JP2012012315A - Skin care external preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a skin care external preparation containing wax stably in the uncrystallized state, and having excellent feeling of use and excellent moisturizing effect.SOLUTION: The skin care external preparation contains following components (A), (B), (C), (D) and (E): (A) an alkyl-modified carboxyvinyl polymer; (B) an oily component which is solid at room temperature, and whose melting point is ≥60°C; (C) an oil whose refractive index is ≥1.46, and whose SP value is ≥17.1; (D) an alkali metal salt; and (E) a nonionic surfactant whose HLB is 1-4.5; wherein the mass ratio between the components (A), (B) and (D) is shown by equality: (D)/((A)+(B))=1/1-1/30.

Description

  The present invention relates to an external preparation for skin.

Various skin external preparations are used to suppress moisture transpiration of the skin and obtain a moisturizing effect. As the dosage form of the external preparation for skin, an oil-in-water emulsion composition and a water-in-oil emulsion composition are typical, and among these, the water-in-oil emulsion composition is applied after being applied to the skin. Although the film feeling is long-lasting, there is a problem that the oily component is sticky and the feeling of use is poor. Further, since the formed coating film repels water, it was difficult to give moisture to the skin even when trying to replenish water.
On the other hand, the oil-in-water type emulsion composition has no stickiness and a refreshing feeling of use, but it was easy to flow off with water and its residual property was low.

  In addition, a moisturizing effect is enhanced by adding a wax or the like to the external preparation for skin. However, although wax is excellent in the action of suppressing moisture evaporation by forming a film on the skin, it has high crystallinity, so when blended in an oil-in-water emulsion composition, wax crystals grow at high temperatures and cycles. Therefore, it was difficult to mix stably.

Therefore, it has been studied to stably disperse the wax in the composition.
For example, Patent Document 1 discloses that skin moisture is evaporated by combining silicone with solid fat such as hydrocarbons and / or semi-solid fat and emulsifying with alkyl acrylate crosspolymer and acrylic acid-long chain alkyl methacrylate copolymer. An emulsified cosmetic which is excellent in inhibitory action and excellent in stability is described. Patent Document 2 describes an oil-in-water emulsion composition in which an oily component that is solid at room temperature, such as solid hydrocarbon, is emulsified with an alkyl-modified carboxyvinyl polymer. Here, an emulsified composition having excellent usability is obtained by emulsifying wax by a high pressure emulsification method or the like without using an activator. Further, Patent Document 3 contains at least two kinds of nonionic surfactants, and a mixture of nonionic surfactants having a HLB of 6 to 13 at room temperature and a high concentration wax under cooling conditions. Is described.

  However, Patent Document 1 has a large amount of solid fat and semi-solid fat component among the lipophilic components, has a heavy stickiness and feeling of use, and it is difficult to give gloss to the skin. In addition to requiring a special emulsification apparatus such as use of a high-pressure emulsifier, Patent Document 2 has the possibility of polymer gelation and wax precipitation. Further, in Patent Document 3, the feeling of use such as the elongation of the preparation is not sufficient. In any of these documents, the wax is stably dispersed, and the elongation during application (use) of the external preparation is good and refreshing. The feeling of use which had the feeling which was made and the feeling which the subsequent moisturizing effect contradicts was not enough.

Japanese Patent No. 3515154 Japanese Patent Laid-Open No. 9-255529 JP 2000-178133 A

  An object of the present invention is to provide an external preparation for skin which contains wax stably without crystallizing, has a good feeling in use, and has an excellent moisturizing effect.

  When the present inventors use an alkyl-modified carboxyvinyl polymer, a wax, a specific oil agent, an alkali metal salt, and a nonionic surfactant having a low HLB in combination at a specific ratio, a skin external preparation that solves the above problems can be obtained. It was found that it can be obtained.

The present invention includes the following components (A), (B), (C), (D) and (E):
(A) an alkyl-modified carboxyvinyl polymer,
(B) an oily component having a melting point of 60 ° C. or higher and solid at normal temperature;
(C) an oil having a refractive index of 1.46 or more and an SP value of 17.1 or more,
(D) an alkali metal salt,
(E) The nonionic surfactant of HLB1-4.5 is contained, and the mass ratio of component (A), (B) and (D) is (D) / ((A) + (B)) = 1. An external preparation for skin that is 1 to 1/30 is provided.

