comprises a lower glycol having up to 6 carbon atoms and/or a lower alcohol having 4-6 carbon atoms and having at least 4 carbon atoms in its principal chain and water. Based on this finding, the present invention has been accomplished. According to the first aspect of the invention, the low-alcohol perfume composition in accordance with the present invention comprises at least 10% by weight of a lower glycol, 40-75% by weight of ethyl alcohol, water in an amount up to 40% by weight, and a perfume component in an amount up to 20% by weight, characterised in that the amount of ethyl alcohol is 40-75% by weight and the ratio of the lower glycol/water is within the range of 2:1 to 6:1 in the composition. In this aspect of the invention the low-alcohol perfume composition is characterised in that the composition is used for application from outside of skin. In a preferred aspect of the invention the low-alcohol perfume composition is characterised in that the lower glycol is at least one component selected from the group consisting of 1,3-butylene glycol 1,2-propylene glycol, and 3-methyl-1,3-butane diol in the composition. It is also preferred that the low-alcohol perfume composition is characterized in that the lower glycol comprises 1,3-butylene glycol and that the quantitative ratio of the lower glycol/water is within the dissolution area in the phase diagram shown in Figure 1 in the composition. In the second aspect of the invention the low-alcohol perfume composition comprises at least 10% by weight of a lower alcohol having 4 to 6 carbon atoms and at least 4 carbon atoms in its principal chain, 10- 75% by weight of ethyl alcohol, water in an amount up to 40% by weight and a perfume component in an amount up to 20% by weight and the ratio of the lower alcohol/water is within the range of 2:3 to 4:1 in the composition. In this aspect of the invention the low-alcohol perfume composition is characterized in the composition is used for application from outside of skin. In this aspect of the invention it is preferred that the low-alcohol perfume composition is characterized in that the lower alcohol comprises 3-methyl-3-methoxy butanol and that the quantitative ratio of the lower alcohol/water is within the dissolution area in the phase diagram shown in Figure 2 in the composition. In the third aspect of the invention the low-alcohol perfume composition comprises 10-50% by weight of a lower glycol and a lower alcohol having 4 to 6 carbon atoms and at least 4 carbon atoms in its principal chain, 10- 75% by weight of ethyl alcohol, water in an amount up to 40% by weight, and a perfume component in an amount up to 20% by weight.. In this aspect of the invention the low-alcohol perfume composition is characterized in that the composition is used for application from outside of skin. In this aspect of the invention it is preferred that the low-alcohol perfume composition is characterized in that the lower glycol is at least one component selected from the group consisting of 1,3-butylene glycol, 1,2-propylene glycol, and 3-methyl-1,3-butane diol and that the lower alcohol is 3-methyl-3-methoxy butanol in the composition. According to the above-mentioned restrictions on volatile organic compounds, the amount of the solvent becomes 85% by weight, for example, when the perfume component is 15% by weight. Since ethyl alcohol cannot be used beyond 75% by weight, at least 10% by weight of the amount of the solvent in this case has to be substituted by other solvents or the like which are not restricted. Also, as the perfume compositions may be applied directly to skin, their safety becomes a very important requirement. The inventors of the present invention have taken notice of lower glycols having up to 6 carbon atoms and lower alcohols