JP5259973B2 - Emulsifier type skin external preparation - Google Patents

Description

The present invention relates to an external preparation for skin, and more particularly to an external preparation for skin in an emulsifier form.

In skin external preparations such as cosmetics, emulsification technology and emulsification preparation are one of key technologies. This is because the lipophilic component and the hydrophilic component can be simultaneously administered to the skin by taking the emulsifier form. For such emulsification, surfactants having amphipathic properties are usually used, but such surfactants have a great influence on biological membranes and may be irritating to sensitive people. Therefore, it is considered that the use of topical skin preparations for people with sensitive skin should be restricted. Among them, surfactants having a polyoxyethylene group as a hydrophilic portion have a high probability of irritation on such sensitive skin, and an alternative means for polyoxyethylene addition type surfactants has been desired.

Examples of the emulsification technique that does not use a polyoxyethylene addition type surfactant include, for example, a method using an alkyl-modified carboxyvinyl polymer and / or a salt thereof (see, for example, Patent Document 1), and alginic acid such as propylene glycol alginate. There are a method using a polyhydric alcohol ester (see, for example, Patent Document 2 and Patent Document 3), a method using a fatty acid ester of polyglycerol (see Patent Document 4), and the like. However, at the method of using the alkyl-modified carboxyvinyl polymer, and decrease of viscosity by the electrolyte, deterioration of the emulsified state becomes an issue, in the method using a polyhydric alcohol ester of alginic acid, harsh, such as sometimes hot There is a stability problem that the emulsified particles become rough under various conditions. In the method using the fatty acid ester of polyglycerin, there is a limit to an acceptable oil phase component, and a polyoxyethylene addition type surfactant is used. It can be said that there is a stability problem compared to the case of As one means for solving such a problem, a method of combining a polyhydric alcohol ester of alginic acid and a phospholipid has been devised (see, for example, Patent Document 5). Although stability has been improved, stability under severe conditions has been devised. It was hard to say that sex was sufficiently secured. Here, although it is stability under severe conditions, such stability is usually not a problem in practical use at all, but is a necessary element in export and import, and in today's remarkable globalization Is the quality that has been newly demanded.

JP 08-217624 A JP 2006-76898 A JP 2004-196728 A JP 2002-114622 A JP 2006-76899 A

The present invention has been made under such circumstances, and is an emulsification technique that does not use a polyoxyethylene addition type surfactant, emulsification using a polyhydric alcohol ester of alginic acid, under severe conditions. It is an object to provide a technology for improving the stability of the Internet.

In view of such a situation, the present inventors sought for a technique for improving the stability under severe conditions in emulsification using a polyhydric alcohol ester of alginic acid, and the result of repeated earnest research efforts The inventors have found that such a stabilization can be obtained by using a fatty acid ester of polyglycerol together, and have completed the invention. That is, the present invention is as follows.
(1) 1) Polyhydric alcohol ester of alginic acid 0.1 to 8% by mass , 2) 0.01 to 1% by mass in terms of alginic acid and / or its salt converted to alginic acid, and 3) a polyvalent metal salt 4) Polyglycerin fatty acid ester (excluding decaglycerin monostearate) 0.1 to 10% by mass, and the degree of neutralization of alginic acid by the polyvalent metal of the polyvalent metal salt is 30 to 80%. characterized in that there, oil-in-water emulsifier type emulsified composition.
(2) The emulsion composition according to (1), wherein the polyhydric alcohol ester of alginic acid is a propylene glycol ester of alginic acid.
( 3 ) The emulsion composition according to (1) or (2 ), wherein the fatty acid ester of polyglycerol is a mono fatty acid ester of polyglycerol having a polymerization degree of 5 to 15.

According to the present invention, there is provided a technique for improving stability under severe conditions in emulsification using a polyhydric alcohol ester of alginic acid, which is an emulsification technique that does not use a polyoxyethylene addition type surfactant. can do.

