JP3529223B2 - Water-in-oil gel emulsion composition and emulsified cosmetic or external preparation using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-in-oil emulsion composition which is useful as a base for cosmetics and external ointments.
More specifically, as an external phase component of the emulsified composition, a water-in-oil type gel-like emulsified composition using an ester-based oil component, which has been difficult to mix conventionally, as a base, and this water-in-oil type gel-like emulsified composition The present invention relates to a water-in-oil type emulsified cosmetic composition and an external preparation which are excellent in emulsion stability and feel when used and have no safety concerns.

[0002]

2. Description of the Related Art Water-in-oil gel emulsion compositions are widely used in a great number of fields and are not only important as a base for emulsified cosmetics or external preparations, but their properties are also important. It is one of the factors that determine quality. Taking skin care cosmetics such as cream as an example, the main purpose of this cosmetic is to supplement moisture and oil to the skin to tone the skin, and the most important function is to It has a water retention function to give moisture and flexibility to the skin and a water evaporation suppression function.

Cosmetics containing oil and water as basic components are generally water-in-oil emulsions in which liquid droplets of an aqueous phase are dispersed in an oil continuous phase, and liquid droplets of an oil phase are dispersed in a water continuous phase. It is known that the water-in-oil emulsion is superior to the oil-in-water emulsion in many respects such as protection of skin and maintenance of flexibility.

[0004]

However, it is relatively difficult to maintain the emulsified state of a product using a water-in-oil emulsion for a long period of time. In order to improve the emulsion stability, a conventional method is to add a large amount of waxes to the oil phase which is a continuous phase to increase the viscosity of the emulsion. With respect to the temperature change, phenomena such as softening and melting of the blended waxes occurred, and the emulsion stability could not be sufficiently improved.

Therefore, in terms of feel in use, problems such as stickiness, oiliness, and heavy spread occur, and as a result, the water-in-oil emulsion has very limited uses, for example, excellent water resistance. Due to its advantages, it was limited to application to dosage forms such as hand creams and foundations.

Various investigations have been made to solve these problems. For example, a gel emulsification method using an amino acid (Japanese Patent Publication No. 53-21393) has been proposed, and an oil agent applicable to this method is liquid paraffin,
Limited to hydrocarbon-based oils such as squalane and microcrystalline wax, polar oils such as esters (hereinafter,
(Sometimes referred to simply as ester oil) is not suitable because it has a problem in emulsion stability and causes phase separation and the like.

[0007] Therefore, ester oils are generally superior in miscibility with sebum as compared with hydrocarbon type oils, and have the advantages that they are not slippery on the skin, have good compatibility, and are difficult to shine. Since it has excellent air permeability and also plays a role of controlling skin occlusivity due to an oil film, it is commonly used in cosmetics using an oil agent, but the practical application of the emulsification method is limited in practical application.

Further, in recent years, a method of emulsifying using a clay mineral hydrophobized and oil-swelled with a quaternary ammonium salt type organic cationic substance (Japanese Patent Publication No. 232015) has been developed. When additional tests were conducted by the authors, in this method as well, when a polar oil such as ester was used, the stability of the emulsified state increased as the blending ratio increased, as compared with the case where the oil agent was a hydrocarbon oil. Is likely to deteriorate, and phase separation occurs when about 20% by weight or more of the ester polar oil in the oil agent is used. In addition, there is a restriction on the formulation that a large amount of the internal water phase must be added in order to maintain the emulsion stability. In addition, when a cationic surfactant is used as an emulsifier, there are concerns about safety such as irritation to skin and mucous membranes.

In addition to these, ethylene oxide and propylene oxide addition type silicone surfactants have also been used as water-in-oil type emulsifiers. As a result, it tends to be disliked, and in order to maintain the emulsion stability, a silicone oil must be used in combination as an oil agent, which also has limited applications. Further, since alkylene oxide addition type surfactants such as ethylene oxide and propylene oxide have high skin permeability, there is a growing concern about safety in recent years.

By the way, in recent years, there is an increasing concern about the effect of UV irradiation on the skin, and the demand for sunscreen cosmetics is increasing. Its formulation is the most common and representative water-in-oil type emulsion cosmetics, and SPF (Su
In order to increase the n Protection Factor value, it is almost always blended with an ultraviolet absorbing oil agent, and for example, ester oils such as paramethoxycinnamic acid ester and dimethylparaaminobenzoic acid ester are widely used. However, these ester oils having a functional group having a function of absorbing ultraviolet rays have a particularly high polarity, and thus it is difficult to maintain the stability when emulsifying the ester oil. Nevertheless, in order to prepare a water-in-oil emulsion composition, the above methods and combinations thereof have to be dealt with, and it is often inevitable to limit the blending amount of such ester oils. It was

In view of such a situation, the present invention solves the above-mentioned problems, is excellent in emulsion stability even when a polar oil such as ester is added, has a good feeling in use, and is safe. There is no concern, and an object is to provide a versatile water-in-oil type gel emulsion composition. Further, the present invention provides a water-in-oil type emulsified cosmetic composition and an external preparation using such a water-in-oil type gel emulsion composition.

