JP2002308962A - Emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new emulsified composition excellent in high-temperature stability. SOLUTION: A polyoxyethylene dipolyhydroxystearate and a 1,1-methylene- bis(4-isocyanatocyclobexane)polypropylene glycol copolymer are incorporated into an emulsion comprising e.g. an O/W or W/O/W emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an emulsified composition useful for an external preparation for skin such as cosmetics.

[0002]

2. Description of the Related Art Emulsion compositions are widely used as useful preparations in the fields of cosmetics, toiletries, foods and pharmaceuticals. This is because, in the emulsifier system, the oily component and the aqueous component are present in a uniform state, and are difficult to exist as they are, and the two components can be combined. . The most important issue in such an emulsified composition is stability. This is because the emulsifying system is originally a metastable system, and a slight change in the system immediately affects the stability. Such a tendency is considered to be an oil-in-water-in-oil emulsified dosage form in which an oil phase is present in the outer phase among the various emulsified forms, in particular, an oil-in-water emulsion is present in the inner phase and the outer phase is the oil phase. In particular, storage stability at 40 ° C. (high temperature) at which the viscosity of the oil phase lowers is important. In other words, in the emulsified form in which the oil phase is present in the external phase, securing high-temperature stability is an important issue. There has not yet been a unified standard for solving such problems, and at present, it has been necessary to formulate a formulation through repeated trial and error of formulation research.

On the other hand, emulsified compositions containing polyoxyethylene dipolyhydroxystearate and 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer are characterized in that There is no known emulsion composition in which an oil phase exists in an external phase such as an oil-in-water emulsion. Therefore, it is not known at all that the emulsified composition having such a constitution has excellent stability in a high temperature range.

[0004]

The present invention has been made under such circumstances, and an object of the present invention is to provide a novel emulsified composition having excellent high-temperature stability.

[0005]

In view of such circumstances, the present inventors have made intensive research efforts for a novel emulsion composition having excellent high-temperature stability. , 1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer, and found such characteristics in an emulsified composition, thereby completing the invention. That is, the present invention relates to the following technology. (1) An emulsified composition containing polyoxyethylene dipolyhydroxystearate and 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer. (2) The oil phase is present in the external phase, (1)
3. The emulsified composition according to item 1. (3) an oil-in-water-in-oil emulsifying agent form,
The emulsion composition according to (1) or (2). (4) excellent in high-temperature stability, (1) to
(3) The emulsified composition according to any one of the above items. (5) It is a skin external preparation, (1) to
(4) The emulsion composition according to any one of (1) to (4). (6) (1) to (5) characterized in that it is a cosmetic.
An emulsified composition according to any one of the preceding claims. (7) The emulsified composition according to any one of (1) to (6), further comprising a sucrose fatty acid ester. Hereinafter, the present invention will be described in more detail focusing on embodiments.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Polyoxyethylene dipolyhydroxystearate contained in the emulsified composition of the present invention The polyoxyethylene polyhydroxystearate contained in the emulsified composition of the present invention is obtained by mixing polyethylene glycol with an alkali. It can be obtained by reacting acid chloride prepared by reacting poly (12-hydroxystearic acid) with a halogenating agent such as thionyl chloride in the presence. At this time, if the amount of the acid chloride is increased, a polyester having two or more diacids can be obtained. If the amount is small, a low acylation rate such as a monoester can be obtained. In this case, the polyethylene glycol preferably has an average molecular weight of 400 to 6000. On the other hand, the other component, poly (12-hydroxystearic acid)
Is a portion which becomes a hydrophobic group in this essential component, and preferably has an average molecular weight of 1,000 to 3,000 in size. Some of these polyoxyethylene dipolyhydroxystearates are already commercially available,
In the present invention, such commercially available products can also be used. Among such commercially available products, particularly preferred is "Aracel P-135", which is commercially available from Unichema. This is polyethylene glycol (average molecular weight 150
0) is a diester of poly (12-hydroxystearic acid) having an average molecular weight of about 5000. In the emulsified composition of the present invention, polyoxyethylene dipolyhydroxystearate may contain only one kind, or may contain two or more kinds in combination.
These have the effect of allowing the continuous phase to stably exist in the emulsification system of the present invention. The preferable content thereof is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the total amount of the emulsified composition. this is,
This is because a stable emulsion composition can be obtained in this amount range.