having 4 to 6 carbon atoms and at least 4 carbon atoms in their principal chain, which have conventionally been registered materials for cosmetics as a moisture-retaining agent, and attained a very usable low-alcohol perfume composition comprising not more than 20% by weight of a perfume component and not more than 75% by weight of ethyl alcohol. Conventionally, these lower glycols and lower alcohols have usually been compounded in cosmetics such as lotion, cleanser, and milky lotion in an amount not more than 10% by weight. They have not been used in low-alcohol perfume compositions such as those of the present invention. According to the experiments of the inventors of the present invention, lower glycols have a function called hydration which has a high affinity to both perfume, which is structurally an oil component, and water, while lower alcohols having at least 4 carbon atoms in their principal chain have a dual solvent affinity for dissolving both oily perfume and water. Figure 1 shows the results of an experiment on solubility conducted by the inventors in which a rose-like perfume and, as an example of the lower glycol, 1,3-butylene glycol (1,3-B.G.) are used. As clearly understood from this drawing, when their usability is not concerned, water and 1,3-butylene glycol can dissolve the perfume without using ethyl alcohol. Similarly, Figure 2 shows the results of an experiment on solubility in which 3-methyl-3-methoxy butanol (MMB) is used as an example of the lower alcohol. As clearly understood from this drawing, when their usability is not concerned, water and MMB can dissolve the perfume without using ethyl alcohol. Further, Figures 3-5 show the results of experiments on solubility in which 1,3-butylene glycol, as an example of the lower glycol, and 3-methyl-3-methoxy butanol, as an example of the lower alcohol, are mixed at the ratios of 1:1, 2:1, and 1:2, respectively, to form a mixed solvent. As clearly understood from these drawings, when their usability is not concerned, there exist dissolution areas when the lower glycol and lower alcohol are used as the mixed solvent. The inventors have taken notice of the affinity of lower glycols to water and the dual solvent affinity of lower alcohol compositions and accomplished the present invention. Namely, the water content in the low-alcohol perfume compositions in accordance with claims 1-5 of the present invention is recited as not more than 40% by weight due to the dual solvent affinity of the lower alcohols and/or the hydration characteristic of the lower glycols. Since the low-alcohol perfume compositions in accordance with the present invention contain water and the lower glycol and/or lower alcohol with a moisture-retaining function, they yield a favorable feeling of use and a moisture- retaining function when applied to skin. BRIEF DESCRIPTIONS OF THE DRAWINGS Figure 1 is a dissolution diagram of a lower glycol, water, and a perfume. Figure 2 is a dissolution diagram of a lower alcohol, water, and a perfume. Figure 3 is a dissolution diagram of a mixed solvent with the ratio of lower glycol/lower alcohol at 1:1, water, and a perfume. Figure 4 is a dissolution diagram of a mixed solvent with the ratio of lower glycol/lower alcohol at 2:1, water, and a perfume. Figure 5 is a dissolution diagram of a mixed solvent with the ratio of lower glycol/lower alcohol at 1:2, water, and a perfume. EXAMPLES The present invention will be explained in more detail with reference to the following examples. The amounts listed below are in percent by weight unless otherwise specified. First, the inventors studied lower glycols as a solvent for diluting the perfume. The results are shown in TABLE 1. Perfume 15 15 15 15 15 15 Ethyl alcohol 40 40 40 40 40 85 1,3-butylene