[0012]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that an oligoesterification product having a specific structure has an extremely excellent water-in-oil emulsification property under certain conditions. In addition, the water-in-oil type gel emulsion composition obtained under this particular condition maintains a stable emulsified state, is excellent in feeling in use, and is extremely useful for water-in-oil type cosmetics and external preparations. The inventors have found that there is something and have completed the present invention.

That is, the first gist of the present invention is to contain an emulsifying base (A), an oil phase base (B) and an aqueous phase base (C) shown below, wherein the base (A), ( The blending ratio of B) and (C) is (A) :( B) = 3: 1 to 1:50 (weight ratio), {(A) + (B)} :( C) = 5: 1 to 1 : 10 (weight ratio), a water-in-oil type gel-like emulsion composition.

Emulsifying base (A): Diglycerin, a fatty acid having 6 to 22 carbon atoms, and a medium-chain dibasic acid having 4 to 10 carbon atoms in reaction molar ratios of X, Y and Z, respectively.
Where, the oligoesterification product obtained by the esterification reaction so that the following conditions (a) and (b) are simultaneously satisfied.

Condition (a): 0.5≤Z / X≤0.95 Condition (b): 0.2≤Y / (2X + 2) ≤0.9 Oil phase base (B): Having a free hydroxyl group An oily component that contains a non-ester as an essential component and has a dielectric constant of 2.5 or more.

Aqueous phase base (C): water-soluble organic acid and /
Alternatively, an aqueous solution containing 0.1 to 10% by weight of a salt thereof or an inorganic salt and having a pH of 3 to 9.

The second aspect of the present invention comprises the emulsifying base (A), the oil phase base (B) and the aqueous phase base (C) described above, and among these bases (A): (B) is in a weight ratio of 3:
1 to 1:50, and a water-in-oil type gel emulsion composition in which {(A) + (B)} :( C) is mixed in a weight ratio of 5: 1 to 1:10 is mixed with an oil component. The water-in-oil type emulsified cosmetic or external preparation.

A third aspect of the present invention comprises the emulsifying base (A), the oil phase base (B) and the aqueous phase base (C) described above, and among these bases (A). : (B) is 3: by weight.
1 to 1:50, and a water-in-oil type gel emulsion composition in which {(A) + (B)} :( C) is mixed in a weight ratio of 5: 1 to 1:10 is mixed with an oil component. Then, a water-in-oil type emulsified cosmetic or external preparation is prepared by further adding an aqueous component and emulsifying the mixture.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION A water-in-oil type gel emulsion composition of the present invention comprises an emulsifying base (A), an oil phase base (B) and an aqueous phase base (C) shown below. Among these bases, (A) :( B) is 3: 1 to 1:50 by weight, and {(A) + (B)} :( C) is 5: 1 by weight. 1: 1
It is prepared by emulsifying into a water-in-oil type gel so that each blending ratio is 0.

Here, the emulsifying base (A) is diglycerin,
Fatty acids having 6 to 22 carbon atoms and 4 to 1 carbon atoms
The reaction molar ratios of the medium-chain dibasic acid which is 0 are X and Y, respectively.
And Z, condition (a): 0.5 ≦ Z / X ≦
0.95 and condition (b): 0.2 ≦ Y / ( 2 X + 2)
An oligoesterification product obtained by performing an esterification reaction so that ≦ 0.9 is simultaneously satisfied, and the oil phase base (B) contains an ester having no free hydroxyl group as an essential component,
An oily component with a dielectric constant of 2.5 or more, and an aqueous phase base (C)
Is an aqueous solution containing 0.1 to 10% by weight of a water-soluble organic acid and / or its salt or an inorganic salt and having a pH of 3 to 9.

The emulsifying base (A), which is an element constituting the water-in-oil type gel emulsion composition of the present invention, comprises diglycerin, a fatty acid having 6 to 22 carbon atoms, and a medium chain having 4 to 10 carbon atoms. Although it is an oligoesterification product obtained by esterifying a dibasic acid at a specific reaction ratio, the fatty acid that can be used here may be a fatty acid that is usually used for the purpose, and may be used in cosmetics and external preparations. In this case, fatty acids commonly used as a raw material thereof, for example, caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, palmitooleic acid,
Isooctylic acid (2-ethylhexanoic acid, etc.), isononanoic acid (3,5,5-trimethylhexanoic acid, etc.), isopalmitic acid, isostearic acid (2-heptylundecanoic acid, multi-methyl branched type manufactured by Emery Co., Ltd.) And so on. Fatty acids having less than 6 carbon atoms are unsuitable in terms of skin irritation and hydrolysis stability. Further, when the carbon number is 23 or more, the esterification reaction does not easily proceed and it becomes difficult to obtain the desired oligoesterification product according to the present invention, which is not suitable.

