JPH1043573A - Liquid composition having solubilized oily component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve temp. stability and to extend utilization range by specifying the weight ratio of a composition consisting of a specific sugar fatty acid ester authorized as a food grade emulsifier, a specific monohydric alcohol, an oily component and water. SOLUTION: A desired liquid composition is prepared by incorporating (a) the sugar fatty acid ester of a 12-22C saturated or unsaturated fatty acid having an ester distribution of 60-90wt.% monoester and 5-40wt.% diester, (b) the 4-20C monohydric alcohol, (c) the oily component and (d) water. In such a case, the weight ratio of the sum of the component (a) and the component (b) is set to >=3wt.% and the ratio of the component (b) to the sum of the component (a) and the component (b) by weight is set to 0.2-0.9. As the alcohol, 1-hexanol, 1-heptanol. and the like and, as the oily component, n-heptane, n-octane and the like are cited.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid composition in which an oil component is solubilized. More specifically, the present invention relates to a liquid composition in which an oil component is solubilized, which is used in a wide range of fields such as cosmetics, pharmaceuticals, and foods.

[0002]

2. Description of the Related Art Conventionally, a liquid composition in which an oil component is solubilized, a so-called microemulsion (hereinafter, a composition in which an oil component is solubilized may be referred to as "microemulsion"). There are roughly two manufacturing methods. That is, the first is a method using an oil component and a normal nonionic surfactant, the second is an oil component, an anionic (anionic) surfactant, and a lipophilic nonionic surfactant, and further necessary. If there is, it is a method to use the electrolyte together.

In the first method, a hydrocarbon (oil) such as cyclohexane or tetradecane (hereinafter referred to as "oil" or "oil component") is added to an aqueous solution of a nonionic surfactant such as polyethylene glycol alkyl ether. Is added) and the temperature is increased, a region where the amount of solubilized hydrocarbons in the aqueous phase rapidly increases before the cloud point of the nonionic surfactant appears. Things. In the region from the solubility limit temperature to the cloud point shown in the phase diagram, it is known that the solubility of the oil in the aqueous phase increases dramatically, forming a so-called microemulsion.

[0004] However, microemulsions in which the amount of oil solubilized in an aqueous phase obtained from a nonionic surfactant-hydrocarbon (oil) system, which has been conventionally studied, have been increased due to the hydrophilic-hydrophobic properties of the system. It can only exist in a very narrow temperature range (usually around -10 ° C) with a balanced (HLB)
Outside this temperature range, the system has the disadvantage that it becomes cloudy immediately or over time and eventually separates into an aqueous phase and an oil phase. For this reason, application to cosmetics and pharmaceuticals has been very limited.

A second method is disclosed in Japanese Patent Laid-Open No. 58-12311.
As described in JP-A-58-131127, a lipophilic nonionic surfactant and a specific anionic surfactant or a lipophilic nonionic surfactant are used. An electrolyte is added to an aqueous solution which is used in combination with an ionic surfactant, and the amount of hydrocarbon (oil) solubilized rapidly within a very narrow ratio of HLB of the composition within the composition. This is to utilize an increasing area.
However, although the methods described in these publications have solved the stability to temperature, those in which the microemulsion can stably exist for a long period of time have a very limited range of the mixed composition, and the actual There are restrictions on the combination in product systems.

[0006] The nonionic surfactants used in the preparation of these conventional microemulsions are mainly
It is impossible to use a polyoxyethylene-based surfactant alone or in combination with an ionic surfactant in the form of a microemulsion for food applications because of safety and health restrictions. Was. Further, JP-A-63-126543, JP-A-63-126544
Publications include hydrophilic nonionic surfactants and inorganic (organic conceptual diagrams, written by Yoshio Koda, Sankyo Publishing, 1984).
Year. ) And a method for preparing a microemulsion from oil and water having a limited number of carbon atoms, and the type of oil used, the amount of surfactant added, and the mixing ratio of oil and water. Is required to be a specific range, so the use range is limited.

[0007]

Therefore, it is difficult to use a conventionally known microemulsion for use in cosmetics, pharmaceuticals, foods, and the like intended for use at a normal temperature. There is a disadvantage that the temperature range that can be stably present is narrow, and the above-mentioned second method has a disadvantage that the viewpoint of compounding, that is, the range of usable compounding ratio is limited, This was a problem in terms of health and safety. Under such circumstances, the completion of a highly safe microemulsion having high temperature stability and an unlimited use range has been strongly desired.