  The external preparation for skin of the present invention contains wax stably without crystallizing, has a good spread, no stickiness, good use feeling, high film feeling and glossy feeling, and excellent moisturizing effect. .

  The alkyl-modified carboxyvinyl polymer of the component (A) used in the present invention is not particularly limited as long as it is used for a normal skin external preparation, but an acrylic acid / alkyl methacrylate copolymer is preferable.

  Specifically, commercially available products such as Pemlen TR-1, Pemlen TR-2, Carbopol ETD2020, Carbopol 1382, Carbopol 1342 (above, Lubrizol Advanced Materials), AQUPEC HV-501ER (Sumitomo Seika) Can be used.

  One or more kinds of the alkyl-modified carboxyvinyl polymer of the component (A) can be used, and the total composition is 0.1 to 2% by mass, particularly 0.2 to 1.5% by mass, and further 0.2 to 0%. .9% by mass is preferable because it suppresses crystallization of wax, can be stably blended (emulsified) with other components such as polar oils and metal salts in the external preparation for skin, and exhibits an excellent feeling of use. .

The oily component of component (B) used in the present invention has a melting point of 60 ° C. or higher and is solid at room temperature (25 ° C.), and preferably has a melting point of 60 to 110 ° C.
By using such a high melting point oily component, it is possible to obtain an excellent moisturizing effect due to high film property and high residual property and a smooth feeling of use.
In this invention, melting | fusing point is a thing measured by the quasi-drug raw material specification I (General test method, 70. Melting | fusing point measuring method 1st method).

Examples of such oily components are those used in normal skin external preparations, and include solid oils such as hydrocarbons, waxes, esters, silicones, animal waxes, vegetable waxes, mineral waxes, synthetic waxes, and the like. It is selected from waxes and mixtures thereof. For example, paraffin, ceresin, synthetic hydrocarbon wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene wax, ethylene propylene copolymer, candelilla wax, beeswax, carnauba wax and the like can be used.
Of these, hydrocarbons are preferable, and ceresin (melting point: 72-76 ° C.), microcrystalline wax (melting point: 60-85 ° C.), polyethylene wax (melting point: 75-105 ° C.), paraffin wax (melting point: 70-78 ° C.) ) Is preferable in terms of the film feeling and the moisturizing effect.

  The oily component of component (B) can be used singly or in combination of 0.5 to 10% by weight, particularly 0.5 to 8% by weight, and more preferably 1 to 6% by weight in the total composition. This is preferable from the viewpoints of coating properties, feeling of use, and stability of external preparations.

The oil agent of component (C) used in the present invention has a refractive index of 1.46 or more and an SP value of 17.1 J / cm ³ or more. Here, the refractive index is a value obtained by an Abbe refractometer (NAR-2T, Atago Co., Ltd.) at 25 ° C.
The SP value represents a solubility parameter δ, which is a substance constant given by δ = (E / V) ^1/2 from the molecular cohesive energy E and molecular volume V of the liquid. The SP value can be determined by the method for determining the solubility parameter described in Kozo Shinoda, “Solution and Solubility 3rd Edition” (Maruzen Co., Ltd., published in 1991), page 78-.
By using an oil agent having such a high refractive index and polarity, high gloss can be drawn on the skin by reflection of light, so that the gloss of the skin can be enhanced.