In order to further improve the long-term stability of the water-in-oil type gel emulsion composition, fatty acids, particularly palmitic acid, stearic acid, behenic acid, etc., are straight-chain long-chain saturated fatty acids having 16 to 22 carbon atoms. It is desirable to use one type or two or more types of Further, in consideration of the familiarity to the skin in terms of feeling in use, the fatty acids further include isooctylic acid, isononanoic acid, isopalmitic acid, 2-hexyldecanoic acid, isostearic acid (multi-methyl branched type manufactured by Emery), 2-
It is preferable to use it as a mixed fatty acid to which one or more branched fatty acids having 8 to 18 carbon atoms such as heptylundecanoic acid are appropriately added.

Examples of the medium-chain dibasic acid include succinic acid,
Examples thereof include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Generally, one or more selected from the group consisting of easily available adipic acid, azelaic acid and sebacic acid may be used. When a dibasic acid having 11 or more carbon atoms is used, the oligoesterification product tends to lose its water-in-oil emulsification property, and even if a water phase base is added to this product, a gel-like emulsified composition is obtained. It does not become a substance, and the separation of the aqueous phase occurs immediately. This tendency becomes remarkable when the carbon number is 14 or more. on the other hand,
When a dibasic acid having 3 or less carbon atoms is used, a polymerized product is produced by an esterification reaction, resulting in high viscosity,
In addition, the physical properties of the obtained product are not stable, so that it is unsuitable as a raw material of the present invention.

In order to prepare the emulsifying base (A) applicable to the present invention, the reaction molar ratios of the above-mentioned diglycerin, fatty acid and medium-chain dibasic acid are respectively X, Y and Z.
Is expressed as 0.5 ≦ Z / X ≦ 0.95, preferably 0.6 ≦ Z / X ≦ 0.9 and 0.2 ≦ Y / (2
X + 2) ≦ 0.9, preferably 0.3 ≦ Y / (2X +
It is important to carry out the esterification reaction so that 2) ≦ 0.8 is satisfied at the same time. When Z / X <0.5, the produced esterification product shows some emulsification characteristics, but the stability of the emulsified composition is poor, and separation of the aqueous phase easily occurs. On the contrary, when 0.95 <Z / X, the product of the esterification reaction has an excessively high degree of polymerization and a high viscosity, which is not suitable as the emulsifying base (A) of the present invention. When Y / (2X + 2) <0.1, the affinity between the esterified product and other known oil agents is deteriorated, and the oil phase is easily separated in the emulsified composition.
On the other hand, in the case of 0.9 <Y / (2X + 2), the water-in-oil type emulsifying property is not exhibited, and even if the water phase is added, the gelled emulsified composition is not obtained and the water phase is easily separated. Like

In the present invention, the esterification reaction of the oligoesterification product which is the emulsifying base (A) uses the above-mentioned diglycerin, fatty acid and medium-chain dibasic acid as raw materials,
It is carried out according to a conventional method (reaction at 100 to 250 ° C. for 1 to 20 hours) under normal pressure or reduced pressure with or without catalyst. After completion of the esterification reaction, if necessary, for example, the reaction product is decolorized with a decoloring agent and further deodorized under reduced pressure for purification to obtain a liquid or pasty oligoesterification product of the present invention.

The oil phase base (B), which is an element constituting the water-in-oil type gel emulsion composition of the present invention, contains an ester having no free hydroxyl group as an essential component, and its dielectric constant is 2.5.
As mentioned above, it is more preferably composed of an oil component of 2.8 to 8.0, and further preferably having a dielectric constant of 2.8 to 7.5. Appropriate esters corresponding to this may be those normally used for the purpose, and in the case of cosmetics and external preparations, they have been conventionally used as oil agents and oily components of cosmetics and external preparations. It can be selected from synthetic esters and natural oils and fats, and for example, synthetic esters include isopropyl myristate, isopalmityl myristate, octyldodecyl myristate, cetyl isooctylate, isononyl isononanoate, isooctyl palmitate, oleyl oleate, stearyl stearate, dicaprine. Acid neopentyl glycol ester, diisooctyl neopentyl glycol ester, diheptyl undecyl adipate, glyceryl triisooctylate, glyceryl triisopalmitate, glyceryl tricaprylate,
Glyceryl tricaprate, glyceryl tristearate, diglyceryl tetraisostearate, pentaerythritol tetraisooctylate, dipentaerythritol hexaisostearate, isooctyl paramethoxycinnamate, isooctyl dimethylaminobenzoate, glyceryl monoisooctyl diparamethoxycinnamate. and so on.

Examples of natural oils and fats include plants such as eucalyptus oil, soybean oil, sesame oil, rice germ oil, safflower oil, palm oil, olive oil, jojoba oil, macadamian nut oil, avocado oil, evening primrose oil, castor oil and the like. Animal fats and oils, such as natural fats, turtle oil, mink oil, and orange laffy oil,
There are waxes such as carnauba wax, candelilla wax and beeswax, hardened oil (hydrogenated oil) such as hardened soybean oil and rapeseed oil, processed fats and oils such as transesterified fats and fractionated fats and oils.