[0008]

Means for Solving the Problems Accordingly, the present inventors have:
In a liquid composition combining an aqueous phase and an oil phase, even in a wide range of composition ratios, thermodynamically stable even near room temperature, and the use range is not limited, and the oily component with excellent safety is solubilized. As a result of intensive research for the purpose of providing a liquid composition (microemulsion), a specific sucrose fatty acid ester approved as a food emulsifier, a monohydric alcohol having 4 to 20 carbon atoms, an oil component ,
It has been found that the above object can be achieved by using a composition having a specific weight ratio consisting of water and water, and the present invention has been achieved.

According to the first aspect of the present invention, which solves the above-mentioned problems, the present invention provides (a) an ester distribution of 60 to 90% by weight of a monoester and 5 to 40% by weight of a diester, and having 12 carbon atoms
To 22 sucrose fatty acid esters of saturated or unsaturated fatty acids {hereinafter referred to as component (a)};
Monohydric alcohols (hereinafter referred to as component (b)),
(C) an oily component {hereinafter referred to as (c) component}, and (d)
A liquid composition containing water {the component (d)} as an essential component, wherein the total weight of the component (a) and the component (b) is 3% by weight or more, and the component (a) (B)
The weight fraction of component (b) to the total weight of components is 0.2
The present invention provides a liquid composition in which the oil component is solubilized, which is in the range of 0.9 to 0.9.

Hereinafter, the present invention will be described in detail. The liquid composition (microemulsion) in which the oily component according to the present invention is solubilized contains a monoester 60 to 60 as a component (a).
A sucrose fatty acid ester of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms having an ester distribution of 90% by weight and a diester of 5 to 40% by weight;
(20) monohydric alcohols, (c) an oil component, and (d) four components of water as essential components. Hereinafter, each component will be described.

Component (a): Component (a) functions to solubilize component (c) into the aqueous phase together with component (b). Specific examples of the sucrose fatty acid ester constituting the component (a) include sucrose laurate ester, sucrose myristate ester, sucrose palmitate ester, sucrose stearate ester, sucrose oleate ester, and sucrose elka. Acid esters and the like. In particular, C ₁₂ ~C
₁₈ are preferred and the ester distribution is monoester 6
0 to 90% by weight, 5 to 40% by weight of diester, especially 70 to 90% by weight of monoester, 10 to 3% of diester
0% by weight is preferred. Incidentally, a polyester exceeding the diester may be mixed. At this time, the content of the polyester exceeding the diester is preferably 10% by weight or less. Since sucrose fatty acid esters are sucrose having a hydrophilic group containing a hydroxyl group, the HLB of the sucrose fatty acid esters changes depending on the temperature, like a polyoxyethylene-based nonionic surfactant conventionally mainly used for preparing microemulsions. There are few things. Therefore, a stable and highly practical microemulsion can be obtained over a wide temperature range without adding an ionic surfactant or the like. Component (a) is 2
It may be a mixture of more than one species.

Component (b): The component (b) functions to solubilize the component (c) into the aqueous phase together with the component (a). Specific examples of the alcohol constituting the component (b) include monohydric alcohols having 4 to 20 carbon atoms, and specifically, 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol. , 1-octanol, 1-
Nonanol, 1-decanol, 1-undecanol, 1
-Dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1
-Nonadecanol, 1-eicosanol and the like. Among them, 1-hexanol, 1-heptanol, 1
-Octanol, 1-nonanol, 1-decanol, 1
-Undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol,
1-hexadecanol is preferred. The component (b) is 1
It may be a seed or a mixture of two or more.

[0013] These monohydric alcohols form an aggregate with sucrose monoester molecules rather than being monodispersed and dissolved in an aqueous phase, and thus greatly affect the structure of the aggregate, that is, the formation of a microemulsion. For example, the difference between the fatty acid chain length of the sucrose fatty acid ester and the chain length of the alcohol is small, so that the associative property increases and the solubilizing ability of the oil component increases, but on the other hand, the liquid crystal is easily formed. Conversely, if the difference in chain length is large, the microemulsion phase can be expanded by the addition of monohydric alcohols even when sucrose palmitate, sucrose stearate, or the like, which easily forms liquid crystals, is used. . Most of the monohydric alcohols having less than 4 carbon atoms are monodispersed and dissolved in the aqueous phase, so that the above-mentioned influence of the hydrophilic group portion of the activator is very small. Is necessary or impossible.

