JP4834278B2 - Emulsified composition based on natural products - Google Patents

Description

−：実施できず
【００１３】
＜実施例２＞
乳化組成物１のアルギン酸プロピレングリコールエステルの量を変化させて、実施例１と同様に乳化組成物２〜４（何れも化粧料）を作成し、評価して、その影響を見た。結果を表２に示す。これより、アルギン酸の多価アルコールエステルの好ましい含有量は、乳化組成物全量に対して、総量で、１〜５重量％であり、更に好ましくは１．２〜２重量％であることがわかる。又、乳化組成物２〜４は専門パネラーによる評価に於いて、化粧料としての要件を備えているとの評価を得た。
イ
アルギン酸ナトリウム ０．１重量部
アルギン酸プロピレングリコールエステル ＊重量部
（キミロイドＮＬＳＫ）
１，２−ヘキシレングリコール ５ 重量部
ロ
水 ７１．５−＊重量部
ハ
塩化カルシウム ０．００１重量部
水 １３．３９９重量部
ニ
スクワラン ５ 重量部
グリセリルトリイソオクタネート ５ 重量部
＊は表２に記す。
【００１４】
【表２】

【００１５】
＜実施例３＞
乳化組成物１の塩化カルシウムの量を変化させて、実施例１と同様に乳化組成物５〜７（何れも化粧料）を作成し、評価して、その影響を見た。結果を表３に示す。これより、塩化カルシウム等の多価金属塩の好ましい含有量は、乳化組成物全量に対して、総量で、１塩化物に換算して、０．０００５〜０．２５重量％、より好ましくは０．００５〜０．２重量％であることがわかる。又、乳化組成物５〜７は専門パネラーによる評価に於いて、化粧料としての要件を備えているとの評価を得た。
イ
アルギン酸ナトリウム ０．１重量部
アルギン酸プロピレングリコールエステル １．５重量部
（キミロイドＮＬＳＫ）
１，２−ヘキシレングリコール ５ 重量部
ロ
水 ７０ 重量部
ハ
塩化カルシウム ＊＊重量部
水 １３．４−＊＊重量部
ニ
スクワラン ５ 重量部
グリセリルトリイソオクタネート ５ 重量部
＊＊は表３に記す。
【００１６】
【表３】

【００１７】
＜実施例４＞
乳化組成物１のアルギン酸プロピレングリコールエステルのグレードを変えて、実施例１と同様に乳化組成物８〜７（何れも化粧料）を作成し、評価して、その影響を見た。結果を表４に示す。これより、何れのグレードのものでも使用可能であることがわかる。
イ
アルギン酸ナトリウム ０．１重量部
アルギン酸プロピレングリコールエステル １．５重量部
（表４に記載の商品）
１，２−ヘキシレングリコール ５ 重量部
ロ
水 ７０ 重量部
ハ
塩化カルシウム ０．００１重量部
水 １３．３９９重量部
ニ
スクワラン ５ 重量部
グリセリルトリイソオクタネート ５ 重量部
【００１８】
【表４】

【００１９】
＜実施例５＞
乳化組成物１の塩化カルシウムを他の多価金属塩化物に置換して、実施例４と同様の検討を行った。何れの多価金属塩化物も使用可能であることがわかる。又、カルシウムが特に好ましいこともわかる。
イ
アルギン酸ナトリウム ０．１重量部
アルギン酸プロピレングリコールエステル １．５重量部
（「キミロイドＮＬＳＫ」）
１，２−ヘキシレングリコール ５ 重量部
ロ
水 ７０ 重量部
ハ
表５に記載の成分 ０．００１重量部
水 １３．３９９重量部
ニ
スクワラン ５ 重量部
グリセリルトリイソオクタネート ５ 重量部
【００２０】
【表５】

