JP4676730B2 - Emulsifier type skin external preparation - Google Patents

Description

  The present invention relates to a skin external preparation, and more particularly to an emulsifier type skin external preparation using a polyhydric alcohol ester of alginic acid.

  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. Among 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. From such a background, the present inventors have found that a surfactant-free oil-in-water emulsion system can be realized by using a salt of alginic acid, an ester and a salt of a polyhydric alcohol of alginic acid. (For example, refer to Patent Document 1) In this technique, a salt of alginic acid is used as an essential component. However, there is a case where the coating property of this component flakes a decorative film. Improvements have come to be desired. In addition, when an anionic substance exists, it may form an insoluble substance with a counter ion of alginic acid such as calcium ion, and in this sense, it can be said that the application range is limited. In other words, it can be said that development of an alginate-free external preparation in an emulsifier form containing a polyhydric alcohol ester of alginic acid has been desired.

  On the other hand, as polyhydric alcohol esters of alginic acid, propylene glycol alginate, glycerin alginate and the like are known and used in an emulsifier form or the like (see, for example, Patent Document 1 or Patent Document 2). A monohydric alcohol ester having an esterification degree of 70% or more and a viscosity in a 1% aqueous solution of 100 mPascal seconds or less under the measurement condition of 20 ° C. is 2 to 5 with respect to the total amount of the external preparation for skin. No emulsifier type skin external preparation containing mass% is known at all, and it is not known at all that an emulsified system of fine emulsified particles can be obtained without using a salt of alginic acid by taking such a constitution. .

JP 2004-196728 A No. 01/93812

  The present invention has been made under such circumstances, and an object of the present invention is to provide an alginate-free dosage form in an emulsifier-type skin external preparation containing a polyhydric alcohol ester of alginic acid.

In view of such a situation, the present inventors have sought for an alginate-free dosage form in an emulsifier type skin external preparation containing a polyhydric alcohol ester of alginic acid. Propylene glycol ester having a degree of esterification of 70% or more and a viscosity in a 1% aqueous solution of 10 to 30 mPascal · sec under a measurement condition of 20 ° C. with respect to the total amount of the external preparation for skin. The inventors have found that an emulsifier-type skin external preparation containing 2 to 5% by mass has such characteristics, and has completed the invention. That is, the present invention is as follows.
(1) Propylene glycol ester of alginic acid having a degree of esterification of 70% or more and a viscosity in a 1% aqueous solution of 10 to 30 mPascal · sec under a measurement condition of 20 ° C. A skin external preparation in the form of an oil-in-water emulsifier, characterized by containing 2 to 5% by mass based on the total amount and containing no alginates.
(2) The skin external preparation in the form of an oil-in-water emulsifier according to (1), which contains no surfactant other than the propylene glycol ester of alginic acid.

(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 propylene glycol ester of alginic acid as an essential component from the balance between hydrophilicity and lipophilicity . Propylene glycol esters of alginic acid are already known compound, and its method of manufacture are already known. A alginic acid propylene glycol esters can be manufacture is reacted in the presence of a such as potassium carbonate sodium alginate and 1-chloro-2-propanol in aqueous alcohol. As the propylene glycol ester of alginic acid used in the external preparation for skin of the present invention, those having the following characteristics can be used.

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

Some propylene glycol esters of alginic acid having such properties are already on the market and 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., etc. Preferred examples can be given . It These can also be contained only species, it can also be contained in a combination of two or more. The preferable content of the polyhydric alcohol ester of alginic acid is the total amount as the lower limit, and is 2 to 3% by mass with respect to the total amount of the cosmetic, and the upper limit is 4 to 5% by mass. If the amount is too small, there are cases where emulsification cannot be performed. If the amount is too large, the hardness becomes too high, and the usability is impaired.