The ratio of the combination of the components (a) and (b) is determined by the weight fraction of the component (b) relative to the sum of the components (a) and (b), that is, [{(b) component} /
{(A) component + (b) component}] is preferably 0.2 to 0.9. When the weight fraction of the component (b) is less than 0.2 or more than 0.9, the liquid composition tends to separate into two phases, and both are not preferred. Further, the ratio of the combination of the component (a) and the component (b) is such that the total weight of the component (a) and the component (b) is
It is preferably at least 3% by weight. (A) component and (b)
If the total amount of the components is less than 3% by weight, the microemulsion becomes unstable and may cause two-phase separation.

Component (c): Specific examples of the oily component constituting the component (c) include n-heptane, n-octane, and n-octane.
-Hydrocarbons such as decane, cyclohexane, squalene, squalane, ethers such as diheptyl ether, diethers such as ethylene glycol dibutyl ether, long chain amino alcohols such as sphingosine,
Long-chain aldehydes, long-chain ketones, terpenoids, steroids, carotenoids, waxes, acylglycerols, ether glycerides, ceramides, phospholipids, glycolipids, phosphoglycolipids, lipid sulfates, amino acid lipids, etc., and liquid paraffin, petrolatum, fish oil A mixture of animal fats and oils, vegetable oils such as soybean oil, and mineral oils may be selected depending on the use of the liquid composition. The component (c) is 1
It may be a seed or a mixture of two or more.

In the liquid composition according to the present invention, (c)
The weight fraction of (c) with respect to the sum of the components and the component (d) is
Optionally, according to experiments performed by the present inventors, from the viewpoint of the stability of the microemulsion, the weight fraction of the component (c) with respect to the sum of the components (c) and (d), that is,
[{(C) component / {(c) component + (d) component}]
It has been found that the content is preferably in the range of 0.05 to 0.95. A particularly preferred range of the total weight of the components (c) and (d) is less than 97% by weight based on the total weight of the solubilized composition.

The transparent solubilized composition of the oily component according to the present invention is characterized by being stable over a wide range of temperatures and temperature stability in a wide range of mixing ratios of an aqueous phase and an oil phase. Does not cause cloudiness or phase separation. In addition, since a large amount of oil can be stably compounded with a much smaller amount of surfactant than the conventional solubilization system, it can be said that the safety is extremely high. The liquid composition in which the oil component of the present invention is solubilized can be prepared by any known method. For example, the preparation can be performed using an emulsifier that gives a strong shearing force, for example, a TK homogenizer.

If the temperature of the system is raised to the solubilization limit temperature or higher of the sucrose fatty acid ester using the system temperature, the oil component can be easily removed with a simple stirrer or shaker and a thermostat for temperature control. A solubilized liquid composition can be prepared. The latter method is advantageous over the former method because it has the advantage that a more stable system can be obtained easily without using a special mixer, and at the same time the labor of the manufacturing process can be reduced.

An ionic surfactant may be further added to the liquid composition according to the present invention in addition to the components (a) and (c) depending on the use of the liquid composition. Further, if necessary, salts, amphiphilic substances and the like may be added. further,
Monohydric alcohols having 1 to 3 carbon atoms, sugars such as glucose and oligosaccharides, linear polyols such as glycerol, sorbitol and ethylene glycol, sugar alcohols such as maltitol and reduced oligosaccharides, proteins and peptides in the aqueous phase If necessary, amino acids, mucopolysaccharides such as chondroitin sulfate and hyaluronic acid, and glycosides such as saponin may be added. Further, to the product to which the liquid composition in which the oil component according to the present invention is solubilized is applied, if necessary, a fragrance, a dye, a preservative, a drug, a thickener, a chelating agent, and the like may be appropriately added. Can be.

The liquid composition according to the present invention comprises a detergent, a shampoo, a rinse, a hair tonic, a hair oil, a hair lotion, an aftershave lotion, a body lotion, an emollient oil, a cosmetic lotion, a cleansing oil, an aerosol product, a deodorant, aromatic,
It can be used for products such as deodorants, medicinal agents and bath salts. Further, a stable o / w emulsion can be prepared by diluting the present composition in water. These emulsions can be used for cream emulsions such as cleansing creams, massage creams, emollient creams, and hair creams, as well as products such as foods and pharmaceuticals.

