JP4931370B2 - Emulsified composition - Google Patents

Description

  The present invention relates to an emulsified composition that can stably contain a high concentration of an amphiphilic substance that is solid at room temperature, has high skin permeability, and is excellent in skin care effects.

Amphiphiles that are solid at room temperature, such as ceramide, fatty acid, and cholesterol, are the main components of intercellular lipids and play an important role in maintaining healthy skin. Therefore, if these are blended into a skin cosmetic, a high skin care effect can be expected, and various skin external preparations have been studied (for example, Patent Document 1 and Patent Document 2).
However, since these amphiphilic substances are substances having high crystallinity and a high melting point, crystals are liable to precipitate when blended in a large amount in cosmetics, and it is difficult to blend them stably.

In order to stably mix amphiphiles in cosmetics, it has been studied to select surfactants or use them in large amounts. However, when a large amount of surfactant is used, there is a problem such as stickiness.
JP 7-33633 A Japanese Unexamined Patent Publication No. 63-192703

  An object of the present invention is to provide an emulsified composition that can stably contain an amphiphilic substance at a high concentration and has an excellent skin care effect.

  The inventors of the present invention provide a composition containing an amphiphilic substance that is solid at room temperature, and an emulsified composition that does not have an endothermic peak at room temperature or higher in differential calorimetry, It has been found that the permeability is high and an excellent skin care effect can be obtained.

That is, the present invention includes the following components (A), (B), (C) and (D):
(A) Nonionic surfactant or ionic surfactant having HLB of 9 or more,
(B) an amphiphilic substance that is solid at 25 ° C.,
(C) an oily component that is liquid at 25 ° C.,
(D) Contains water, and the mass ratio of components (A) and (B) is (A) :( B) = 1: 11 to 1:20, and is obtained by emulsification at a processing pressure of 50 MPa or more. In the differential calorimetry, an emulsion composition having no endothermic peak at room temperature or higher is provided.
The present invention also includes the following components (A), (B), (C) and (D):
(A) Nonionic surfactant or ionic surfactant having HLB of 9 or more,
(B) an amphiphilic substance that is solid at 25 ° C.,
(C) an oily component that is liquid at 25 ° C.,
(D) Contains water, and the mass ratio of components (A) and (B) is (A) :( B) = 1: 11 to 1:20, and is obtained by emulsification at a processing pressure of 50 MPa or more. In the differential calorimetry, the emulsion composition is composed of an emulsion composition having no endothermic peak at room temperature or higher, and (B) an emulsion composition for allowing a solid amphiphile to penetrate into the skin at 25 ° C. Is to provide.

  The emulsified composition of the present invention can stably contain a high concentration of an amphiphilic substance that is solid at room temperature, has high permeability to the skin of the amphiphilic substance, and is excellent in skin care effect.

  Among the components (A) used in the present invention, the nonionic surfactant is HLB 9 or more, preferably HLB 10 to 17, particularly preferably HLB 12 to 17. Here, HLB is an index indicating a hydrophilic-lipophilic balance, and is defined by the following equation by Oda and Teramura et al.

  As such a nonionic surfactant, those having an alkyl group, an alkenyl group or an acyl group having 10 to 24 carbon atoms, particularly 12 to 18 carbon atoms as a hydrophobic group are preferable. For example, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, fatty acid sucrose ester, polyglycerin fatty acid Examples thereof include esters, polyglycerin alkyl ethers, and alkyl glucoside surfactants.

  In addition, among the component (A), examples of the ionic surfactant include an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. These preferably have an alkyl or alkenyl group having 10 to 24 carbon atoms, particularly 12 to 18 carbon atoms, as a hydrophobic group.

  Examples of the anionic surfactant include fatty acid salts such as sodium laurate, potassium palmitate and triethanolamine; alkyl sulfates such as sodium lauryl sulfate, potassium lauryl sulfate, sodium stearyl sulfate and sodium cetyl sulfate; Alkyl ether sulfate esters such as oxyethylene lauryl sulfate triethanolamine; polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene (6) tridecyl ether; N-acyl sarcosine salts such as sodium lauroyl sarcosine; N-myristoyl -Higher fatty acid amide sulfonates such as sodium N-methyltaurine and N-stearoyl-N-methyltaurine; alkylphosphoric acids such as sodium monostearyl phosphate Polyoxyethylene alkyl ether phosphate ester salts such as sodium polyoxyethylene oleyl ether phosphate and sodium polyoxyethylene stearyl ether phosphate; long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate; N-lauroyl glutamic acid Long-chain N-acyl glutamates such as monosodium, monosodium N-stearoyl-L-glutamate, disodium N-stearoyl-L-glutamate, and monosodium N-myristoyl-L-glutamate.

  Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts, trialkylmethylammonium salts, and alkylamine salts.

  Examples of amphoteric surfactants include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, and the like. Imidazoline-based amphoteric surfactants; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaines and other betaine-based amphoteric surfactants; N -Amino acid type amphoteric surfactants such as lauryl glycine, N-lauryl β-alanine, N-stearyl β-alanine and the like.

  Of these, ionic surfactants are preferred, alkyl sulfate salts, long chain N-acyl glutamates, fatty acid amide sulfonates, fatty acid salts, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene alkyl ether acetic acid. Preferred are salts and alkyltrimethylammonium salts. More specifically, sodium stearyl sulfate, sodium cetyl sulfate, monosodium N-stearoyl arginine, monosodium N-stearoyl-L-glutamate, disodium N-stearoyl-L-glutamate, sodium N-myristoyl-N-methyltaurine , N-stearoyl-N-methyltaurine sodium, oleic acid triethanolamine salt, polyoxyethylene (4) sodium lauryl ether phosphate, polyoxyethylene (6) sodium tridecyl ether acetate, stearyltrimethylammonium chloride, cetyl bromide Trimethylammonium is preferred.

  One or more surfactants as the component (A) can be used, and a nonionic surfactant and an ionic surfactant can also be used in combination. Component (A) is preferably contained in the total composition in an amount of 0.01 to 7% by mass, particularly 0.05 to 5% by mass, and more preferably 0.05 to 4% by mass.

The component (B) amphiphile used in the present invention is solid at 25 ° C., and examples thereof include higher fatty acids, higher alcohols, cholesterol, cholesterol esters, aliphatic amide derivatives, and aliphatic amine derivatives. .
The higher fatty acid is preferably a saturated fatty acid having 12 to 24 carbon atoms, and examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. The higher alcohol is preferably a saturated aliphatic alcohol having 12 to 24 carbon atoms, and examples thereof include lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, and behenyl alcohol.
Further, as the cholesterol ester, those having a higher fatty acid residue having 12 or more carbon atoms, particularly 12 to 24 carbon atoms are preferable, and cholesterol palmitate, cholesterol isostearate, N-lauroyl-L-glutamic acid (cholesterol, 2-octyldodecyl). ), Lanolin fatty acid cholesterol, macadamia nut oil fatty acid cholesterol and the like.

  Examples of the aliphatic amide derivative include ceramides represented by the general formula (1) and synthetic ceramides represented by the general formula (2).

(Wherein R ¹ represents a hydrocarbon group having 12 to 32 carbon atoms, R ² represents a hydrocarbon group having 10 to 26 carbon atoms, X is a single bond, —CH (OR ³ ) —, —CH═ CH— or —OCH ₂ — is represented (R ³ represents a hydrogen atom or —COCH (OH) —R ¹ , and n represents 0 or 1).

(In the formula, R ⁴ represents a hydrocarbon group having 10 to 26 carbon atoms, R ⁵ represents a hydrocarbon group having 9 to 25 carbon atoms, and Y represents — (CH ₂ ) _m — (m represents 2 to 6 carbon atoms). Indicates an integer)

For example, natural ceramides of type II, type III, type VI, type V, type VI and the like can be mentioned as the compound of general formula (1). Moreover, as a compound of General formula (2), N- (2-hydroxy-3-hexadecyloxypropyl) -N-2-hydroxyethyl hexadecanamide (melting point 69-77 degreeC), N- (2- Hydroxy-3-hexadecyloxypropyl) -N-2-hydroxyethyldecanamide (melting point: 51.5-53 ° C.) and the like.
Furthermore, the following natural ceramides and synthetic ceramides can be used.

These may be any of natural extracts and synthetic products, and commercially available products can be used.
Examples of such commercially available ceramides include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (above, manufactured by Cosmo Farm), Ceramide TIC-001 (manufactured by Takasago Fragrance Co., Ltd.), CERAMIDE II (manufactured by Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (manufactured by DOOSAN), and CERAMIDE2 (manufactured by Sederma).