An ester having a hydroxyl group in the molecule, such as castor oil, is not suitable in the present invention because it acts to destabilize the emulsified state. However, it may be added in an amount that does not impair the gist of the present invention (eg, emulsion stability). Further, in the oil phase base (B) of the water-in-oil type gel emulsion composition of the present invention, a hydrocarbon oil or a silicone oil may be used in combination with the ester. However, in this case, the ester and the other than the ester are so selected that the oil phase base has a dielectric constant of 2.5 to 8.0, preferably 2.8 to 8.0, and more preferably 2.8 to 7.5. It is important to adjust the blending ratio with the oily component. Oil phase base (B)
The content of the ester therein is difficult to specify uniformly, but is generally 20 to 100% by weight.

The water phase base (C), which is a component of the water-in-oil type gel emulsion composition of the present invention, contains a water-soluble organic acid and / or its salt or an inorganic salt of 0.1 to 10 parts. An aqueous solution containing 3% by weight and having a pH of 3-9. Examples of the organic acid include citric acid, malic acid, tartaric acid, fumaric acid, succinic acid, lactic acid, oxalic acid, pyrrolidonecarboxylic acid, ascorbic acid, glycyrrhizic acid, and the like. Examples thereof include tritype potassium salt and sodium salt, and examples of the inorganic salt include sodium chloride, potassium chloride, sodium sulfate, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, zinc sulfate and the like. These can be used alone or as a mixture in an arbitrary ratio, and it is necessary to contain 0.1% by weight to 10% by weight in the aqueous phase base (C), preferably 0.2% by weight or more.

When such an organic acid and / or salt is not added to the aqueous phase base (C), the oligoesterification product of the emulsification base (A) has a free hydroxyl group, Has a good miscibility, the emulsion base (A), the oil phase base (B) and the aqueous phase base (C) are mixed to form a cloudy emulsion composition, but the gel property is weak. When this is observed under a microscope, it is found that, when 0.1% by weight or more of the organic acid and / or salt is added, droplets of an aqueous phase of several microns or submicrons are uniformly dispersed in a continuous oil phase. On the other hand, it is observed as a state in which a portion in which the water phase is dispersed as droplets and a portion in which the water phase does not form droplets and continuously exists are mixed. That is, a good water-in-oil type emulsion composition is not formed, and the separation of the aqueous phase occurs 2-3 days after the preparation of this emulsion composition.
Further, when the amount of the organic acid and / or salt added is less than 0.1%, the same tendency is exhibited, and the emulsion stability with time is slightly better than in the case of no addition, but the aqueous phase eventually separates. . Addition of 0.1% by weight or more, especially 0.2% by weight or more solves such a problem.

The pH of the aqueous phase base (C) needs to be 3-9, preferably 4-8.5. pH is 3
When it is less than 9 or higher than 9, the emulsified particles generated upon emulsification are coarse and the emulsion stability is poor. Note that this pH adjustment is preferably performed in a buffer solution considering the quality of the product.

In the present invention, a polyhydric alcohol such as propylene glycol, 1,
Including glycols such as 3-butylene glycol, 3-methyl-1,3-butylene glycol and hexylene glycol, glycerin, sorbitol, diglycerin, erythritol, and sugars such as glucose, galactose, fructose, xylose, arabinose and maltose. Polyhydric alcohols can be added. The amount of the polyhydric alcohol blended is 1 with respect to the aqueous phase base (C).
-80 wt%, preferably 2-60 wt%. In this way, the water retaining function of the water-in-oil type gel emulsion composition of the present invention can be improved.

In the water-in-oil type gel emulsion composition of the present invention, the weight ratio of the emulsification base (A) to the oil phase base (B) is 3:
It is 1 to 1:50, preferably 2: 1 to 1:30. When the amount of the oil phase base (B) is less than 3: 1, the amount of the aqueous phase that can be dispersed in the mixed oil phase of the emulsification base (A) and the oil phase base (B) is small, It has practically no versatility. When the amount of the oil phase base (B) is more than 1:50, the emulsified particles become coarse and the emulsion stability deteriorates.

Further, in the water-in-oil type gel emulsion composition of the present invention, the weight ratio of the total of the emulsification base (A) and the oil phase base (B) to the water phase base (C) is 5: 1. ˜1: 10, preferably 3: 1 to 1: 8. Water phase base (C)
Is less than 5: 1, there is no particular problem in terms of emulsion stability, but the emulsion base (A) is used as effectively as possible, that is, an emulsion composition stable with a small amount of the emulsion base (A). Is not necessarily appropriate in the sense of obtaining When the amount of the aqueous phase base (C) is more than 1:10, the entire amount of the aqueous phase cannot be completely dispersed in the oil phase, and the undispersed aqueous phase is separated into the lower layer. .