(1) Polyhydric alcohol ester of alginic acid which is an essential component of the emulsified composition of the present invention The emulsified composition of the present invention contains an ester of polyhydric alcohol of alginic acid as an essential component. Here, the polyhydric alcohol constituting the polyhydric alcohol ester of alginic acid can be used without particular limitation as long as it is used in a skin external preparation or the like, and those having 2 to 4 carbon atoms. Those having no ether bond are preferred. Specifically, propylene glycol, glycerin, 1,3-butanediol, ethylene glycol and the like can be preferably exemplified, and propylene glycol can be particularly preferably exemplified from the balance between hydrophilicity and lipophilicity. All of these polyhydric alcohol esters of alginic acid are known compounds, and their production methods are already known. Examples of the method for producing an ester of a polyhydric alcohol of alginic acid include a reaction of a salt of alginic acid such as sodium alginate with a monohalide of the corresponding polyhydric alcohol in the presence of an alkali. For example, in the case of propylene glycol alginate, sodium alginate and 1-chloro-2-propanol may be reacted in the presence of potassium carbonate in hydrous alcohol, and in the case of glyceryl alginate, It can be produced by treating 1-chloro-2-propanol in the same manner in place of 1-chloro-2,3-propanediol. In the external preparation for skin of the present invention, alginic acid propylene glycol ester is particularly preferable as the polyhydric alcohol ester of alginic acid. This is because the emulsion stability is excellent.

Some of these esters are already on the market, and such commercial products can be purchased and used. Suitable commercially available products, for example, if propylene glycol alginate, available from Inc. KIMICA, "Kimiroido LLV", "Kimiroido LV", "Kimiroido MV", "Kimiroi de HV", "Kimiroido BF ", Kimiloid NLS-K" and the like are preferable. These differ in viscosity and degree of esterification. Among these, preferable characteristic values of propylene glycol alginate are as follows.

(Characteristics of polyhydric alcohol ester of alginic acid)
1) The degree of esterification is 70% or more, more preferably 80% or more.
2) The viscosity of a 1% aqueous solution at 20 ° C. is 10 to 100 mPascal · second, more preferably 10 to 30 mPascal · second as measured with a No. 1 rotor with a B-type viscometer.

Among the polyhydric alcohol esters of alginic acid having such properties, there are already commercially available ones that can be purchased and used. As such a polyhydric alcohol ester of alginic acid, “Kimiloid LLV” (1% aqueous solution, viscosity at 20 ° C. of 10 to 30 mPascal · sec, esterification degree 80%) sold by Kimika Co., Ltd., “ “Chimiloid NLS-K” (1% aqueous solution, viscosity at 20 ° C. is 30 to 60 mPascal · second, esterification degree 80%), “Chimiloid LV” (1% aqueous solution, viscosity at 20 ° C. is 60 to 100 mPascal · second, A preferred example is an esterification degree of 80%. Among these, “Chimiloid LLV” is particularly preferable. These can contain only the seed | species, and can also be made to contain in combination of 2 or more type. The preferable content of the polyhydric alcohol ester of alginic acid is the total amount as a lower limit, preferably 0.1% by mass, more preferably 1% by mass with respect to the total amount of the cosmetic, and the upper limit is 8%. % By mass is preferable, and more preferably 3% by mass. If the amount is too small, there are cases where emulsification cannot be performed.

(2) Alginic acid which is an essential component of the external preparation for skin of the present invention The external preparation for skin of the present invention further contains alginic acid and / or a salt thereof in addition to the polyhydric alcohol ester of alginic acid. Such a component has a function of reinforcing the emulsion structure of the polyhydric alcohol ester of alginic acid. Alginic acid can be used as a free form, but it is preferably used in the form of a metal salt. As such a metal salt, a polyvalent metal salt is preferable, and among them, an alkaline earth metal salt such as a calcium salt, a barium salt, and a magnesium salt is particularly preferable, and a calcium salt is particularly preferable. This is because the emulsifying structure reinforcing action is particularly remarkable in calcium salts. In order to achieve such an effect, the amount of alginic acid and / or a salt thereof is preferably 0.01% by mass, more preferably 0.1% by mass, and more preferably as the upper limit in terms of alginic acid. Is preferably 1% by mass, and more preferably 0.3% by mass. This is because if the amount is too small, the above-described effect may not be achieved, and if the amount is too large, the effect may reach its peak and a loss of feeling of use may occur. Further, the neutralization degree of alginic acid with metal is preferably 30 to 80%.