【００２１】
＜実施例６＞
実施例１と同様に操作して、乳化組成物１８（皮膚外用医薬）を作成した。
イ
アルギン酸ナトリウム ０．１重量部
アルギン酸プロピレングリコールエステル １．５重量部
（キミロイドＮＬＳＫ）
１，２−ヘキシレングリコール ５ 重量部
ロ
水 ７０ 重量部
ハ
塩化カルシウム ０．００１重量部
水 １１．３９９重量部
ニ
スクワラン ５ 重量部
グリセリルトリイソオクタネート ５ 重量部
テルビナフィン ２ 重量部
【００２２】
【発明の効果】
本発明によれば、皮膚外用剤として好適な、合成ポリマーも、界面活性剤も使用しない乳化組成物を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an emulsified composition suitable for an external preparation for skin, and more particularly to an emulsified composition suitable for an external preparation for skin using a natural product-derived thickening emulsifier.
[0002]
[Prior art]
Since the emulsified composition contains an aqueous component and an oily component separately in a continuous phase and emulsified particles, it is suitable as a carrier for an oil-soluble component and a carrier for a water-soluble component. It is used as a formulation useful in the fields of cosmetics and external medicine for skin. Such an emulsified composition is mainly composed of a hydrophilic component, an oily component and a surfactant as components. Above all, the surfactant is an essential component for dispersing a hydrophilic component and an oil component that are not mixed with each other in a uniform dispersion state. As surfactants, anionic surfactants such as soap and alkyl sulfate esters, polyoxyethylene addition type, or partial ester type nonionic surfactants of polyhydric alcohols are widely used in the field of topical skin preparations. ing. Of these, anionic surfactants should be improved in terms of temporary irritation, and nonionic surfactants should be improved in terms of generation of formalin over time. Furthermore, because of its characteristics that are not easily biodegradable, environmental science is incompatible with the main points of the Sustainable Development Protocol in Kyoto, leaving room for improvement. For this reason, the development of an emulsifying system that does not use a surfactant has been a long-standing problem in the field of topical skin preparations.
[0003]
Against this background, several emulsion formulations that do not use a surfactant have been devised. For example, those using an acrylic acid copolymer having a long-chain alkyl group in the side chain as shown in Patent Documents 1 and 2 can be exemplified as typical examples. However, in such a polymer, there is a concern from the viewpoint of safety of residual monomers generated when the polymer is produced. In addition, like surfactants, such polymers are also difficult to biodegrade in terms of environmental science, leaving room for improvement in the pursuit of “sustainable development” Kyoto Protocol. That is, development of an emulsified composition that uses neither a synthetic polymer nor a surfactant is desired.
[0004]
On the other hand, alginic acid has its calcium salt used as a film-forming agent in cosmetics, and alginic acid polyhydric alcohol ester may be used as a skin protecting component or as a thickening component in cosmetics. Are known. (Patent Documents 3 to 10) However, an emulsion comprising 1) a polyhydric alcohol ester of alginic acid and 2) alginic acid and / or a salt thereof is not known, and synthesis is performed by taking such a configuration. It is not known at all that an emulsified composition using neither a polymer nor a surfactant can be obtained.
[Patent Document 1]
JP 2002-265319 A
[Patent Document 2]
JP2002-234830
[Patent Document 3]
JP 2002-194168 A
[Patent Document 4]
JP 2002-97125 A
[Patent Document 5]
JP 2002-47123 A
[Patent Document 6]
Japanese Patent Laid-Open No. 10-67643
[Patent Document 7]
JP-A-10-67642
[Patent Document 8]
JP 09-255562 A
[Patent Document 9]
JP 09-124441 A
[Patent Document 10]
JP 09-77628 A
[0005]
[Problems to be solved by the invention]
The present invention has been made under such circumstances, and an object of the present invention is to provide an emulsified composition that does not use a synthetic polymer or a surfactant, which is suitable as an external preparation for skin.
[0006]
In light of such circumstances, the present inventors sought an emulsion composition suitable for use as an external preparation for skin, which does not use a synthetic polymer or a surfactant.
The inventors have found that an emulsion composition containing 1) a polyhydric alcohol ester of alginic acid and 2) alginic acid and / or a salt thereof has such characteristics, and has completed the invention. That is, the present invention relates to the following technique.
(1) An emulsion composition comprising 1) a polyhydric alcohol ester of alginic acid and 2) alginic acid and / or a salt thereof , wherein the content of the polyhydric alcohol ester of alginic acid is 1 with respect to the total amount of the emulsion composition. ˜5 wt%, wherein the alginic acid and / or salt thereof contains 0.001 to 0.25 wt% (in terms of chloride) of a polyvalent metal salt of alginic acid with respect to the total amount of the emulsion composition. An emulsified composition.
(2) The emulsion composition according to (1), wherein the polyhydric alcohol ester of alginic acid is alginic acid propylene glycol ester.
(3) polyvalent metal salt of A alginic acid, characterized in that calcium alginate, magnesium alginate, is one to be selected from alginic aluminum and zinc alginate is 2 or more, (1) or (2) The emulsion composition described in 1.
( 4 ) The emulsified composition according to any one of (1) to ( 3 ) , which is an external preparation for skin.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
(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. 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 NLSK "and the like. These differ in viscosity and degree of esterification. Particularly preferred for use as the emulsified composition of the present invention is “Chimiloid NLSK”. In the emulsified composition of the present invention, the polyhydric alcohol ester of alginic acid has an action of stably emulsifying and dispersing the oil component. These esters of polyhydric alcohols of alginic acid can contain only one species or a combination of two or more species. The preferable content of the polyhydric alcohol ester of alginic acid in the emulsified composition of the present invention is 1 to 5% by weight, more preferably 1.2 to 2%, based on the total amount of the emulsified composition. % By weight. This is because if the amount is too small, the emulsion stability may be impaired. If the amount is too large, the emulsion becomes too hard and the usability may be impaired.
[0008]