The water-in-oil type gel emulsion composition of the present invention comprises the above-mentioned emulsifying base (A), oil phase base (B) and water phase base (C) in the above-mentioned specific mixing ratio by a conventional method. It can be prepared by mixing. That is, the emulsification base (A) and the oil phase base (B) are mixed at room temperature or under heating (up to about 80 ° C.) to form an oil phase, and an appropriate stirrer such as a homodisper or a homomixer is added to this. It is obtained by adding the aqueous phase base (C) with stirring and emulsifying it into a water-in-oil type.

Next, the case where the water-in-oil type gel emulsion composition of the present invention is applied to a water-in-oil type emulsion cosmetic and an external preparation will be described. The water-in-oil type emulsion cosmetic composition and the external preparation of the present invention are prepared by mixing the above-mentioned water-in-oil type gel emulsion composition and a known component used in general cosmetics or external preparations. That is, for example, the water-in-oil gel emulsion composition of the present invention is uniformly mixed with the oil component such as the ester oil, the hydrocarbon oil, and the silicone oil to form a water-in-oil emulsion product, Alternatively, it is used as a water-in-oil type product by further adding an aqueous component and emulsifying it. Such products include creams, emulsions,
Intended for lipsticks, lipsticks, eye creams, foundations, hair dressings and ointments.

In order to further exert the function of the composition of the present invention as a skin care cosmetic, it is preferable to add the above-mentioned polyhydric alcohols to the water phase base (C) or the water phase part. . Conventionally, in a system in which such a polyhydric alcohol and an ester are allowed to coexist, there was a great concern about the stability thereof, but the present invention can sufficiently cope with this. The polyhydric alcohol aqueous solution type gel-like emulsion composition obtained in the present invention has propylene glycol, 1,3-butylene glycol, 3-methyl-1,3 in the aqueous phase.
-Butylene glycol, glycols such as hexylene glycol, 3-methyl-1,3-butylene glycol,
Glycols such as hexylene glycol and polyhydric alcohols such as glycerin, sorbitol, diglycerin, erythritol, fructose and glucose can be blended, the water retention effect is significantly improved, and it is extremely useful as a moisturizing cosmetic composition. be able to.

[0038]

【Example】

[Synthesis Examples AH, Comparative Synthesis Examples ah] In the present invention,
An oligoesterification product as an emulsifying base (A) and an esterification product for comparison were synthesized by the following method. That is, in a 2-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a water separator,
Each raw material having a predetermined molar ratio shown in Table 1 was charged, 5% by weight of xylene and 0.3% by weight of tin chloride as a catalyst were added to the total charged amount, and the calculated amount of water was a water separator at 160 to 240 ° C. Then, the esterification reaction was carried out until the acid value and the hydroxyl value of the reaction product decreased almost completely. After the completion of the reaction, a deoxidation treatment using sodium hydroxide, a decolorization treatment using activated carbon and / or activated clay, and a deodorization treatment under reduced pressure were performed to obtain a liquid or pasty oligoesterification product (Synthesis Examples A to H). ).

The molar ratio of the charged diglycerin, fatty acid and dibasic acid used in the esterification reaction was X,
It is represented by Y and Z, and the values of Z / X and Y / (2X + 2) at that time are shown in Table 1. For comparison, each raw material having a predetermined molar ratio shown in Table 2 was charged and treated under the same conditions to obtain esterified products (Comparative Synthesis Examples a to h).

[0040]

[Table 1] Note 1) Chisso Chemical Co., Ltd., 2-ethylhexanoic acid 2) Nissan Chemical Co., Ltd., 3,5,5-trimethylhexanoic acid 3) Emery Co., polymethyl-branched isostearic acid

[0041]

[Table 2] Note 1) and 3): Same as Note 1) and 3) in Table 1.

Examples 1 to 8 and Comparative Examples 1 to 5 [Preparation of water-in-oil type gel emulsion composition]
A water-in-oil emulsion composition was prepared as described below using some of the esterification products prepared in H and comparative synthesis examples a to h, and the storage stability of each was investigated.

To 70 g of glyceryl triisooctylate (manufactured by Nisshin Oil Co., Ltd., TIO) was added 30 g of any of the esterification products obtained in Synthesis Examples A to H and Comparative Synthesis Examples a to c, g and h. , And mixed and dissolved at 60 ° C. to prepare an oil solution. Then, at 40 ° C., a homodisper (TK-16 type manufactured by Tokushu Kika Kogyo Co., Ltd .; the same applies hereinafter) (rotation speed:
Citric acid 0.
Aqueous solution containing 9% by weight and 0.1% by weight of trisodium citrate (1) 300 ml or (2) 100 ml
Was added to prepare a water-in-oil emulsion composition. In Comparative Synthesis Examples d and f, a high-viscosity product was produced during the esterification reaction and the reaction did not proceed thereafter, and in Comparative Synthesis Example e, the acid value of the reaction product did not decrease during the esterification reaction. Since the reaction did not proceed thereafter, neither preparation nor evaluation of the emulsion composition was carried out.

The stability of the emulsion composition is evaluated at 40 ° C.
After 1 day and 3 months of storage, the following criteria were used with the appearance, viscosity (as a gel property) and average emulsion particle size as indicators.