  Examples of such oil agents are those used for normal skin external preparations such as alkyl benzoate (C12-15), methylphenylpolysiloxane, reaction product of diphenylamine and acetone, diphenyl sulfide, N-phenyl-γ-aminopropyl. Trimethoxysilane, β-phenylethyl alcohol, phenylxylylethane, phenylglycidyl ether, phenylacetic acid ethyl, phenylphosphonic acid dichloride, phenylphosphonic acid dimethyl ester, 2-phenoxyethanol, phenoxyethyl acrylate, phenylacetaldehyde, p-methylphenylacetaldehyde , Ethyl methylphenylglycidate, [mono (di or tri)] (α-methylbenzyl) phenol, [mono (di or tri)] (α-methylbenzyl) phenol , [Mono (di or tri)] (α-methylbenzyl) phenol, rosinol, polymethylene polyphenyl polyisocyanate, phosphoric acid (trisisopropylphenyl), nonylphenyl; phenyl phosphates such as octyl diphenyl phosphate, cresyl diphenyl phosphate; Diphenylisodecyl phosphite, tris (nonylphenyl) phosphite, tris (mono or dinonylphenyl) phosphite, triphenyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6- and phosphites such as t-butylphenyl-di-tridecyl) phosphite.

Of these, alkyl benzoate (C12-15) (refractive index 1.48, SP value 19.0 J / cm ³ ), methylphenylpolysiloxane (refractive index 1.58, SP value 20.3 J / cm ³ ). preferable.

  Component (C) can be used singly or in combination of two or more, and the total composition contains 1 to 20% by mass, particularly 1 to 15% by mass, and more preferably 1 to 10% by mass. It is preferable from the point of drawing out.

Examples of the alkali metal salt of component (D) used in the present invention include primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, pyrophosphoric acid, polyphosphoric acid, carbonic acid, citric acid, succinic acid, tartaric acid, and lactic acid. And the sodium salt or potassium salt of the acid, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. Of these, potassium dihydrogen phosphate and potassium lactate are particularly preferable.
In the present invention, by using an alkali metal salt, water retention in the stratum corneum can be improved, and the effect of giving moisture to the skin can be enhanced.

  Component (D) can be used singly or in combination of 0.1 to 5% by weight, particularly 0.1 to 3% by weight, and further 0.2 to 1.5% by weight in the total composition. It is preferable in terms of the moisturizing effect.

  In the present invention, the mass ratio of the components (A), (B) and (D) is (D) / ((A) + (B)) = 1/1 to 1/30, preferably 1/1 to 1. / 15. By setting the component (A), the component (B), and the component (D) within this range, gelation due to an increase in the concentration of the components (A) and (B) is suppressed, and the wax is stably emulsified. it can. In addition, a smooth finger cream can be realized, it has a good stretch, and a high coating feeling can be obtained.

The nonionic surfactant of the component (E) used by this invention is a thing of HLB1-4.5.
Here, HLB (hydrophilic / lipophilic balance) is calculated by the following Griffin equation.

Specifically, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene core Stanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene modified Organopolysiloxane, polyoxyalkylene-alkyl co-modified organopolysiloxanes, and the like. The fatty acid moiety is preferably composed of a saturated or unsaturated fatty acid residue having 8 to 24 carbon atoms. Of these, glycerin fatty acid esters are preferred.
By using the nonionic surfactant of component (E), the polar oil of component (C) can be stably emulsified while suppressing crystallization of the wax.

  Component (E) can be used singly or in combination of two or more, and 0.5 to 10% by weight, particularly 0.5 to 5% by weight in the total composition is high in the coating feeling and elongation is high. It is preferable because the feeling of use with no stickiness is also good.

The external preparation for skin of the present invention can further contain (F) an anionic surfactant and (G) a nonionic surfactant of HLB 8 to 16, and can further enhance the stability.
Examples of the component (F) anionic surfactant include higher fatty acid salts such as sodium laurate and potassium palmitate; alkyl sulfate salts such as sodium lauryl sulfate and potassium lauryl sulfate; and alkyl ethers such as sodium polyoxyethylene lauryl sulfate. Sulfate ester salt; N-acyl sarcosine salt such as sodium lauroyl sarcosine; higher fatty acid amide sulfonate such as sodium N-myristoyl-N-methyltaurine; sodium monostearyl phosphate, sodium polyoxyethylene lauryl ether, polyoxy Phosphate ester salts such as sodium ethylene stearyl ether phosphate; Sulfosuccinates such as sodium di-2-ethylhexylsulfosuccinate; Sodium linear dodecylbenzene sulfonate, Lini Alkylbenzene sulfonates such as dodecylbenzene sulfonic acid triethanolamine salt; N- lauroyl glutamate monosodium, N- stearoyl disodium sodium, N- acyl glutamates such as N- myristoyl -L- monosodium glutamate and the like.
Among these, phosphate ester salts such as sodium monostearyl phosphate, sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene stearyl ether phosphate are preferable. A polyoxyethylene addition mole number of 3-30 is preferable.