(2) Alginic acid and / or salt thereof, which is an essential component of the emulsion composition of the present invention The emulsion composition of the present invention contains alginic acid and / or a salt thereof as an essential component. As such alginic acid and / or a salt thereof, a form containing an alginate is preferable. Examples of the alginate include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium and magnesium, neutral metal salts such as zinc salt and aluminum salt, manganese salt, iron salt and nickel salt. Preferred examples include transition metal salts such as ammonium salts, organic amine salts such as triethanolamine salts and triethylamine salts, and basic amino acid salts such as lysine salts and arginine salts. Especially, what contains the form which uses polyvalent metal salts , such as calcium, magnesium, zinc, and aluminum, as a counter ion is more preferable. In the emulsified composition of the present invention, alginic acid and / or a salt thereof has an action of stabilizing a system emulsified with an ester of a polyhydric alcohol of alginic acid. In the emulsified composition of the present invention, the preferable content of alginic acid and / or a salt thereof is preferably 0.05 to 5% by weight, more preferably 0.1 to 2% by weight in terms of sodium alginate. In addition, the polyvalent metal salt is more preferably 0.0005 to 0.25% by weight, more preferably 0.005 to 0.2% by weight in terms of chloride.
[0009]
(3) Emulsion composition of this invention The emulsion composition of this invention contains the said essential component, It is characterized by the above-mentioned. The emulsified composition of the present invention can be applied to the whole composition in which an emulsified form is usually used as a preparation. For example, skin external preparations such as food compositions, pharmaceutical compositions, cosmetics and skin external medicines can be preferably exemplified, and skin external preparations are particularly suitable. In the emulsified composition of the present invention, in addition to the essential components, optional components usually used in the emulsified composition can be contained within a range not impairing the effects of the present invention. Examples of such optional components include hydrocarbons such as squalane, liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, microcrystalline wax, and solid paraffin, dimethicone, femethicone, cyclomethicone, amodimethicone, polyether-modified silicone, and the like. Silicones, jojoba oil, carnauba wax, mole, beeswax, geiwa, octyldodecyl oleate, isopropyl myristate, neopentyl glycol diisostearate, malate diisostearate, stearic acid, lauric acid, Fatty acids such as myristic acid, palmitic acid, isostearic acid, isopalmitic acid, behenic acid, oleic acid, behenyl alcohol, cetanol, oleyl alcohol, octadecyl alcohol Higher alcohols such as coal, castor oil, coconut oil, hydrogenated coconut oil, coconut oil, wheat germ oil, triglycerides such as isostearic acid triglyceride, isooctanoic acid triglyceride, olive oil, 1,3-butanediol, glycerin, diglycerin , Dipropylene glycol, polyethylene glycol, 1,2-pentanediol, 1,2-hexylene glycol, isoprene glycol and other polyhydric alcohols, sorbitan sesquioleate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquistearate, sorbitan mono Stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene stearate, polyoxyethylene oleate, polio Nonionic surfactants such as ciethylene glyceryl fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, anionic surfactants such as sodium lauryl stearate, polyoxyethylene alkyl sulfate, sulfosuccinate ester salt, Cationic surfactants such as quaternary alkyl ammonium salts, amphoteric surfactants such as alkyl betaines, organic powders such as crystalline cellulose, cross-linked methylpolysiloxane, polyethylene powder, acrylic resin powder, talc, mica, Sericite, magnesium carbonate, calcium carbonate, titanium dioxide, iron oxide, bitumen, ultramarine, titanium mica, titanium sericite, silica and other surface-treated powders, acrylic acid / alkyl methacrylate copolymers and / or Its salt, carboxybi Nyl polymers and / or salts thereof, thickeners such as xanthan gum and hydroxypropyl cellulose, vitamins such as retinol, retinoic acid, tocopherol, riboflavin, pyridoxine, ascorbic acid, ascorbic acid phosphate ester, glycyrrhetinate, glycyrrhetin, ursolic acid , Terpenes such as oleanolic acid, active ingredients such as steroids such as estradiol, ethinyl estradiol, estriol, preservatives such as phenoxyethanol, parabens, hibiten gluconate, benzalkonium chloride, dimethylaminobenzoic acid esters, cinnamon Preferred examples include ultraviolet absorbers such as acid esters and benzophenones. Of these, surfactants, acrylic acid / alkyl methacrylate copolymers and / or salts thereof, carboxyvinyl polymers and / or salts thereof, and the like are not substantially contained according to the gist of the present invention. Is preferred. Moreover, since the emulsified composition of the present invention has the advantage that it is susceptible to biodegradation, there is a weak antiseptic effect, which is a disadvantage of this, and in the sense of complementing it, 1,3-butanediol, 1,2-pentanediol, isoprene glycol, 1,2-hexylene glycol, more preferably an antibacterial polyhydric alcohol such as 1,2-pentanediol, 1,2-hexylene glycol. The preferable content of such polyhydric alcohol is 1 to 10% by weight based on the total amount of the emulsion composition. The emulsified composition of the present invention can be produced by treating these essential components and optional components according to a conventional method.
[0010]
【Example】
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 only to the examples.
[0011]
<Example 1>
The emulsified composition 1 (cosmetics) of the present invention was prepared according to the formulation shown 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, ni was gradually added to emulsify, and the mixture was stirred and cooled to obtain emulsion composition 1 as an emulsion. At the same time, Comparative Example 1 in which sodium alginate was replaced with propylene glycol alginate, Comparative Example 2 in which propylene glycol alginate was replaced with alginic acid, Control Example 1 in which sodium alginate was replaced with water, and Comparative example in which propylene glycol alginate was replaced with water 2. A control example 3 in which sodium alginate and propylene glycol alginate were substituted with alginic acid was also prepared. About these, emulsifiability was evaluated with a microscope, and stability was evaluated by a storage test for 2 weeks at 5 ° C., 20 ° C., and 40 ° C. As evaluation criteria, ◯: good, Δ: partially defective, and x: defective were used. The results are shown in Table 1. From this, it can be seen that the emulsified composition of the present invention has very good emulsifiability and stability. The emulsion composition 1 was evaluated as having a requirement as a cosmetic in the evaluation by a specialized panelist.
Sodium alginate 0.1 parts by weight Propylene glycol ester alginate 1.5 parts by weight (Chimiloid NLSK)
1,2-hexylene glycol 5 parts by weight Ro water 70 parts by weight Calcium chloride 0.001 part by weight Water 13.399 parts by weight Nisqualane 5 parts by weight Glyceryl triisooctanoate 5 parts by weight
[Table 1]