[0045]   Appearance evaluation: ○ -No phase separation observed △ -Oil phase separated ▲ -Water phase separated               × -Separated from oil phase and water phase   Viscosity measurement: When less than 10,000 cps, BL type viscometer, rotor No. 3, 30               rpm, 25 ° C               At 10,000 cps or more, BH type viscometer, rotor No. 6, 4r               pm, 25 ℃   Average particle size: Observed with an optical microscope, randomly select 30 dispersed droplets, and             The average particle size of the drops was determined.

The results of this measurement are shown in Tables 3 and 4.
The evaluation results are shown in the form of evaluation after 1 day → evaluation after 3 months. In addition, a symbol indicating a phase separation that made measurement impossible or unnecessary was marked with- (also indicated in the table below). From these results, the emulsion base (A) of the present invention
It was found that the use of the oligoesterification product having the following is advantageous in producing a water-in-oil type gel emulsion composition.

[0047]

[Table 3] Note (1): Using 300 ml of an aqueous solution containing citric acid and trisodium citrate.

(2): Using 100 ml of an aqueous solution containing citric acid and trisodium citrate.

[0049]

[Table 4] Note (1) and (2): Same as the notes in Table 3.

Comparative Examples 6 to 8 Instead of the oligoesterification product of the present invention, glyceryl monooleate (Riken Vitamin Co., Ltd., Poem OL-20) generally used as a water-in-oil emulsifier.
0), sorbitan monooleate (Kao Corporation)
Manufactured by Leodol Super SP-O10) or polyether modified silicone (manufactured by Toray Dow Corning, SH-
3749) was used and the same operation as in Example 1 was performed.
The results obtained are shown in Table 5. As can be seen from Table 5, in any case, the emulsion stability was low, and it was observed that the viscosity as a gel property and the emulsion particle size greatly changed with time.

[0051]

[Table 5] Note (1) and (2): Same as the notes in Table 3.

Examples 9 to 16 and Comparative Examples 9 to 15 The oligoesterification products obtained in the above Synthesis Examples A, C, D and G were used as the emulsifying base (A) and the oil phase groups shown in Table 6 were used. A water-in-oil type gel emulsion composition was prepared in the same manner as in Example 1 together with the agent (B) and the aqueous phase base (C) (Examples 9 to 16). Further, for comparison with these, emulsion compositions were prepared in the same manner with the compounding compositions shown in Table 7 (Comparative Examples 9 to 15). These emulsion compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8 and Table 9.
(The display methods in Tables 8 and 9 are the same as those in Table 3). From these results, it was revealed that the present invention can provide a water-in-oil type gel emulsion composition having good emulsion stability.

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

[Table 8]

[0056]

[Table 9] A variety of cosmetics were produced using the above water-in-oil emulsion composition.

Examples 17-20, Comparative Examples 16-19 (water-in-oil type cream) Examples 9-12 and Comparative Examples 9-
Using the water-in-oil type emulsion composition obtained in 12, a water-in-oil type cream having an oil phase: water phase in a weight ratio of about 1: 1 was experimentally produced and their emulsion stability was evaluated.

That is, Examples 9 to 12 and Comparative Examples 9 to
Any of the water-in-oil emulsion compositions obtained in 12 above
7 g, and mixed oil phase of 10 g of neopentyl glycol dicaprate mixed and dissolved by heating at 80 ° C., 10 g of glyceryl triisooctylate (same as in Example 1), 10 g of squalane, 2 g of microcrystalline wax and 1 g of candelilla wax. 33 g and with stirring,
After uniformly mixing, the mixture was cooled to 30 ° C to obtain a cream.

The stability of the cream was evaluated by the same criteria as in Example 1 based on the appearance and average particle size after storage at 40 ° C. for 1 day and 12 months after preparation of the cream. The results are shown in Tables 10 and 11 (the display method in the table is the same as in Table 3).

From these results, it was found that the water-in-oil type gel-like emulsion composition of the present invention gives a water-in-oil type cream excellent in emulsion stability.

[0061]

[Table 10]

[0062]

[Table 11] Example 21, Comparative Example 20 (Emulsion) Using the water-in-oil type emulsion compositions obtained in Example 14 and Comparative Example 11, a water-in-oil type having an oil phase: water phase weight ratio of about 6: 4 was prepared. Emulsions were made as prototypes and their emulsion stability was evaluated.

That is, 80 g of any of the water-in-oil type emulsion compositions obtained in Example 14 and Comparative Example 11,
20 g of a mixed oil phase of isooctyl palmitate, 7 g of diheptylundecyl adipate, 1 g of microcrystalline wax and 2 g of beeswax, which had been mixed and dissolved by heating at 80 ° C., were uniformly mixed with stirring and then cooled to 30 ° C. , An emulsion was obtained.

Evaluation of emulsion stability was performed in the same manner as for cream. The evaluation results are shown in Tables 12 and 13 (the display method in the table is the same as in Table 3). From these results, it was found that the water-in-oil type gel-like emulsion composition of the present invention gives a water-in-oil type emulsion having excellent emulsion stability.