  Examples of the aliphatic amine derivatives include sphingosines, sphingosine analogs described in JP-A-6-271446, JP-A-6-271447, JP-A-6-271448, JP-A-5-194185, and the like. And amine derivatives thereof. Of these, sphingosines and amine compounds represented by the general formula (3) described in JP-A-5-194185 or acid addition salts thereof are preferable.

(In the formula, R ¹¹ represents a hydrocarbon group having 4 to 40 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ are each a hydrogen atom or a carbon atom 1 optionally substituted by a hydroxyl group. To 10 hydrocarbon groups)

Examples of the sphingosines include sphingosine, dihydrosphingosine, phytosphingosine, dehydrosphingosine, dehydrophytosphingosine, sphingadienin and their N-methyl or N, N-dimethyl forms.
Examples of the compound represented by the general formula (3) include 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol (light yellow paste).

  As the amphiphilic substance of component (B), an aliphatic amide derivative and an aliphatic amine derivative are preferable.

One or more kinds of the amphiphilic substance of the component (B) can be used, and 0.11 to 77% by mass, further 0.55 to 55% by mass, particularly 0.55 to 44% by mass in the total composition. Preferably it is done.
Moreover, in this invention, the mass ratio of component (A) and (B) is (A) :( B) = 1: 11-1: 20, Preferably it is 1: 12-1: 15.

The oily substance of the component (C) used in the present invention is liquid at 25 ° C., and those usually incorporated in cosmetics can be suitably used. For example, hydrocarbon oil, ester oil, ether oil, silicone oil, fluorine oil and the like are included.
More specifically, vegetable oils such as jojoba oil and olive oil; animal oils such as liquid lanolin; hydrocarbon oils such as liquid paraffin and squalane; diisostearyl malate, octyldodecyl lactate, isotridecyl isononanoate, isopropyl isostearate, myristic acid Fatty acid esters such as octyldodecyl; ester oils composed of fatty acids such as neopentyl glycol dicaprate and polyhydric alcohols; ester oils such as glycerin derivatives and amino acid derivatives; dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methyl Examples include silicone oils such as hydrogen polysiloxane and higher alcohol-modified organopolysiloxane; fluorine oils such as fluoropolyether and perfluoroalkyl ether silicone.

  As the oily component of component (C), one or more kinds can be used, and the total composition preferably contains 0.01 to 40% by mass, particularly 0.05 to 20% by mass, and more preferably 1 to 15% by mass. .

In this invention, it is preferable to contain the water of a component (D) in 16-99 mass% in the whole composition, and also 45-98 mass%.
In addition, other aqueous bases such as lower alcohols having 1 to 4 carbon atoms such as ethanol and propanol; polyhydric alcohols such as glycerin and propylene glycol can also be contained.

  The emulsified composition of the present invention is an active ingredient or additive used in normal cosmetics, for example, water-soluble vitamins such as ascorbic acid, nicotinic acid amide, and nicotinic acid; buckwheat extract, licorice extract, aloe extract, Animal and plant extracts such as horsetail extract, tea extract, cucumber extract, clove extract, carrot extract, clam melon extract, placenta extract, seaweed extract, maronier extract, yuzu extract, eucalyptus extract, asunaro extract; potassium hydroxide, hydroxylated Bases such as sodium, triethanolamine, sodium carbonate; pH adjusters such as citrate, tartrate, lactate, phosphate, succinate, adipate; carboxyvinyl polymer, sodium alginate, carrageenan, carboxymethylcellulose Hydroxyethyl cellulo Scan, guar gum, xanthan gum, carboxymethyl chitosan, also contain such thickeners such as sodium hyaluronate.

The emulsified composition of the present invention can be produced by mixing the blending components and emulsifying at a processing pressure of 50 MPa or more, preferably 70 to 280 MPa, more preferably 100 to 280 MPa.
A general high-pressure emulsifier can be used as an apparatus for performing such high-pressure emulsification. As a usable high-pressure emulsifier, for example, a liquid-liquid collision type high-pressure emulsifier (for example, a microfluidizer (micro Fluidics Co., Ltd.), DeBEE2000 (Bee E. E.), Nanomizer (Nanomizer), Ultimateizer (Tau Technology), etc.), and Menton-Gaulin type high-pressure homogenizer.

