JPS5814814B2 - Stable water-in-oil emulsifier composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention contains urocanic acid, which is present in large amounts in the skin, especially sweat, and has excellent safety, and basic amino acids (diaminomonocarboxylic acid) which have excellent effects on the skin. The purpose of this invention is to provide a stable water-in-oil emulsifier composition that has an ultraviolet absorption effect, and furthermore, to provide a stable emulsified cosmetic that contains this emulsifier composition and has an ultraviolet absorption effect. be.

More specifically, (A) urocanic acid, L-arginine, L-lysine, L-histidine, L-oxylysine, L-
- an aqueous solution containing one or more basic amino acids such as ornithine and having a pH of 6.9 to 8; and (B) a polyhydric alcohol having at least three or more hydroxyl groups in one molecule. An appropriate mixing ratio with one or more selected from the group consisting of partial esters with fatty acids that are liquid at room temperature and ethylene oxide adducts of 1 to hydroxy fatty acids and liglycerides that are liquid at room temperature;
A novel water-in-oil emulsifier composition with ultraviolet absorption effect consisting of a mixture of (B) to (A) in a weight ratio of 1:1 to 1:22, preferably 1:2 to 1:10, and the present emulsifier composition The invention relates to cosmetic sticks and pharmaceuticals such as water-in-oil creams, foundations, stick-like cosmetics, snack-like hair sticks, gels, oil-based and hydrophilic ointments containing at least 5% by weight or more.

The present inventors previously reported in JP-A-51-46588 that a stable water-in-oil emulsifier composition was obtained by using an aqueous solution of one or two amino acids or their salts and the substance of group (B). However, as a result of further intensive research, the present inventors have discovered that an aqueous solution of urocanic acid and basic amino acids can be used. It was discovered that by doing so, a stable water-in-oil emulsifier composition that also has an ultraviolet absorption effect that could not be expected with the above-mentioned invention could be obtained, and the present invention was completed.

It has been known for a long time that urocanic acid according to the present invention exists in large amounts in human sweat, and has a specific wavelength (290 to 310 mμ) that causes erythema and blisters caused by sunlight.
It has the function of absorbing light rays and protecting the epidermis.

The superiority of urocanic acid is that, unlike conventional ultraviolet absorbers such as para-aminobenzoic acid derivatives and salicylic acid derivatives, urocanic acid is superior to NMF (Natural M
It is a member of the Oisturizing Factor) and is an amino acid that is safe for the human body, and has advantages in terms of the amount of addition.

However, the problem with urocanic acid is that it is poorly soluble in various cosmetic solvents such as water and oils.

Regarding this solubility, conventionally, ethyl esterified products of urocanic acid and acylated products of urocanic acid with fatty acids have been used.

The present inventors have conducted intensive research to utilize natural urocanic acid without relying on such synthetic products, and as a result, as described above, by using basic amino acids in combination with urocanic acid, these He has overcome his shortcomings.

In other words, it has become possible to easily adjust the pH range suitable for ultraviolet absorption and increase the solubility in water.

Basic amino acids are important and safe amino acids that are known to exist not only in natural products but also in the human body.

In particular, L-lysine is an essential amino acid that is essential for the growth of the human body and the maintenance of life, and L-arginine and L-histidine are also widely known to be important as semi-essential amino acids, although they are not essential amino acids. .

Oxylysine is present in animal collagen and gelatin derived therefrom.

Furthermore, L-ornithine is a member of the urea production cycle in living organisms and is biochemically important.

The present invention creates a novel water-in-oil emulsifier by mixing the aqueous solution containing urocanic acid and basic amino acids prepared in this way with a substance in the group (B), such as a fatty acid partial ester of a polyhydric alcohol. The present invention was completed based on the discovery that a water-in-oil emulsion that is safe for the human body, has excellent stability, and also has ultraviolet absorption effects can be obtained by blending scales and the emulsifier composition thereof into cosmetics. This is what I came to do.