(2) 1,1 contained in the emulsified composition of the present invention
1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer The emulsion composition of the present invention comprises 1,1-methylene-bis (4-
(Isocyanate cyclohexane) polypropylene glycol copolymer. This is known to form a film having a barrier function on the skin, and is contained in a skin external preparation such as a cosmetic for this purpose. Some of these are already commercially available, and such commercially available products can be used in the emulsion composition of the present invention. As a preferable commercial product, for example, polyol prepolymer 2 sold by Nippon Surfactant Co., Ltd. can be preferably exemplified. Such 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer may contain only one kind or two or more kinds in combination. 1,1-methylene-bis (4
-Isocyanate cyclohexane) The preferable content of the polypropylene glycol copolymer is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the emulsion composition. If the amount is too large, the emulsifiability may be impaired. If the amount is too small, a stabilizing effect may not be obtained in a high temperature range.

(3) Form of the emulsified composition of the present invention A preferable form of the emulsified composition of the present invention is a form in which an oil phase is present in an external phase.
For example, a water-in-oil emulsified form in which water droplets are present in a continuous phase of oil, an oil-in-water-in-oil emulsified form in which an oil-in-water emulsion is present in a continuous phase of oil, etc. An oil emulsified form is particularly preferred. This is because the addition of the sucrose fatty acid ester of the present invention significantly improves the low-temperature stability in this emulsified form. In such a form, a secondary effect of having a comfortable use feeling at the time of application is also exhibited. As a preferred embodiment, the field of application of the emulsified composition of the present invention, which takes such an emulsified form, is not particularly limited as long as it is a field to which the emulsion is applied. For example, foods, cosmetics, pharmaceuticals and the like Can be preferably exemplified. Among them, particularly preferable ones are those which can make the best use of the good use feeling of the emulsified composition of the present invention.

(4) Emulsified Composition of the Present Invention The emulsified composition of the present invention is characterized in that it contains the above essential components and has a preferred form of an emulsified form having the above-described oil phase as an external phase. The emulsified composition of the present invention may contain, in addition to the essential components described above, optional components usually used in the emulsified composition as long as the effects of the present invention are not impaired. Such optional components include, for example, hydrocarbons such as squalane, petrolatum, and microcrystalline wax, jojoba oil, carnauba wax, esters such as octyldodecyl oleate,
Triglycerides such as olive oil, beef tallow, and coconut oil; fatty acids such as stearic acid, oleic acid, and ritinoleic acid;
Higher alcohols such as oleyl alcohol, stearyl alcohol and octyl dodecanol; anionic surfactants such as sulfosuccinates and sodium polyoxyethylene alkyl sulfate; amphoteric surfactants such as alkyl betaine salts; cationic interfaces such as dialkyl ammonium salts. Activators, nonionic surfactants such as sorbitan fatty acid esters, fatty acid monoglycerides, their polyoxyethylene adducts, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyethylene glycol, glycerin, 1,3-butanediol And the like, polyhydric alcohols such as, for example, thickening / gelling agents, antioxidants, ultraviolet absorbers, coloring agents, preservatives, and powders. Of these, particularly preferred are olive oils that make a favorable contribution to low-temperature stability, and among them, olive oil from which impurities have been removed by column chromatography or the like is particularly preferred because of its remarkable effect of improving low-temperature stability. As such a refined olive oil, "Cropure OL" commercially available from Kuroda can be preferably exemplified. The preferred content of such olive oil is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
The emulsion composition of the present invention can be produced by treating these essential components and optional components according to a conventional method.

The emulsion composition of the present invention preferably contains a sucrose fatty acid ester as an optional component.
The sucrose fatty acid ester preferably contained in the emulsified composition of the present invention has an effect of also improving the stability in a low-temperature region in the emulsified system of the emulsified composition of the present invention. The sucrose fatty acid ester that can be used in the emulsion composition of the present invention can be used without any particular limitation as long as it is usually used in such an emulsion composition. For example, lauric ester, Myristate, palmitate, stearate, behenate,
Oleic acid ester, linoleic acid ester, linoleic acid ester, ritinoleic acid ester, acetate ester,
Examples thereof include isostearic acid esters, isooctanoic acid esters, and mixed esters thereof. Preferred examples include esters of fatty acids having 12 or more carbon atoms with saturated fatty acids. Particularly preferred are those having a fatty acid composition constituting an ester. Particularly preferred is a stearic acid-based palmitic acid mixed fatty acid having a stearic acid: palmitic acid ratio of about 7: 3, which is mainly composed of stearic acid. Such a product is commercially available from Daiichi Kogyo Seiyaku Co., Ltd. “Sugar wax S”
E-10 "can be particularly preferably exemplified. The preferred content of such sugar wax in the emulsion composition of the present invention is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the emulsion composition. is there. This is because if the amount is too small, the stabilizing effect may not be obtained, and if the amount is too large, the freedom of formulation may be impaired.

[0011]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to these examples.