[0021]

The liquid composition in which the oil component according to the present invention is solubilized has the following advantageous effects, and its industrial value is extremely large. 1. The conventional microemulsion using a nonionic surfactant has a drawback that the temperature range in which it can be stably present is narrow, but the liquid composition according to the present invention, which essentially requires four components, has a temperature of 0 ° C to 90 ° C. And the temperature stability is extremely excellent. 2. The liquid composition according to the present invention uses a surfactant that is widely used as a food additive, and the amount of sucrose fatty acid ester is at least 3% by weight based on the total amount of the composition. Since it can be compounded stably, it is extremely excellent in safety. 3. Although the liquid composition according to the present invention requires four components, it is very useful because it is easy to prepare and efficient.

[0022]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In the following examples, the “stable temperature range (° C.)” of the liquid composition was measured according to the method described below. The liquid compositions prepared in Examples and Comparative Examples were sealed in a glass tube having a diameter of 10 mm,
After shaking the glass tube and uniformly mixing the liquid composition in the tube, the glass tube is immersed in a constant temperature water bath set at a predetermined temperature, and allowed to stand for several days to one week, to determine whether or not the liquid composition in the tube has been separated.
This is a method for visual observation. Repeat the above operation according to the temperature while changing the temperature of the constant temperature water bath, confirm the temperature at which the liquid composition does not separate into two phases, and indicate the upper and lower temperature ranges as "stable temperature range (° C)". Was. The wider the upper and lower temperature ranges, the better the temperature stability.

Examples 1 to 3 Sucrose palmitate (P-1) was used as the component (a).
670, Mitsubishi Chemical Foods Corporation), hexanol (special grade, Tokyo Chemical Industry Co., Ltd.) as component (b), decane (special grade, Tokyo Chemical Industry Co., Ltd.) as component (c), and distillation as component (d) Water was weighed according to the formulation shown in Table 1, placed in a container, shaken while heating to 95 ° C, and then cooled to room temperature to obtain a transparent liquid composition. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above.
The results are shown in Table 1. Table 1 also shows the ester fraction of the sucrose palmitate used.

Examples 4 to 5 Two kinds of sucrose palmitate (P-1670, P-595, Mitsubishi Chemical Foods Co., Ltd.) as components (a) and hexanol as alcohols (special grade, Tokyo Chemical Industry Co., Ltd.) )), Decane (special grade, Tokyo Chemical Industry Co., Ltd.) and distilled water were weighed in the composition shown in Table 1, placed in a container, shaken while heating to 95 ° C., and then cooled to room temperature to obtain a transparent liquid. A composition was obtained. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above.
The results are shown in Table 1. Table 1 also shows the ester fraction of the sucrose palmitate used.

Example 6 Sucrose laurate (L-16) was used as the component (a).
95, Mitsubishi Chemical Foods Co., Ltd., alcohols such as hexanol (special grade, Tokyo Chemical Industry Co., Ltd.), decane (special grade, Tokyo Chemical Industry Co., Ltd.), and distilled water were weighed according to the formulations shown in Table 1. And shaken while heating to 95 ° C., and then cooled to room temperature to obtain a transparent liquid composition. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above. The results are shown in Table 1. Table 1 also shows the ester fraction of the sucrose laurate used.

Comparative Examples 1-2 Sucrose palmitate (P-1) was used as the component (a).
670, Mitsubishi Chemical Foods Corporation), hexanol (special grade, Tokyo Chemical Industry Co., Ltd.) as component (b), decane (special grade, Tokyo Chemical Industry Co., Ltd.) as component (c), and distillation as component (d) Water was weighed according to the formulation shown in Table 2, placed in a container, shaken while heating to 95 ° C, and then cooled to room temperature to obtain a liquid composition. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above. Table 2 shows the results. Table 2 also shows the ester fraction of the sucrose palmitate used.