glycol 30 0 0 45 0 0 1,2- propylene glycol 0 30 0 0 0 0 3-methyl-1,3-butane diol 0 0 30 0 0 0 Ion-exchanged water 15 15 15 0 45 0 Solubility o ○ o ○ o ○ o ○ × o ○ Quick diyness o ○ o ○ Δ Δ - o ○ Anti- stickiness ○ ○ ○ × - o ○ As shown in the above results, the composition exhibited excellent solubility, quick dryness, and very low stickiness when ethyl alcohol was the sole component other than perfume. When the components other than perfume were constituted by 40% of ethyl alcohol, 15% of ion-exchanged water, and the remaining 1,3-butylene glycol, 1,2-propylene glycol, or 3-methyl-1,3-butane diol, the composition practically exhibited no problems though slight stickiness was perceived. Also, in particular, there were no problems concerning the quick dryness when 1,3-butylene glycol or 1,2-propylene glycol was used. In the next experiment, the inventors studied lower alcohols as a solvent for diluting the perfume. The results are shown in Table 2. Perfume 20 20 20 20 20 20 Ethyl alcohol 35 35 35 35 35 80 3-methyl-3-methoxy butanol 30 0 0 45 0 0 3-methoxy-1-butanol 0 30 0 0 0 0 1-methoxy-2-butanol 0 0 30 0 0 0 Ion- exchanged water 15 15 15 0 45 0 Solubility o ○ o ○ o ○ o ○ × o ○ Quick dryness o ○ o ○ o ○ o ○ - o ○ Anti- stickiness o ○ o ○ o ○ ○ - o ○ Smell of solvent o ○ ○ Δ ○ - o ○ As shown in the above results, the composition exhibited excellent solubility, quick dryness, and very low stickiness when ethyl alcohol was the sole component other than perfume. When the components other than perfume were constituted by 35% of ethyl alcohol, 15% of ion-exchanged water, and the remaining lower alcohol, namely, 3-methyl-3-methoxy butanol, 3-methoxy-1-butanol, or 1-methoxy-2-butanol, though a smell of the solvent was perceived when 1-methoxy- 2-butanol was used, the composition practically had no problems when the other lower alcohol compounds having at least 4 carbon atoms in their principal chain were used. Also, in particular, there were no problems concerning the quick dryness and the smell of the material when 3-methyl-3-methoxy butanol or 3-methoxy-1-butanol was used. Then, the inventors studied the compounding ratio of the lower glycol and lower alcohol using 1,3-butylene glycol and 3-methyl-3-methoxy butanol, respectively, as their examples. The results are shown in TABLE 3. Perfume 20 20 20 20 20 20 20 20 20 Ethyl alcohol 30 30 30 30 30 30 30 30 30 1,3-butylene glycol 30 29 25 20 15 10 5 1 0 3-methyl-3-methoxy butanol 0 1 5 10 15 20 25 29 30 Ion-exchanged water 20 20 20 20 20 20 20 20 20 Solubility o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ Quick dryness o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ Smell of solvent o ○ o ○ o ○ o ○ o ○ o ○ ○ ○ ○ Anti-stickiness ○ ○ ○ o ○ o ○ o ○ o ○ o ○ o ○ As shown in the above results, mixed solvents of the lower glycol and lower alcohol can be used in lieu of ethyl alcohol regardless of their compounding ratio. A particularly preferable compounding ratio of the lower glycol/lower alcohol is within the range of from 2:1 to 1:2. Further, the inventors studied the composition of diluting solvents using 1,3-butylene glycol, as an example of the lower glycol. The results are shown in TABLE 4. Perfume 10 10 10 10 10 10 10 Ethyl alcohol 80 75 60 50 45 40 35 1,3-butylene glycol 7 10 20 27 30 34 37 Ion-exchanged water 3 5 10 13 15 16 18 Solubility o ○ o ○ o ○ o ○ o ○ o ○ o ○ Quick dryness o ○ o ○ o ○ o ○ ○ ○ Δ Anti- stickiness o ○ o ○ o ○ ○ ○ ○ Δ Namely, a part of ethyl alcohol was substituted while the ratio of 1,3-butylene glycol/ion-exchanged water is fixed at about 2:1. The results show that favorable usability of the composition can be maintained even when the amount of ethyl alcohol is reduced to 40% and, more preferably, to 50%. Then, the inventors studied the compounding