Furthermore, as shown in the data below, the present inventors found that by dissolving urocanic acid in an aqueous solution of basic amino acids, the pH could be adjusted to exhibit the ultraviolet absorption effect (see Figure 1).
, and the aqueous solution of the above basic amino acid and urocanic acid is mixed with the above (B
) It has been confirmed that a water-in-oil emulsion composition can be obtained by mixing with substances of the group (see Table 1).

Furthermore, as is well known, water-in-oil emulsions have excellent water resistance and are difficult to remove even with sweat or water bathing, so the cosmetic composition according to the present invention can maintain its sunburn prevention effect for a long time.

Moreover, the emulsified composition according to the present invention is safe for the skin, so it can be said to be a truly useful cosmetic.

Next, the configuration of the present invention will be described.

The present invention consists of <A) an aqueous solution containing urocanic acid and a basic amino acid (diaminomonocarboxylic acid) and having a pH of 6.9 to 8, and (B) at least three or more hydroxyl groups in one molecule. (B) and a substance that is liquid at room temperature selected from the group consisting of a partial ester of a polyhydric alcohol and a fatty acid, and an ethylene oxide adduct of a hydroxy fatty acid triglyceride;
The ratio of A) is 1=1 to 1:22 by weight, preferably 1
The present invention relates to a water-in-oil emulsifier composition characterized by having an ultraviolet absorption effect of :2 to 1:10, and a stable water-in-oil cosmetic containing the composition.

In the aqueous solution of urocanic acid and basic amino acid used in the emulsifier composition of the present invention, it is important that the pH of the aqueous solution is neutral.

Preferably, the pH of the aqueous solution is about 7-8.

In terms of blending ratio, the basic amino acid is preferably used in an equivalent or more amount to 1.0 times the amount of urocanic acid, for example, about 1.2 times the amount of L-arginine.

An emulsifier composition prepared on the alkaline side with an excess of the latter added is unsuitable for long-term storage.

Moreover, if the latter compounding ratio is low, crystal precipitation will occur, and its aqueous solution is not practical for preparing compositions.

Next, as basic amino acids (diaminomonocarboxylic acids), L-arginine, L-lysine, L-histidine, L-
-oxylysine, L-ornithine, etc.

The D-form and DL-form as these optical isomers also belong to this category.

Among these, particularly preferred are aqueous solutions of urocanic acid to L-arginine.

Table 1 shows the strength of water-in-oil emulsifier compositions obtained with (A) various pH aqueous solutions adjusted with urocanic acid - L - arginine and (B) diglyceryl diisooctadecanoate.

The strength is 200g using a card tension meter.
It is the scale value when it starts to flow when it is continuously penetrated by a load and a pressure sensitive shaft of 8 mmφ, and the sample is (A): (
B) prepared at 4:1 was used.

From Table 1, it can be seen that the strength of the composition is maximum when the pH of the aqueous solution is around 7.

Next, FIG. 1 shows changes in the ultraviolet absorption curves depending on the pH of each aqueous solution prepared between urocanic acid and L-arginine.

As the pH increases, the ultraviolet absorption curve shifts to higher wavelengths, and the absorption rate of wavelengths that cause erythema and blisters increases.

(The numerical values attached to the graph in FIG. 1 indicate the pH of the aqueous solution.

) Next, in the present invention, partial esters of polyhydric alcohol and fatty acid used in the emulsifier composition can be derived from the following substances.

The polyhydric alcohols used have three or more hydroxyl groups, such as glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, octaglycerin, nonaglycerin, decaglycerin, trimethylolethane, and trimethylolpropane. , Penqueryslit, sorbitan, sorbitol, etc.

The fatty acids that react with these polyhydric alcohols to form partial esters include caprylic acid, capric acid, oleic acid,
It may be selected from linoleic acid, isooctanoic acid, isohexadecanoic acid, isooctadecanoic acid, and the like.

These partial esters are generally mainly mono, di,
Refers to a mixture of triester, one part tetraester, and one part pentaester.

Among these partial esters, particularly preferred are glycerin mono-2-heptyl undecanoate, trimethylolpropane mono-2-heptyl undecanoate, diglycerin di-2-heptyl undecanoate, glycerin monooleate, trimethylol These include propane monooleate, diglycerine dioleate, glycerine diricinolate, sorbitan mono(or di, tri)oleate, and the like.