  One or more anionic surfactants of the component (F) can be used, and 0.05 to 10% by mass, particularly 0.1 to 3% by mass in the total composition is good and sticky. It is preferable because it is excellent in use feeling.

The nonionic surfactant of component (G) is from HLB 8 to 16, and those used for normal skin external preparations can be used. HLB is as described above.
Specifically, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene core Stanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene modified Organopolysiloxane, polyoxyalkylene-alkyl co-modified organopolysiloxanes, and the like.

  One or more nonionic surfactants of the component (G) can be used, and 0.05 to 10% by mass, particularly 0.1 to 3% by mass in the total composition is good and sticky. It is preferable because it has an excellent feeling of use.

  In the present invention, the mass ratio of the components (B), (C) and (G) is (C) / ((B) + (G)) = 1/6 to 3/1, particularly 1/4. It is preferable that the ratio is ˜2 / 1 because sufficient gloss can be obtained. Oils with a high refractive index can bring out a high gloss on the skin due to light reflection, but if the residue on the skin increases, the skin becomes rather shiny and cannot be said to be a natural gloss. . In the present invention, by using in such a range, a natural gloss can be derived from the inside of the skin by appropriately holding the oil agent on the surface of the skin by the wax coating.

  The skin external preparation of this invention can contain the other component used for a normal skin external preparation other than the said component. Examples include lower alcohols, moisturizers, antioxidants, preservatives, chelating agents, whitening agents, UV absorbers, vitamins, various other medicinal ingredients, powders, fragrances, and coloring materials.

  The external preparation for skin of the present invention is further prepared as an oil-in-water emulsion composition by blending water and using an ordinary method. It is preferable to contain 30-90 mass% of water in the whole composition.

The external preparation for skin of the present invention comprises an oil-in-water emulsion composition in which the solid oily component of component (B) is combined with components (A) and components (C) to (E) at a specific ratio. Thus, a smooth cream of a finger can be realized, and there is little stickiness, and it is possible to achieve both a smooth and good feeling of use and a high coating property and its high persistence.
Due to the interaction between the component (A) and the component (B), the crystallization of the component (B) is suppressed, and a stable oil-in-water emulsion composition can be obtained. That is, in the composition of the present invention, a large gel-like dispersed droplet constituted by the interaction of the component (A) and the component (B) and a small particle in which the oil agent of the component (C) is emulsified with the active agent The diameter-emulsified droplets coexist with a specific composition, and thereby, the spread is good and a high film feeling can be obtained.

Examples 1-9, Comparative Examples 1-6
A skin external preparation having the composition shown in Table 1 was produced, and the stability, the spread of the agent, the coating feeling and the gloss feeling were evaluated. The results are also shown in Table 1.

(Production method)
(1) A water-soluble component ((A) alkyl-modified carboxyvinyl polymer, (D) alkali metal salt, other water-soluble polymer) is combined with water, and stirred and dissolved at 70 to 80 ° C. To do.
(2) Next, an oil component ((B) solid oil component, (C) oil agent, other oil components) and surfactants ((E) nonionic surfactants, other surfactants), Stir and dissolve at 70 to 80 ° C. to obtain an oil phase part.
(3) The oil phase portion was stirred and mixed in the water phase portion at 80 ° C. and cooled to prepare an oil-in-water emulsified cosmetic, whereby a skin external preparation was obtained.

(Evaluation methods)
(1) Stability:
With regard to the stability of the obtained external preparation for skin, the appearance and properties of the initial state and the state after 6 months at room temperature were evaluated by paying attention to the precipitation of wax crystals.
A: The same as the initial state.
○: Difficult to understand, although slightly different from the initial state.
Δ: Although different from the initial state, there is no problem as a product.
X: There is a problem as a product, which is greatly different from the initial state.