ratio of 1,3-butylene glycol, as an examples of the lower glycol, and ion-exchanged water. The results are shown in TABLE 5. Perfume 10 10 10 10 10 10 Ethyl alcohol 40 40 40 40 40 40 1,3-butylene glycol 30 33 35 40 43 45 Ion-exchanged water 20 17 15 10 7 5 Solubility × ○ ○ o ○ o ○ o ○ Quick dryness - ○ o ○ o ○ ○ ○ Anti-stickiness - ○ o ○ o ○ ○ ○ As shown in above results, the compounding ratio of 1,3-butylene glycol/ ion- exchanged water is within the range of from 2:1 to 6:1. Further, the inventors studied the composition of diluting solvents using 3-methyl-3-methoxy butanol, as an example of the lower alcohol having at least 4 carbon atoms in its principal chain. The results are shown in TABLE 6. Perfume 20 20 20 20 20 20 20 20 Ethyl alcohol 40 35 30 25 20 15 10 5 3-methyl-3-methoxy butanol 27 30 33 37 40 43 47 50 Ion-exchanged water 13 15 17 18 20 22 23 25 Solubility o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ Quick dryness o ○ o ○ o ○ o ○ ○ ○ ○ ○ Smell of solvent o ○ o ○ o ○ o ○ ○ Δ Δ Δ Anti-stickiness o ○ o ○ o ○ ○ ○ ○ Δ Δ Namely, a part of ethyl alcohol was substituted while the ratio of 3-methyl-3-methoxy butanol/ion- exchanged water is fixed at about 2:1. The results show that favorable usability of the composition can be maintained even when the amount of ethyl alcohol is reduced to 10% and, more preferably, to 20%. Then, the inventors studied the compounding ratio of 3-methyl-3-methoxy butanol, as an examples of lower alcohol at least 4 carbon atoms in its principal chain, and ion-exchanged water. The results are shown in TABLE 7. Perfume 20 20 20 20 20 20 20 20 Ethyl alcohol 30 30 30 30 30 30 30 30 3-methyl-3-methoxy butanol 10 15 20 25 30 35 40 45 Ion-exchanged water 40 35 30 25 20 15 10 5 Solubility × × ○ o ○ o ○ o ○ o ○ o ○ Quick dryness - - o ○ o ○ o ○ o ○ ○ ○ Smell of solvent - - o ○ o ○ o ○ o ○ ○ Δ Anti-stickiness - - o ○ o ○ o ○ ○ ○ ○ As shown in above results, the compounding ratio of 3-methyl-3-methoxy butanol/ion- exchanged water is within the range of from 2:3 to 4:1. Further, the inventors studied the composition of diluting solvents using 1,3-butylene glycol, as an example of the lower glycol, and 3-methyl-3-methoxy butanol, as an example of the lower alcohol having at least 4 carbon atoms in its principal chain, to make a mated solvent with their mixing ratio of 1:1. The results are shown in TABLE 8. Perfume 20 20 20 20 20 20 20 20 Ethyl alcohol 40 35 30 25 20 15 10 5 Mixed solvent 25 30 33 37 40 43 46 50 Ion-exchanged water 15 15 17 18 20 22 24 25 Solubility o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ Quick dryness o ○ o ○ o ○ o ○ ○ ○ ○ ○ Smell of solvent o ○ o ○ o ○ o ○ ○ Δ Δ Δ Anti- stickiness o ○ o ○ o ○ ○ ○ ○ Δ × Namely, a part of ethyl alcohol was substituted while the ratio of the mixed solvent/ion-exchanged water is fixed at about 2:1. The results show that favorable usability of the composition can be maintained even when the amount of ethyl alcohol is reduced to 10% and, more preferably, to 20%. Then, the inventors studied the compounding ratio of water by using a mixed solvent comprising 1,3-butylene glycol and 3-methyl-3-methoxy butanol with their mixing ratio of 1:1. The results are shown in TABLE 9 to TABLE 11. Perfume 20 20 20 20 20 20 20 20 20 20 Ethyl alcohol 70 60 60 50 50 50 40 40 40 40 Mixed solvent 10 20 10 30 20 10 40 30 20 10 Ion-exchanged water 0 0 10 0 10 20 0 10 20 30 Solubility o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ Quick dryness o ○ o ○ o ○ o ○ o ○ o ○ ○ o ○ o ○ o ○ Smell of solvent o ○ o ○ o ○ o ○ o ○ o ○ ○ ○ o ○ o ○ Anti-stickiness o ○ o ○ o ○ o ○ o ○ o ○ ○ o ○ o ○ o ○ Perfume 20 20 20 20 20 20 20 20 20 20 Ethyl alcohol 30 30 30 30 30 20 20 20 20 20 Mixed solvent 50 40 30 20 10 60 50 40 30 20 Ion-exchanged water 0 10 20 30 