-: Cannot be implemented [0013]
<Example 2>
Emulsified compositions 2 to 4 (both cosmetics) were prepared and evaluated in the same manner as in Example 1 by changing the amount of propylene glycol alginate in the emulsified composition 1, and the effect was observed. The results are shown in Table 2. This shows that the preferable content of the polyhydric alcohol ester of alginic acid is 1 to 5% by weight, more preferably 1.2 to 2% by weight, based on the total amount of the emulsified composition. In addition, the emulsion compositions 2 to 4 were evaluated as having requirements as cosmetics in the evaluation by a specialized panel.
Sodium alginate 0.1 parts by weight Propylene glycol ester alginate * parts by weight (Chimiloid NLSK)
1,2-hexylene glycol 5 parts by weight water 71.5- * parts by weight calcium chloride 0.001 part by weight water 13.399 parts by weight Nisqualane 5 parts by weight glyceryl triisooctanoate 5 parts by weight To
[0014]
[Table 2]

[0015]
<Example 3>
Emulsified compositions 5 to 7 (both cosmetics) were prepared and evaluated in the same manner as in Example 1 by changing the amount of calcium chloride in the emulsified composition 1, and the effect was observed. The results are shown in Table 3. From this, the preferable content of the polyvalent metal salt such as calcium chloride is 0.0005 to 0.25% by weight in terms of the total amount with respect to the total amount of the emulsified composition, converted to 1 chloride, more preferably 0. It turns out that it is 0.005-0.2 weight%. In addition, the emulsified compositions 5 to 7 were evaluated as having cosmetic requirements in the evaluation by a specialized panel.
Sodium alginate 0.1 parts by weight Propylene glycol ester alginate 1.5 parts by weight (Chimiloid NLSK)
1,2-hexylene glycol 5 parts by weight B water 70 parts by weight calcium chloride ** parts by weight water 13.4-** parts by weight Nisqualane 5 parts by weight glyceryl triisooctanoate 5 parts by weight ** in Table 3 I write.
[0016]
[Table 3]