(2) The external preparation for skin of the present invention The external preparation for skin of the present invention contains the essential components and is in the form of an emulsifier. As the form of emulsification in such an emulsifier form, an emulsifier form in which an aqueous phase is present in the external phase is preferable, and both simple emulsions and complex emulsions of such form can be applied. The W emulsifier type (oil-in-water emulsifier type) can be particularly preferably exemplified. In the external preparation for skin according to the present invention, the content of the surfactant is preferably reduced as much as possible from the gist of the development, and is preferably at least 0.5 mass or less with a low environmental load, and is free of surfactant. More preferably. Further, from the viewpoint of usability, such as flaking, a A alginic acid salt-free.

  In the external preparation for skin of the present invention, in addition to the above-mentioned components, optional components usually used in external preparations for skin can be contained. 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, hardened 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, 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 (glyceryl monostearate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), 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 alkyl phenyl 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-hexylene glycol, 1,2-hexanediol, 1,2-octanediol, pyrrolidone carboxylic acid Moisturizing ingredients such as sodium, lactic acid, sodium lactate, guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, chondroitin sulfate , Dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hyaluronan Droxyethyl guar gum, carboxymethyl guar gum, dextran, keratosulfuric acid, locust bean gum, succinoglucan, carolinic acid, chitin, chitosan, carboxymethylchitin, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol , Thickeners such as bentonite, surface may be treated, powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, barium sulfate, The surface may be treated, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, the surface may be treated, mica titanium, fish phosphorus Foil, bismuth oxychloride, etc. Red, No. 202, Red No. 228, Red No. 226, Yellow No. 4, Blue No. 404, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201 Organic dyes such as red 213, yellow 204, yellow 203, blue 1, green 201, purple 201, red 204, polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer, etc. Organic powders, paraaminobenzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2 UV absorption of '-hydroxy-5'-t-octylphenyl) benzotriazole, 4-methoxy-4'-t-butyldibenzoylmethane, etc. , Lower alcohols such as ethanol and isopropanol, vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its derivatives, vitamin B12, vitamin B15 or its derivatives Preferred examples include vitamins such as vitamins, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin Ds, vitamin D, vitamin H, pantothenic acid, pantethine, pyrroloquinoline quinone, and the like. In particular, in the external preparation for skin of the present invention, examples of the component preferably contained include polyhydric alcohols, among which 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, and the like. An antibacterial polyhydric alcohol can be illustrated preferably. These can be contained alone or in combination of two or more. The preferable content of the polyhydric alcohol is 1 to 10% by mass, more preferably 3 to 8% by mass, based on the total amount of the external preparation for skin, as a total amount. The external preparation for skin of the present invention can be produced by treating these components according to a conventional method.

  The external preparation for skin of the present invention can be applied without particular limitation as long as it is administered externally to the skin. As such a skin external preparation, for example, a skin external medicine, cosmetics or skin external goods can be suitably exemplified. Particularly preferred are cosmetics. This is because cosmetics have many repetitions of use and the effects of the present invention can be exhibited more effectively.

  Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to such examples.

[Reference Example 1]
According to the formulation shown below, cosmetic 1 as an external preparation for skin of the present invention was produced. That is, the component (a) is stirred well, combined with the component (b), uniformly dispersed, heated to 80 ° C., and the mixture previously heated to 80 ° C. is gradually added with stirring. Then, homogenizer treatment was performed, followed by stirring and cooling to obtain a cosmetic 1 which is a skin external preparation of the present invention.

I)
Alginic acid propylene glycol ester ("Chimiloid NLS-K" (1% aqueous solution, viscosity at 20 ° C. is 30 to 60 mPascal · second, degree of esterification 80%) ) 2% by mass
1,3-butanediol 5% by mass
B)
77% by mass of water
Ascorbic acid-2-glucoside 1% by mass
C)
Squalane 15% by mass

(Comparative Example 1)
Similar to the cosmetic 1, an attempt was made to produce the cosmetic of Comparative Example 1 according to the following formulation, but emulsification was difficult.

I)
Alginic acid propylene glycol ester ("Chimiloid NLS-K") 1.5% by mass
1,3-butanediol 5% by mass
B)
Water 77.5% by mass
Ascorbic acid-2-glucoside 1% by mass
C)
Squalane 15% by mass

(Comparative Example 2)
Similarly to the cosmetic 1, the cosmetic of Comparative Example 2 was produced according to the following formulation.