40 0 10 20 30 40 Solubility o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ o ○ Quick dryness ○ ○ o ○ o ○ o ○ Δ ○ ○ ○ o ○ Smell of solvent Δ Δ o ○ o ○ o ○ Δ Δ Δ ○ o ○ Anti- stickiness × Δ ○ o ○ o ○ × × Δ ○ o ○ Perfume 20 20 20 20 20 20 20 20 Ethyl alcohol 20 10 10 10 10 10 10 10 Mixed solvent 10 70 60 50 40 30 20 10 Ion- exchanged water 50 0 10 20 30 40 50 60 Solubility × o ○ o ○ o ○ o ○ o ○ × × Quick dryness - Δ ○ ○ ○ ○ - - Smell of solvent - Δ ○ ○ ○ ○ - - Anti-stickiness - Δ ○ ○ ○ ○ - - As shown in TABLE 9 to TABLE 11, favorable usability of the composition could be maintained when not more than 50%, or more preferably not more than 40%, by weight of the 1:1 mixed solvent of 1,3-butylene glycol and 3- methyl-3-methoxy butanol was compounded therein. When water exceeded 40% by weight, the usability of the composition was deteriorated due to problems in solubility. Accordingly, the amount of water should be limited to 40% by weight or less. As described in the foregoing, both product value and usability can be sufficiently maintained when the compounding amounts of lower glycol or/and lower alcohol, ion- exchanged water, and ethyl alcohol are appropriately selected. Thus, when the perfume composition is made within the range where the total amount of lower glycol, lower alcohol, and ion- exchanged water is at least 10% by weight, the amount of ethyl alcohol can be reduced while maintaining the usability of the composition. These tendencies are observed when the amount of the perfume is up to about 50% by weight.

Claims: A perfume composition comprising a lower glycol having up to 6 carbon atoms and /or a lower alcohol having 4-6 carbon atoms and having at least 4 carbon atoms in its principal chain, ethyl alcohol, water and a perfume component, wherein the condition (a), (b) or (c) in the following is satisfied: (a) comprising at least 10% by weight of the lower glycol, 40-75% by weight of ethyl alcohol, water in an amount up to 40% by weight and a perfume component in an amount up to 20% by weight, and the ratio of the lower glycol / water is 2 :1 to 6 : 1; (b) comprising at least 10% by weight of the lower alcohol, 10-75% by weight of ethyl alcohol, water in an amount up to 40% by weight and a perfume component in an amount up to 20% by weight, and the ratio of the lower alcohol / water is 2 : 3 to 4:1; (c) comprising 10-50% by weight of the lower glycol and the lower alcohol, 10-75% by weight of ethyl alcohol, water in an amount up to 40% by weight and a perfume component in an amount up to 20% by weight. A composition according to claim1, wherein said condition (a) is satisfied, and the lower glycol is selected from 1,3-butylene glycol, 1,2-propylene glycol and 3-methyl-1,3-butanediol. A composition according to claim 2, wherein the lower glycol comprises 1,3-butylene glycol and the ratio of the lower glycol / water / the perfume component is within a dissolution area in the phase diagram shown in figure 1. A composition according to claim 1, wherein said condition (b) is satisfied, and the lower alcohol comprises 3-methyl-3-methoxybutanol and the ratio of the lower alcohol /water/ the perfume component is within a dissolution area in the phase diagram shown in figure 2. A composition according to claim 1, wherein said condition (c) is satisfied, and the lower glycol is as defined in claim 2, and the lower alcohol is 3-methyl-3-methoxybutanol.. A cosmetic method comprising the application to the skin of a composition according to any preceding claim.

Inventors: EBISAWA TOSHIHIDE, TESHIMA YO, EBISAWA, TOSHIHIDE, TESHIMA, YO, EBISAWA, TOSHIHIDE, C/O THE SHISEIDO RESEARCH, TESHIMA, YO, C/O THE SHISEIDO RESEARCH
Applicants: SHISEIDO CO LTD, SHISEIDO COMPANY LIMITED
Application year: 1995
Main classification: A61K7