Comparative Examples 3 and 4 Two kinds of sucrose palmitate (P-1670, P-595, Mitsubishi Chemical Foods Co., Ltd.) as components (a) and hexanol as alcohols (special grade, Tokyo Chemical Industry Co., Ltd.) )), Decane (special grade, Tokyo Chemical Industry Co., Ltd.) and distilled water were weighed in the composition shown in Table 2, placed in a container, shaken while heating to 95 ° C., and then cooled to room temperature to obtain a liquid composition. I got The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above. Table 2 shows the results. Table 2 also shows the ester fraction of the sucrose palmitate used.

Comparative Examples 5 to 6 Octaethylene glycol dodecyl ether (NIKKOL BL) was used as a polyethylene glycol type surfactant.
-8SY, HLB value 13, Nikko Chemicals Co., Ltd., Hexanol (special grade, Tokyo Chemical Industry Co., Ltd.), decane (special grade, Tokyo Chemical Industry Co., Ltd.), and distilled water are weighed in the composition shown in Table-2. Then, the mixture was placed in a container, shaken while heating to 95 ° C., and then cooled to room temperature to obtain a liquid composition. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above. Table 2 shows the results.

Comparative Examples 7 and 8 As a polyethylene glycol type surfactant, tetraethylene glycol dodecyl ether (NIKKOL BL) was used.
-4SY, HLB value 9.5, Nikko Chemicals Co., Ltd.) and octaethylene glycol dodecyl ether (NI
KKOL BL-8SY, HLB value 13, Nikko Chemicals Co., Ltd., heptane (special grade, Tokyo Chemical Industry Co., Ltd.),
Distilled water was weighed according to the formulation shown in Table 2, placed in a container,
After shaking while heating to 95 ° C., the mixture was cooled to room temperature to obtain a liquid composition. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above. Table 2 shows the results.

Comparative Example 9 Sucrose lauric acid monoester (SM) was used as the component (a).
-1200, Mitsubishi Chemical Foods Co., Ltd.), Hexanol (special grade, Tokyo Chemical Industry Co., Ltd.) as component (b), (c)
Decane (special grade, Tokyo Chemical Industry Co., Ltd.) as an ingredient,
(D) Distilled water was weighed as a component according to the formulation shown in Table 2, placed in a container, shaken while heating to 95 ° C, and then cooled to room temperature to obtain a liquid composition. The stable temperature range (° C.) of the obtained liquid composition was measured by the method described above.
Table 2 shows the results. Table 2 also shows the ester fraction of the sucrose lauric acid monoester used.

[0031]

[Table 1]

[0032]

[Table 2]

From Tables 1 and 2, the following matters become clear. 1. The liquid composition according to the present invention is not only transparent at room temperature, but also stable without two-phase separation in a wide temperature range (Examples 1 to 6). 2. On the other hand, although it contains four components (a) to (d), [{(b) component} / ｛(a) component +
In Comparative Examples 1 to 4 in which the component (b) is out of the range of 0.2 to 0.9, in each case, two phases are separated, and a transparent liquid composition cannot be obtained. 3. In Comparative Examples 5 and 6, which do not contain the component (a), the temperature range in which the liquid composition shows a transparent state is narrow, and the object of the present invention is not achieved. 4. Furthermore, in Comparative Examples 7 and 8, which do not contain the component (a) and the component (b), the temperature range in which the transparent state is exhibited is higher than room temperature and the range is narrow, and the object of the present invention is not achieved. 5. Furthermore, in Comparative Example 9 using sucrose lauric acid monoester in which the component (a) ester distribution does not satisfy claim 1, two phases are separated, and a transparent liquid composition cannot be obtained.

Claims (3)

[Claims] (1) 60-90% by weight of a monoester,
A sucrose fatty acid ester of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms having an ester distribution of 5 to 40% by weight of diester {hereinafter referred to as "component (a)"; (b) a monohydric alcohol having 4 to 20 carbon atoms A liquid composition comprising, as essential components, a class {the component (b)), (c) an oil component, a component (c), and (d) a component {d). The total weight of the components (a) and (b) is 3% by weight or more, and the weight fraction of the component (b) with respect to the total of the components (a) and (b) is 0.1%.
A liquid composition having an oily component solubilized in the range of 2 to 0.9. 2. The liquid composition according to claim 1, wherein the weight fraction of (c) with respect to the sum of the components (c) and (d) is in the range of 0.05 to 0.95. 3. The liquid composition according to claim 1, which has a uniform appearance in a temperature range of 0 ° C. to 90 ° C.