Example 1 An emulsified composition 1 of the present invention was prepared according to the following formulation. That is, the components a and b are 70
The mixture was heated to 0 ° C., and the mixture was gradually added to the mixture while stirring, emulsified, and stirred and cooled to obtain a water-in-oil emulsion composition 1. This was suitable as a cosmetic. Separately, Comparative Example 1 was also prepared in which the polyol prepolymer 2 (1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer) of this emulsion composition was replaced with water. Further, the emulsified composition 1 and the comparative example 1 were subjected to a storage test at 40 ° C. The results are shown in Table 1 as changes in hardness. Hardness was measured using a card meter and the hardness was 1
The measurement was performed with a 6φ attachment. This indicates that the emulsified composition of the present invention has excellent high-temperature stability.
In addition, it had a smooth growth property and was suitable as a cosmetic. A “Aracel P-135” 2 parts by weight Femethicone 10 parts by weight Dimethicone 5 parts by weight “Cropure OL” 3 parts by weight Crill 61 1 part by weight Sugar ester SE-10 1 part by weight glycerin 5.4 parts by weight Polyethylene glycol 1500 3 parts by weight Part "Polyol prepolymer 2" 2 parts by weight Water 69.6 parts by weight

[0013]

[Table 1]

Example 2 An emulsified composition of the present invention was prepared according to the following formulation. That is, (a) and (b) were each heated to 70 ° C., and (b) was gradually added to (a) to obtain an intermediate oil-in-water emulsion 1. Using this, C, D and E are each heated to 80 ° C., D is gradually added to C, and finally E is added and stirred and cooled to obtain an oil-in-water-in-oil emulsified composition of the present invention. Composition 2 (Example 2) was obtained. This product had a smoother spreading property and was suitable as a cosmetic. Comparative Example 2 was also made by replacing the polyol prepolymer with water. The stability is shown in Table 2 as a change in hardness after storage at 40 ° C. The hardness was determined in the same manner as in Example 1. From this, it can be seen that the effect of adding the polyol prepolymer of the present invention is more clearly exhibited by forming a multiple emulsion. A 10% aqueous solution of potassium hydroxide 0.1 part by weight 1,3-butanediol 3 parts by weight Water 15.5 parts by weight Lo behenyl alcohol 0.4 parts by weight Hydrogenated tallow 0.1 part by weight Squalane 5 parts by weight Sugar wax SE- 10 2 parts by weight Phenoxyethanol 0.2 parts by weight Mixed fatty acid triglyceride * 0.1 parts by weight Behenic acid 0.1 parts by weight Stearic acid 0.5 parts by weight Glycerin 3 parts by weight C methyl paraben 0.1 parts by weight 1,3-butanediol 5 parts by weight Glycerin 5 parts by weight Polyethylene glycol 1500 1 part by weight Poly MPC *** 0.1 part by weight "Polyol prepolymer 2" 2 parts by weight Water 24.88 parts by weight D "Arcel P-135" 1 part by weight "Eldew" PS-304 "** 0.1 part by weight Macadamia fatty acid phytosteryl 5 parts by weight Camellia oil 0.5 parts by weight Decamethylcyclopentasiloxane 4 parts by weight Cetyl 2-ethylhexanoate 19 parts by weight "Cropure OL" 1 part by weight Crill 6 1 part by weight Butyl paraben 0.1 part by weight δ Tocopherol 0.02 Parts by weight E Intermediate oil-in-water emulsion 1 30 parts by weight Touki extract 1 part by weight Chorei extract 0.7 part by weight Tonin extract 0.8 part by weight Chimpi extract 0.5 part by weight * N-lauroyl-L-glutamate di (phytosteryl- 2-octyldodecyl) ** tri (capric acid, caprylic acid, myristic acid, stearic acid) glyceride *** polymethacryloyloxyethyl phosphorylcholine

[0015]

[Table 2]