The ethylene oxide adduct of hydroxy fatty acid triglyceride is preferably at least about 1 mol to about 10 mol of ethylene oxide adduct of castor oil or hydrogenated castor oil.

In addition to the above-mentioned substances, partial esters of polyhydric alcohols with fatty acids that are liquid at room temperature include polyhydric alcohols and partial esters of fatty acids with 1 to 10 moles of ethylene oxide added, or polyhydric alcohols with 1 to 10 moles of ethylene oxide added. Also included are partial esters of 1 to 10 moles of ethylene oxide and fatty acids.

Specific examples of the former include 1 to 10 moles of ethylene oxide adducts such as glycerin di-2-heptyl undecanoate, glycerin diolate, sorbitane di-2-heptyl undecanoate, and sorbitan diolate.

A specific example of the latter is a compound obtained by partially esterifying 2-heptylundecanoic acid or oleic acid to a product obtained by adding 1 to 10 moles of ethylene oxide to glycerin or sorbitan.

Both of these are mixed with an aqueous solution of urocanic acid and a basic amino acid (diaminomonocarboxylic acid) to form a stable water-in-oil emulsifier composition with UV absorption effect.

Next, the method for producing the water-in-oil emulsifier composition of the present invention will be described.

The water-in-oil emulsifier composition of the present invention is an aqueous solution of various concentrations of urocanic acid and a basic amino acid (diaminomonocarboxylic acid), which is mixed with a fatty acid partial ester of a polyhydric alcohol or an ethylene oxide adduct of a hydroxy fatty acid triglyceride. It is obtained by adding the mixture at a suitable ratio and stirring at room temperature.

This mixing ratio is 1:1 to (B) to (A) by weight.
The ratio is 1:22, preferably 1:2 to 1:1o.

The water-in-oil emulsifier composition thus obtained can be used alone in water-in-oil creams, sticks, and foundations without using any other emulsifier, and is stable and UV-resistant like the above. Provides a water-in-oil emulsion cosmetic with absorption effect.

At that time, when manufacturing these water-in-oil emulsified cosmetics or pharmaceuticals, the present invention is added to the oil phase in an amount of at least 5% by weight based on the entire emulsion or ointment, and the state is uniformly dispersed and mixed. Use with.

Other ingredients of the above products include oil and fat substances, humectants, powders, preservatives, perfumes, metallic soaps, dyes and water, etc., which are commonly used in cosmetics or medicines.

Cream (1) obtained as above and JP-A-51-
Table 2 shows a formulation example of the cream (2) obtained by the method described in Japanese Patent No. 46588, and FIG. 2 shows a comparison of the ultraviolet absorption effects of each cream.

As shown in Figure 2, the cream according to the present invention has a
It is clear that ultraviolet rays of mμ are well absorbed.

Another feature of the cosmetics obtained by the present invention is that there is less oiliness and glare that is common with conventional oil-based water-in-oil creams, and it is possible to incorporate a large amount of water in a stable form. It absorbs into the skin extremely quickly, gives a moist feeling after use, and also has an ultraviolet absorption effect, so when you consider these points, it can be said that it is an extremely excellent cosmetic or pharmaceutical product.

Next, examples of water-in-oil emulsifier compositions and cosmetics obtained by the method of the present invention will be shown.

The following examples serve to explain the subject matter of the invention in more detail without limiting it.

Example I 4.0 parts of L-arginine and 3.2 parts of urocanic acid were dissolved in 72.6 parts of ion-exchanged water, and then added to 20.2 parts of diglyceryl diisooctadecanoate at room temperature, and stirred. A water-in-oil emulsifier composition was obtained by mixing.

Example 2 100 parts of pentaerythritol dioleate, 1.8 parts of urocanic acid, 2.2 parts of L-lysine, 860 parts of ion-exchanged water
A water-in-oil emulsifier silk composition was obtained in the same manner as in Example 1.

Example 3 Hydrogenated castor oil polyoxyethylene (5 mol) adduct 25
．． A water-in-oil emulsifier and a composition were obtained in the same manner as in Example 1 from 3 parts of urocanic acid, 51 parts of L-arginine, and 633 parts of ion-exchanged water.