[0065]

[Table 12]

[0066]

[Table 13] Examples 22 and 23, Comparative Example 21 (lipstick-like emulsifying stick) Further Examples 13 and 1
5. Using the water-in-oil type emulsion composition obtained in Comparative Example 10, lipstick-like emulsified sticks having an aqueous phase ratio of about 5% by weight were prepared and their stability was evaluated.

That is, Examples 13 and 15 and Comparative Example 1
The water-in-oil emulsion composition obtained in Example No. 0 was heated to 85 ° C. and uniformly mixed with a mixed oil phase such as a predetermined oily component mixed and dissolved based on the composition shown in Table 14 under stirring. After that, it was poured into a mold and rapidly cooled to obtain a stick-shaped cosmetic.

The stability of this lipstick-like emulsified stick was evaluated by preparing the stick at 40 ° C. for 1 day and 12 days.
It depends on the appearance and the breaking strength after storage for one month. The evaluation criteria are as follows.

Evaluation of appearance: ○ -No change △ -Sweating is present × -Sweating is present and bending strength is thin: The following load tests were conducted. That is, the prepared stick body was fixed on a horizontal table so that it was positioned upward at an angle of inclination of 45 degrees, kept at 20 ° C for 24 hours, and then an adapter was applied to the tip of the stick to apply a vertical load. The load value when the stick was broken was measured. Measure 5 times, excluding maximum and minimum load values 3
The average load value for each time was defined as the bending strength.

The evaluation results are shown in Table 15 (the display method in the table is the same as in Table 3). From these results, it was found that the water-in-oil type gel emulsion composition of the present invention gives a stable water-in-oil emulsion stick.

[0071]

[Table 14] Note 1) Diisostearyl malate mixed with 40% by weight of pigment (titanium oxide, yellow and red pigments).

[0072]

[Table 15] Example 24 (Water-in-oil type sunscreen cosmetics) Raw material composition Weight part 1. Oligoesterification product of Synthesis Example A 20 2. Isooctyl paramethoxycinnamate 60 3. Isooctyl dimethylaminobenzoate 10 4. Oxybenzone 10 5. Methylparaben 0.4 6. Citric acid 0.4 7. Trisodium citrate 1.6 8.1,3-butylene glycol 40 9. Purified water 357.6 10. Cetyl isooctylate 50 11. Triisostearic acid trimethylolpropane ester 50 12. Jojoba oil 10 13. Squalane 50 14. Microcrystalline wax 6 15. Beeswax 4 16. Silicone treated titanium dioxide 30 (Production method) (1) The raw materials 1 to 5 are heated and dissolved at 70 ° C. (2) The raw materials 6 to 9 are heated and melted at 70 ° C. (3) The raw materials 10 to 16 are heated and melted at 70 ° C. (4) The mixture of (2) is gradually dispersed in the mixture of (1) under homodispersion (5000 rpm) stirring. (5) The mixture of (3) is mixed with the mixture of (4) under homodisper (2000 rpm) stirring. (6) Cool to 30 ° C.

The obtained creamy water-in-oil type sunscreen cosmetics were stored at 40 ° C. for 12 months, at room temperature for 12 months, and at 5 ° C. for 12 months. Maintained stable quality. In addition, it had a refreshing feeling without stickiness.

Example 25 (Water-in-oil type emulsion foundation) Raw material composition Weight part 1. Purified water 20 2. Sodium lactate 0.9 3. 3. Oligoesterification product of Synthesis Example C 4. Glyceryl triisooctylate 2 5. Diisooctylic acid neopentyl glycol ester 3 6. Isononyl isononanoate 2 7. Methylphenyl polysiloxane 3 8. Squalane 5 9. Octamethylcyclotetrasiloxane 5 10. Sericite 4.5 11. Kaolin 4 12. Titanium dioxide 10 13. Bengal 0.5 14. Yellow iron oxide 1 15. Purified water 20 16. 1,3-Butylene glycol 10 17. Methylparaben 0.1 (Production method) (1) The raw materials 1 and 2 are heated and dissolved at 60 ° C. (2) The raw materials 3 to 7 are heated and melted at 60 ° C. (3) The raw materials 7 to 8 are heated and melted at 60 ° C. (4) The raw materials 15 to 18 are heated and melted at 60 ° C., and the raw materials 10 to 14 are dispersed therein under stirring with a homodisper (3000 rpm). (5) The mixture of (2) is gradually dispersed in the mixture of (1) under homodispersion (4000 rpm) stirring. (6) The mixture of (3) is mixed with the mixture of (5) under homodisper (2000 rpm) stirring. (7) The mixture of (4) is gradually dispersed in the mixture of (6) under homodisper (3000 rpm) stirring. (8) Cool to 30 ° C.

The water-in-oil type emulsion foundations obtained were stored at 40 ° C., room temperature and 5 ° C. for 12 months, respectively, and as a result, maintained stable quality. Also,
It was not sticky and had a refreshing feel.