Example 3 An emulsified composition of the present invention was prepared according to the following formulation. That is, (a) and (b) were each heated to 70 ° C., and (b) was gradually added to (a) to obtain an intermediate oil-in-water emulsion 1. Using this, C, D and E are each heated to 80 ° C., D is gradually added to C, and finally E is added and stirred and cooled to obtain oil-in-water-in-oil emulsified composition of the present invention. Composition 3 (Example 3) was obtained. This product had a smoother spreading property and was suitable as a cosmetic. Comparative Example 2 was also made by replacing the polyol prepolymer with water. The stability is shown in Table 3 as a change in hardness after storage at 40 ° C. The hardness was determined in the same manner as in Example 1. Thus, in the emulsified composition of the present invention, the preferable content of 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer is 0.1.
It turns out that 5-5 weight% is especially preferable. A 10% aqueous potassium hydroxide solution 0.1 part by weight 1,3-butanediol 3 parts by weight Water 15.5 parts by weight Lo behenyl alcohol 0.4 parts by weight Hydrogenated tallow 0.1 part by weight Squalane 5 parts by weight Sugar wax SE- 10 2 parts by weight Phenoxyethanol 0.2 parts by weight Mixed fatty acid triglyceride * 0.1 parts by weight Behenic acid 0.1 parts by weight Stearic acid 0.5 parts by weight Glycerin 3 parts by weight C methyl paraben 0.1 parts by weight 1,3-butanediol 5 parts by weight Glycerin 5 parts by weight Polyethylene glycol 1500 1 part by weight Poly MPC *** 0.1 part by weight "Polyol prepolymer 2" 1 part by weight Water 25.88 parts by weight d "Arcel P-135" 1 part by weight "Eldew" PS-304 "** 0.1 part by weight Macadamia fatty acid phytosteryl 5 parts by weight Camellia oil 0.5 parts by weight Decamethylcyclopentasiloxane 4 parts by weight Cetyl 2-ethylhexanoate 19 parts by weight "Cropure OL" 1 part by weight Crill 6 1 part by weight Butyl paraben 0.1 part by weight δ Tocopherol 0.02 Parts by weight E Intermediate oil-in-water emulsion 1 30 parts by weight Touki extract 1 part by weight Chorei extract 0.7 part by weight Tonin extract 0.8 part by weight Chimpi extract 0.5 part by weight * N-lauroyl-L-glutamate di (phytosteryl- 2-octyldodecyl) ** tri (capric acid, caprylic acid, myristic acid, stearic acid) glyceride *** polymethacryloyloxyethyl phosphorylcholine

[0017]

[Table 3]

Example 4 An emulsion composition of the present invention was prepared according to the following formulation. That is, (a) and (b) were each heated to 70 ° C., and (b) was gradually added to (a) to obtain an intermediate oil-in-water emulsion 1. Using this, C, D and E are each heated to 80 ° C., D is gradually added to C, and finally E is added and stirred and cooled to obtain an oil-in-water-in-oil emulsified composition of the present invention. Composition 4 (Example 4); a skin external medicine was obtained. A 10% aqueous solution of potassium hydroxide 0.1 part by weight 1,3-butanediol 3 parts by weight Water 15.5 parts by weight Lobehenyl alcohol 0.4 parts by weight Hydrogenated tallow 0.1 part by weight Dexamethasone 1 part by weight Squalane 5 parts by weight Sugar wax SE-10 2 parts by weight Phenoxyethanol 0.2 parts by weight Mixed fatty acid triglyceride * 0.1 parts by weight Behenic acid 0.1 parts by weight Stearic acid 0.5 parts by weight Glycerin 3 parts by weight C methyl paraben 0.1 parts by weight 1, 3-butanediol 5 parts by weight Glycerin 5 parts by weight Polyethylene glycol 1500 1 part by weight Poly MPC *** 0.1 part by weight "Polyol prepolymer 2" 2 parts by weight Water 21.88 parts by weight D "Aracel P-135" 1 Parts by weight "Eldew PS-304" ** 0.1 parts by weight Macadamia Phytosteryl fatty acid 0.5 parts by weight Camellia oil 0.5 parts by weight Decamethylcyclopentasiloxane 4 parts by weight Cetyl 2-ethylhexanoate 19 parts by weight "Cropure OL" 1 part by weight Kuril 6 1 part by weight Butyl paraben 0.1 part by weight δ tocopherol 0.02 parts by weight E Intermediate oil-in-water emulsion 1 30 parts by weight Touki extract 1 part by weight Chorei extract 0.7 part by weight Tonin extract 0.8 part by weight Chimney extract 0.5 part by weight * N-lauroyl-L-glutamic acid Di (phytosteryl-2-octyldodecyl) ** tri (capric acid / caprylic acid / myristic acid / stearic acid) glyceride *** polymethacryloyloxyethyl phosphorylcholine

[0019]

According to the present invention, a novel emulsified composition having excellent high-temperature stability can be provided.

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Claims (7)

[Claims] 1. An emulsion composition comprising polyoxyethylene dihydroxystearate and 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer. 2. The emulsion composition according to claim 1, wherein an oil phase is present in the external phase. 3. The emulsified composition according to claim 1, which is in the form of an oil-in-water-in-oil emulsion. 4. An excellent high-temperature stability.
The emulsion composition according to claim 1. 5. The emulsion composition according to claim 1, which is an external preparation for skin. 6. The emulsion composition according to claim 1, which is a cosmetic. 7. The emulsion composition according to claim 1, further comprising a sucrose fatty acid ester.