(2) Agent spread:
Apply 0.5g of the obtained external preparation on the back of the hand, blend the agent on the back of the hand, and use the specialized panel (N = 5) to evaluate the goodness of elongation on the back of the hand in the following five criteria. Went. Results are shown as average values. The smaller the score, the better the elongation.
1; Excellent elongation.
2; Elongation is good.
3; Usually.
4; It does not grow a little.
5; Elongation is bad.

(3) Coating feeling:
In the evaluation of (1), 5 minutes after applying the topical skin preparation on the back of the hand, touch the feeling that the preparation is on the back of the hand with the hand, and feel that the skin is covered, as in (1). N = 5), the film feeling was evaluated in five levels according to the following criteria. Results are shown as average values. The smaller the score, the better the coating feeling.
1: The film feeling is high.
2; There is a slight film feeling.
3; I can't say either.
4; Slightly no film feeling.
5: There is no film feeling.

(5) Glossy feeling:
Five minutes after application to the back of the hand in the evaluation of (1), the appearance gloss of the back of the hand was evaluated under a fluorescent lamp. As in (1), the glossiness of the appearance on a specialized panel (N = 5) was evaluated in five levels according to the following criteria. Results are shown as average values. A smaller score indicates that the coated part is glossy.
1; glossy.
2; Somewhat glossy.
3; I can't say either.
4; Somewhat dull.
5: There is no gloss.

  From the results shown in Table 1, the external preparation for skin of the present invention contained a wax stably without crystallizing, had a good feeling of use (drug feeling and glossiness), and had an excellent moisturizing effect. . Comparative Example 1 in which the alkyl-modified carboxyvinyl polymer as the component (A) of the present invention is made into another water-soluble polymer cannot suppress the crystallization of the wax even when used in combination with a surfactant having a low HLB, and the time. Crystals precipitated over time. In Comparative Example 2 in which Vaseline having a melting point of less than 60 ° C. was blended in place of the component (B), the composition was stable (emulsified and dispersed) over time, but the feeling of use (spreading and gloss of the agent) None of the moisturizing effects were sufficient. In Comparative Example 3 using a non-polar oil having a low SP value instead of the component (C), the emulsification stability of the wax was inferior and the glossiness was hardly exhibited. In Comparative Example 4 containing no alkali metal salt, the stability of the wax was inferior and the elongation of the agent was poor. In Comparative Example 5 in which the wax and polar oil were emulsified and dispersed only with a water-soluble polymer without containing a surfactant having a low HLB, crystallization of the wax could not be suppressed, and crystals were precipitated over time. In Comparative Example 6 in which a large amount of an alkali metal salt was blended with the alkyl-modified carboxyvinyl polymer and the wax, the stability of the wax was poor, and neither the feeling of use (spreading or glossiness of the agent) nor the moisturizing effect was sufficient. .

Claims (5)

The following components (A), (B), (C), (D) and (E):
(A) an alkyl-modified carboxyvinyl polymer,
(B) an oily component having a melting point of 60 ° C. or higher and solid at normal temperature;
(C) an oil having a refractive index of 1.46 or more and an SP value of 17.1 or more,
(D) an alkali metal salt,
(E) The nonionic surfactant of HLB1-4.5 is contained, and the mass ratio of component (A), (B) and (D) is (D) / ((A) + (B)) = 1. / 1 to 1/30 skin external preparation.   Further, 30 to 90% by mass of water is contained in the total composition, 0.1 to 2% by mass of component (A), 0.5 to 10% by mass of component (B), and 1 to 2 of component (C). The skin external preparation according to claim 1, comprising 20% by mass, 0.1-5% by mass of component (D), and 0.5-10% by mass of component (E).   The skin external preparation according to claim 1 or 2, wherein the oil agent of component (C) is selected from alkyl benzoate and methylphenyl polysiloxane.   Furthermore, the skin external preparation of any one of Claims 1-3 containing the nonionic surfactant of (F) anionic surfactant and (G) HLB8-16.   The skin external preparation according to claim 4, wherein the mass ratio of the components (B), (C) and (G) is (C) / ((B) + (G)) = 1/6 to 3/1.