Example 26 (Water-in-oil type emulsified ointment) Raw material composition (parts by weight) Purified water 31.6 2. Dipotassium glycyrrhizinate 0.2 3. Sorbitol 5 4.1, 3-butylene glycol 5 5. Urea 10 6. 6. Oligoesterification product of Synthesis Example D 7. Glyceryl tricaprylate 20 8. Corn oil 20 9. Paraffin wax 5 10. Methyl paraben 0.1 11. Propyl paraben 0.1 (Production method) (1) The raw materials 1 to 5 are heated and melted at 60 ° C. (2) The raw materials 6 to 11 are heated and melted at 80 ° C. (3) The mixture of (2) is gradually dispersed in the mixture of (1) under stirring with a homomixer (5000 rpm). (4) Cool to 30 ° C.

The water-in-oil type emulsion ointments obtained were stored at 40 ° C., room temperature and 5 ° C. for 12 months, respectively, and as a result, maintained stable quality. Further, as compared with the oil-in-water type ointment, the effect of improving rough skin after water work was remarkable.

[0078]

INDUSTRIAL APPLICABILITY According to the present invention, even when a polar oil such as an ester is blended, the emulsion stability is excellent, the feeling in use is good, and there is no concern about safety. A water-based gel emulsion composition can be provided. Further, the water-in-oil type emulsion cosmetics and external preparations containing the water-in-oil type gelled emulsion composition have creams, emulsions, lipsticks and lipsticks because of their excellent stability, safety and touch feeling. , Eye cream, foundation, hairdressing, cosmetics such as ointments, quasi-drugs,
Widely applicable to pharmaceuticals.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-66637 (JP, A) JP-A-56-40605 (JP, A) JP-A-56-104807 (JP, A) FRAGRANCE JOURNA L, 1995 , Vol. 24, No. 1, pp. 90-98 (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K ⁷ /00-7/50 A61K 47/00-47/48

Claims (11)

(57) [Claims] 1. A mixture of the base (A), (B) and (C) containing an emulsifying base (A), an oil phase base (B) and an aqueous phase base (C) shown below. Oil whose ratio is (A) :( B) = 3: 1 to 1:50 (weight ratio) {(A) + (B)} :( C) = 5: 1 to 1:10 (weight ratio) A water-in-water gel emulsion composition. Emulsifying base (A): When the reaction molar ratios of diglycerin, a fatty acid having 6 to 22 carbon atoms, and a medium-chain dibasic acid having 4 to 10 carbon atoms are X, Y, and Z, respectively,
An oligoesterification product obtained by performing an esterification reaction so that the following conditions (a) and (b) are simultaneously satisfied. Condition (a): 0.5 ≦ Z / X ≦ 0.95 Condition (b): 0.2 ≦ Y / (2X + 2) ≦ 0.9 Oil phase base (B): an ester having no free hydroxyl group An oily component that contains as an essential component and has a dielectric constant of 2.5 or more. Aqueous phase base (C): 0.1 to 10% by weight of water-soluble organic acid and / or salt thereof or inorganic salt, pH 3
An aqueous solution that is ~ 9. 2. The emulsified base (A), wherein the fatty acid is one or two or more selected from the group consisting of branched fatty acids having 8 to 18 carbon atoms, and the water-in-oil gel form according to claim 1. Emulsified composition. 3. The emulsified base (A), wherein the medium chain dibasic acid is one or more selected from the group consisting of adipic acid, azelaic acid and sebacic acid. -Type gel emulsion composition. 4. The dielectric constant of the oil phase base material (B) is 2.8 to 8.
The water-in-oil type gel emulsion composition according to claim 1, which is 0. 5. Emulsifying base (A): Oil phase base (B) = 2:
The water-in-oil gelled emulsion composition according to any one of claims 1 to 4, which is 1 to 1:30 (weight ratio). 6. The water-in-oil type gel emulsion composition according to claim 1, wherein the pH of the aqueous phase base (C) is 4 to 8.5. 7. The water-in-oil type according to claim 1, wherein the content of the water-soluble organic acid and / or its salt or the inorganic salt in the water phase base (C) is 0.2% by weight or more. Gel-like emulsion composition. 8. The water-in-oil type gel emulsion composition according to claim 1, wherein the aqueous phase base (C) further contains a polyhydric alcohol. 9. The water-in-oil type gel emulsion composition according to claim 1, wherein the emulsification base (A) satisfies the following conditions (a) and (b) at the same time. (A): 0.6 ≦ Z / X ≦ 0.9 (b): 0.3 ≦ Y / (2X + 2) ≦ 0.8 10. A water-in-oil emulsion cosmetic or an external preparation obtained by mixing the water-in-oil gel emulsion composition according to any one of claims 1 to 9 with an oil component. 11. A water-in-oil emulsion obtained by mixing the water-in-oil gel emulsion composition according to any one of claims 1 to 9 with an oily component and further adding an aqueous component to emulsify the mixture. Cosmetics or external preparations.