(3) Fatty acid ester of polyglycerol which is an essential component of the external preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing a fatty acid ester of polyglycerin as an essential component. The polyglycerol moiety in the fatty acid ester of polyglycerol preferably has a polymerization degree of 5 or more and 20 or less, and more preferably 6 or more and 15 or less. The acyl group constituting the ester can be applied without particular limitation as long as it is an acyl group used in an external preparation for skin, for example, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, behenoyl group, isostearoyl group. Group, isooctanoyl group, oleoyl group, linoloyl group and the like can be suitably exemplified, and saturated and linear acyl groups are preferable, and lauroyl group and stearoyl group are particularly preferable. Further, the number of acyl groups is preferably less than the number of free hydroxyl groups, and particularly preferably has 1 to 4 acyl groups. It is preferably 8 to 16 in terms of HLB. Specific examples include decaglycerin, nonaglycerin, octaglycerin, heptaglycerin, hexaglycerin tetraester, triester, diester, monoester and the like. They separate polyglycerin obtained by polymerizing glycidol by ultrafiltration or distillation for each degree of polymerization, react with acyl chloride in the presence of alkali, acylate, and separate and purify it with a silica gel column etc. It is obtained by doing. There are already commercially available polyglycerin fatty acid esters under such conditions, and such commercially available products can be purchased and used. Examples of such commercially available products include decaglycerol monostearate (Sakamoto Yakuhin "SY Glyster MSW750", HLB14.5), hexaglycerol monostearate (Sakamoto Yakuhin "SY Glyster MS500", HLB12.2), Preferred examples include decaglycerol tristearic acid ester (Sakamoto Yakuhin "SY Glyster TS750", HLB 9.1), decaglycerol monolauric acid ester (Sakamoto Yakuhin "SY Glyster ML750", HLB 15.7), and the like. In the external preparation for skin according to the present invention, such a component has an effect of enhancing the stability of the emulsified structure with a polyhydric alcohol ester of alginic acid under severe conditions. In order to exhibit such an action, such a component can contain only one kind, or a combination of two or more kinds. Content of this component for producing such an effect is 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the external preparation for skin, as a total amount. This is because if the content is too small, the above effects may not be achieved, and if the content is too large, the stability may be impaired.

(4) External preparation for skin of the present invention The external preparation for skin of the present invention is an emulsifier type and contains the essential components. The emulsifier form is not particularly limited, but is preferably an oil-in-water emulsifier form. Here, the oil-in-water emulsifier form is an emulsified form in which an aqueous phase is present in the outermost phase and oil phase particles are present therein. Therefore, composite dosage forms such as water-in-oil-in-water are also classified as oil-in-water emulsifier forms.

The external preparation for skin of the present invention can contain, in addition to such components, optional components that are usually used in external preparations for skin. Examples of such optional ingredients include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, and hardened coconut oil. Oils such as hardened oil, mole, castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, waxes, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum , Hydrocarbons such as microcrystalline wax, higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl Alcohol, behenyl alcohol, octyldodecanol, higher alcohol such as myristyl alcohol, cetostearyl alcohol, etc., cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, malic acid Diisostearyl, di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, tri Synthetic ester oils such as trimethylolpropane isostearate and pentane erythritol tetra-2-ethylhexanoate, dimethylpolysiloxane, methylphenylpoly Loxane, linear polysiloxane such as diphenylpolysiloxane, cyclic polysiloxane such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, Oil agents such as silicone oil such as modified polysiloxane such as fluorine-modified polysiloxane, anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, triethanolamine ether of alkyl sulfate, chloride Cationic surfactants such as stearyltrimethylammonium, benzalkonium chloride, laurylamine oxide, imidazoline-based amphoteric surfactants (2-cocoyl-2-imida Zolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan) Monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (eg, glyceryl monostearate), propylene glycol fatty acid esters (eg, propylene glycol monostearate), hardened castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid ester Tells (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl) Ethers, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), Nonionic surfactants such as sucrose fatty acid ester and alkyl glucoside, polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene Polyols such as recall, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol, sodium pyrrolidonecarboxylate Moisturizing ingredients such as lactic acid and sodium lactate, surface may be treated, powder such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate Body, surface may be treated, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, surface may be treated, mica titanium Pearls such as fish phosphorus foil, bismuth oxychloride, red 202 which may be raked, red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213, Yellow 204, Yellow 203, Blue 1 Organic dyes such as green 201, purple 201 and red 204, polyethylene powder, polymethyl methacrylate, nylon powder, organic powders such as organopolysiloxane elastomer, paraaminobenzoic acid UV absorber, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4 UV absorbers such as -methoxy-4'-t-butyldibenzoylmethane, lower alcohols such as ethanol and isopropanol Vitamin B or its derivatives, vitamin B ₆ hydrochloride, vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ or its derivatives, vitamin B ₁₂ such as vitamin B ₁₂ , vitamin B ₁₅ or its derivatives, α Preferred examples include vitamin E such as tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin D, vitamin H, pantothenic acid, pantethine, vitamins such as pyrroloquinoline quinone, and antibacterial agents such as phenoxyethanol. it can. The skin external preparation of this invention can be manufactured by processing the said component in accordance with a conventional method.