I)
Alginic acid propylene glycol ester ("Chimiloid NLS-K") 1.5% by mass
Sodium alginate 0.1% by mass
1,3-butanediol 5% by mass
B)
Water 77.3 mass%
Ascorbic acid-2-glucoside 1% by mass
1% calcium chloride aqueous solution 0.1% by mass
C)
Squalane 15% by mass

(Test Example 1)
A low temperature storage test was conducted using the cosmetic 1 and the cosmetic of Comparative Example 2. That is, after these cosmetics were stored at 5 ° C. for 3 months, 0.1 g was taken and spread on a standard black plate to 20 mils using a doctor blade, and the number of occurrences of irregularities per 3 cm × 3 cm was counted. did. While cosmetic 1 was 0, Comparative Example 2 was 12. This shows that the external preparation for skin of the present invention is excellent in stability.

(Test Example 2)
A high temperature storage test was performed using the cosmetic 1 and the cosmetic of Comparative Example 2. That is, these cosmetics were stored at 50 ° C. for 3 weeks, and their properties were observed. In Comparative Example 2, water separation was clearly observed, but cosmetic 1 showed only slight water separation. From this, it can be judged that the cosmetic of the present invention is a preparation that further enhances the stability of the conventional alginate-alginate polyhydric alcohol ester emulsion system.

[Reference Example 2]
Similarly to cosmetic 1, cosmetic 2 (oil-in-water emulsified cosmetic), which is an external preparation for skin of the present invention, was prepared according to the formulation shown below. In this, no appearance of bumps was observed in the same storage test as in Test Example 1, and no water separation was observed in the storage test of Test Example 2.

I)
Alginic acid propylene glycol ester ("Chimiloid NLS-K") 3% by mass
1,3-butanediol 5% by mass
B)
76% by weight of water
Ascorbic acid-2-glucoside 1% by mass
C)
Squalane 15% by mass

  Similarly to cosmetic 1, cosmetic 3 (oil-in-water emulsified cosmetic), which is an external preparation for skin of the present invention, was prepared according to the formulation shown below. In this, no appearance of bumps was observed in the same storage test as in Test Example 1, and no water separation was observed in the storage test of Test Example 2. From this, it can be seen that as the polyhydric alcohol ester of alginic acid, a 1% aqueous solution having a viscosity at 20 ° C. of 30 mPascal · second or less is preferable.

I)
Alginic acid propylene glycol ester (“Chimiloid LLV” (1% aqueous solution, viscosity at 20 ° C. is 10 to 30 mPascal · second, degree of esterification 80%) ) 2% by mass
1,3-butanediol 5% by mass
B)
77% by mass of water
Ascorbic acid-2-glucoside 1% by mass
C)
Squalane 15% by mass

  Similarly to cosmetic 1, cosmetic 4 (oil-in-water emulsified cosmetic), which is an external preparation for skin of the present invention, was prepared according to the formulation shown below. In this, no appearance of bumps was observed in the same storage test as in Test Example 1, and no water separation was observed in the storage test of Test Example 2. This indicates that the skin external preparation of the present invention can emulsify not only hydrocarbons but also nonpolar oils such as silicone.

I)
Propylene glycol alginate ("Chimiloid LLV") 2% by mass
1,3-butanediol 5% by mass
B)
77% by mass of water
Ascorbic acid-2-glucoside 1% by mass
C)
Dimethicone (1000 mPascal · sec) 15% by mass

  The present invention can be applied to a stable surfactant-free emulsified cosmetic.

Claims (2)

A propylene glycol ester of alginic acid having a degree of esterification of 70% or more and a viscosity in a 1% aqueous solution of 10 to 30 mPascal · sec under a measurement condition of 20 ° C. with respect to the total amount of the external preparation for skin. An oil-in-water emulsifier type skin external preparation characterized by containing 2 to 5% by mass and containing no alginate.   The oily-in-water emulsifier-type skin external preparation according to claim 1, which contains no surfactant other than the propylene glycol ester of alginic acid.