Example 4 Water-in-oil sunscreen cream (formulation) (% by weight) Emulsifier composition of Example 1 5.0 Vaseline
10.0 Microcrystalline wax 50 Mineral oil 23
．． 0 Isoprobyl myristate (IPM) 3.
0 Ion-exchanged water 50.0 Glycerin 30 Metallic soap 10 Preservative Appropriate amount Fragrance Appropriate amount (manufacturing method) Dissolve metal stone life in mineral oil and IPM, then add Vaseline, microcrystalline wax, preservative, and fragrance, and mix evenly. After dissolving and mixing, a water-in-oil emulsifier condensate is added and heated to 70° C. while stirring and mixing uniformly.

To this are added ion exchange water and glycerin heated to 70'C.

Next, these mixtures are stirred with a homogenizer for a predetermined period of time, and cooled to room temperature with stirring.

Example 5 Water-in-oil sunscreen cream A water-in-oil sunscreen cream was obtained in the same manner as in Example 4 using the following formulation.

(Formulation) (% by weight) Emulsifier composition of Example 2 30 Vaseline
10 Microcrystalline wax 5 Mineral oil 18 IPM 3 Ion exchange water
35 glycerin
3 Metal soap 1 Preservative Appropriate amount Fragrance Appropriate amount Example 6 Sunscreen stick (prescription) (% by weight) Emulsifier composition of Example 2 8 Ceresin 20 piece wax 2 Mineral oil 48 Ion exchange water 5 Coloring material 18 Preservative Appropriate amount Fragrance Appropriate amount (Manufacturing method) Heat the other components except for the ion-exchanged water to 75-85°C to completely dissolve and mix.

Next, ion exchange water is added, and the coloring material is dispersed and emulsified using a homogenizer.

This emulsified mixture was poured into a predetermined container and cooled to room temperature to obtain a sunscreen stick.

Example 7 Hair Stick (Formulation) (% by weight) Emulsifier composition of Example 3 10 Castor oil
50 piece wax
20 Hydrogenated castor oil 8 Candelilla wax 5 Fragrance 2 (Production method) Heat and dissolve castor oil, beeswax, hydrogenated castor oil, and candelilla wax.

After adding the emulsifier composition and uniformly dispersing it, the fragrance is added.

These mixtures were poured into a predetermined container and cooled to room temperature to obtain hair sticks.

Although the embodiments of the present invention have been described above, it is within the scope of the present patent claims to further replace a part of the formulation with another substance, change the concentration ratio, and replace or omit a treatment step. It is clear that

[Brief explanation of drawings]

Figure 1 shows the pH dependence of the ultraviolet absorption curve of the urocanic acid-L-arginine aqueous solution used in the present invention, and Figure 2 shows the ultraviolet absorption curve of the cream of the present invention and the conventional cream. Figure 2 is a graph showing a comparison.

Claims (1)

[Scope of Claims] 1 (A) an aqueous solution containing urocanic acid and one or more basic amino acids and having a pH of 6.9 to 8, and (B) 3 amino acids in one molecule. A substance that is liquid at room temperature and is selected from the group consisting of the above partial esters of polyhydric alcohols and fatty acids having hydroxyl groups, and hydroxy fatty acid triglyceride ethylene oxide adducts.
A stable water-in-oil emulsifier composition having an ultraviolet absorption effect, characterized in that the weight ratio of (B):(A) is in the range of 1:1 to 1:22. . 2. The water-in-oil emulsifier composition according to claim 1, wherein the number of moles of ethylene oxide added to the hydroxy fatty acid triglyceride is 1 to 10 moles. 3. The water-in-oil emulsifier composition according to claim 1 or 2, wherein the basic amino acid is L-arginine. 4 (A) an aqueous solution containing urocanic acid and one or more basic amino acids and having a pH of 6.9 to 8; and (B) a polyhydric solution containing three or more hydroxyl groups in one molecule. (B) : (A ) in a weight ratio of 1:1 to 1:22 in a weight ratio of 5% or more of a water-in-oil emulsifier composition.