[0017]
<Example 4>
Emulsified compositions 8 to 7 (both cosmetics) were prepared and evaluated in the same manner as in Example 1 by changing the grade of propylene glycol alginate of the emulsified composition 1, and the effect was observed. The results are shown in Table 4. This shows that any grade can be used.
Sodium alginate 0.1 parts by weight Propylene glycol ester alginate 1.5 parts by weight (products listed in Table 4)
1,2-hexylene glycol 5 parts by weight B water 70 parts by weight Calcium chloride 0.001 part by weight Water 13.399 parts by weight Nisqualane 5 parts by weight Glyceryl triisooctanoate 5 parts by weight
[Table 4]

[0019]
<Example 5>
The same examination as in Example 4 was performed by replacing calcium chloride in the emulsified composition 1 with another polyvalent metal chloride. It can be seen that any polyvalent metal chloride can be used. It can also be seen that calcium is particularly preferred.
Sodium alginate 0.1 parts by weight Propylene glycol ester alginate 1.5 parts by weight ("Chimiloid NLSK")
1,2-hexylene glycol 5 parts by weight B water 70 parts by weight C Components listed in Table 5 0.001 part by weight Water 13.399 parts by weight Nisqualane 5 parts by weight Glyceryl triisooctanoate 5 parts by weight
[Table 5]

[0021]
<Example 6>
In the same manner as in Example 1, an emulsified composition 18 (medicinal preparation for skin) was prepared.
Sodium alginate 0.1 parts by weight Propylene glycol ester alginate 1.5 parts by weight (Chimiloid NLSK)
1,2-hexylene glycol 5 parts by weight water 70 parts by weight calcium chloride 0.001 part by weight water 11.399 parts by weight Nisqualane 5 parts by weight glyceryl triisooctanoate 5 parts by weight terbinafine 2 parts by weight
【The invention's effect】
According to the present invention, it is possible to provide an emulsified composition that is suitable as an external preparation for skin and uses neither a synthetic polymer nor a surfactant.

Claims (4)

An emulsion composition containing 1) a polyhydric alcohol ester of alginic acid and 2) alginic acid and / or a salt thereof,
The content of the polyhydric alcohol ester of alginic acid is 1 to 5% by weight with respect to the total amount of the emulsion composition,
The emulsified composition , wherein the alginic acid and / or salt thereof contains 0.001 to 0.25% by weight (in terms of chloride) of a polyvalent metal salt of alginic acid with respect to the total amount of the emulsified composition. 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 polyvalent metal salt of alginic acid is one or more selected from calcium alginate, magnesium alginate, aluminum alginate and zinc alginate. . It is a skin external preparation, The emulsion composition of any one of Claims 1-3 characterized by the above-mentioned.