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 such examples.

<Reference Example 1>
An emulsified composition 1 (cosmetic material) of Reference Example was prepared according to the formulation shown in Table 1 below. That is, a, b, c, and d are each adjusted to a temperature of 80 ° C., b is added to the b under stirring, uniformly dispersed and dissolved, and further, c is added under agitation to perform base exchange. Under stirring, the mixture was gradually added to emulsify, and stirred and cooled to obtain the emulsion composition 1 of Reference Example as an emulsion. Simultaneously, Comparative Example 1 in which decaglycerol monostearic acid ester, which is a polyglycerin fatty acid ester, was replaced with water, Comparative Example 2 in which propylene glycol alginate was replaced with water, Comparative Example 3, in which propylene glycol alginate was replaced with sodium alginate, Alginic acid Comparative Example 4 in which sodium was replaced with water, Comparative Example 5 in which sodium alginate was replaced with propylene glycol alginate, Comparative Example 6 in which sodium alginate and propylene glycol alginate were replaced with water, Polyglycerin fatty acid ester as a POE nonionic interface Comparative Example 7 was prepared by substituting the activator POE25 stearate. About these, stability was visually evaluated as an emulsified state by the storage test for 2 weeks at -30 degreeC, 20 degreeC, and 60 degreeC. The judgment criteria were: ○: good product, Δ: problematic for handling as good product, ×: defective product. The results are shown in Table 2. From this, it can be seen that the emulsified composition 1 of the reference example has extremely good emulsifiability and stability and high commercial value. Moreover, evaluation that the emulsified composition 1 of the reference example was provided with the requirements as cosmetics was also obtained in the evaluation by a specialized panelist.

<Example 1>
In the same manner as in Reference Example 1 , an emulsified composition 1 (cosmetic) of the present invention was prepared and evaluated according to the formulation shown in Table 3 below. The results are shown in Table 4. It turns out that it has the same effect.

<Example 2>
In the same manner as in Reference Example 1 , an emulsion composition 2 (cosmetics) of the present invention was prepared and evaluated according to the formulation shown in Table 5 below. The results are shown in Table 6. It turns out that it has the same effect.

<Example 3>
In the same manner as in Reference Example 1 , an emulsified composition 3 (cosmetic) of the present invention was prepared and evaluated according to the formulation shown in Table 7 below. The results are shown in Table 8. It turns out that it has the same effect.

<Reference Example 2>
In the same manner as in Reference Example 1 , emulsified composition 2 (cosmetic material) of Reference Example was prepared and evaluated according to the formulation shown in Table 9 below. The results are shown in Table 10. It turns out that it has the same effect.

The present invention can be applied to an external preparation for emulsifiers such as cosmetics.

Claims (3)

1) 0.1 to 8% by mass of polyhydric alcohol ester of alginic acid, 2) 0.01 to 1% by mass of alginic acid and / or its salt converted to alginic acid , 3) polyvalent metal salt and 4) poly Glycerin fatty acid ester (excluding decaglycerin monostearate) 0.1 to 10% by mass, and the degree of neutralization of alginic acid by the polyvalent metal of the polyvalent metal salt is 30 to 80% An emulsified composition in the form of an oil-in-water emulsifier. The emulsion composition according to claim 1, wherein the polyhydric alcohol ester of alginic acid is a propylene glycol ester of alginic acid. The emulsion composition according to claim 1 or 2 , wherein the fatty acid ester of polyglycerin is a mono fatty acid ester of polyglycerin having a polymerization degree of 5 to 15.