  The emulsion composition of the present invention thus obtained does not have an endothermic peak at room temperature or higher in differential calorimetry (DSC). The endothermic peak (transition temperature) is based on the phase transition, and means a gel state or a crystalline state below the phase transition temperature, but the emulsified composition of the present invention has no endothermic peak at room temperature or higher. This means that the hydrophobic part of the amphiphile is in a fluid state. Therefore, the amphiphilic substance does not crystallize in the emulsion composition and is stably contained.

The emulsified composition of the present invention can be suitably used as an emulsified cosmetic as it is.
In addition, the emulsion composition obtained by high-pressure emulsification is diluted with an aqueous component such as water, or a water-soluble active ingredient or additive added thereto, for example, as a cosmetic such as a skin lotion or a cosmetic liquid. Can be used. In this invention, it can be set as the oil-in-water emulsion composition whose average particle diameter of an oil droplet is 0.02-2 micrometers. In particular, from the viewpoint of the skin care effect, it is more preferably 0.02 to 0.4 μm, and further preferably 0.02 to 0.3 μm.

Example 1 and Comparative Example 1
An emulsion composition having the composition shown in Table 1 was produced, and the presence or absence of an endothermic peak in DSC and the average particle diameter of oil droplets were measured to evaluate the skin care effect. The results are also shown in Table 1.

(Production method)
(1) High pressure emulsification:
Ingredients (A), (B) and (C) are heated to 80 ° C., dissolved, and then added with component (D) and other ingredients at 80 ° C. with propeller stirring. After emulsification, cooled to 25 ° C. Thus, a pre-emulsion was prepared. This was emulsified with a microfluidizer at a predetermined treatment pressure (3 times treatment) and cooled to 25 ° C. to obtain an emulsified composition.

(2) Normal emulsification:
Ingredients (A), (B) and (C) were heated to 80 ° C. and dissolved, and then component (D) and other ingredients were added at 80 ° C. with stirring with a disper (3000 rpm). The emulsion composition was obtained by cooling to ° C.

(Evaluation methods)
(1) Confirmation of endothermic peak:
Using a differential scanning calorimeter (Seiko Electronics Co., Ltd., DSC6100), the temperature was increased at a rate of 0.5 ° C./min, and the presence or absence of an endothermic peak was observed. The sample used the emulsified composition as it was. The results are shown in FIG.

(2) Measurement of average particle size:
The average particle size of the oil droplets was measured using a particle size distribution measuring device (manufactured by Horiba, Ltd., LB-500). The sample used the emulsified composition as it was.

(3) Skin care effect:
The inner surface of the upper arm of 5 subjects was treated with acetone / ether (1: 1) for 30 minutes to obtain rough model skin. Each emulsified composition was applied twice a day for one week to this rough model skin portion (application area 26 mmφ, application amount 20 μL). The model rough skin was set to 1, healthy skin was set to 5, and the degree of improvement after one week was evaluated in five stages, and the average score of five people was calculated.

Examples 2-3 and Comparative Example 2
In the same manner as in Example 1, emulsion compositions having the compositions shown in Table 2 were produced. Ethanol was added after cooling to 40 ° C. or lower during preliminary emulsification. The presence or absence of an endothermic peak in DSC and the average particle diameter of oil droplets were measured to evaluate the skin care effect. The results are also shown in Table 2.

Examples 4-5
In the same manner as in Example 1, an emulsion composition having the composition shown in Table 3 was produced, and the presence or absence of an endothermic peak in DSC and the average particle diameter of oil droplets were measured to evaluate the skin care effect. The results are also shown in Table 3.

Example 6 and Comparative Example 3
In the same manner as in Example 1 and Comparative Example 2, an emulsion composition having the composition shown in Table 4 was produced, and the presence or absence of an endothermic peak in DSC and the average particle diameter of oil droplets were measured to evaluate the skin care effect. The sticky feeling was also evaluated. The results are also shown in Table 4.

(Evaluation methods)
Stickiness:
20 females in their 30s used each emulsified composition (10 persons each), and evaluated it on a five-point scale, with 1 being non-sticky and 5 being sticky. The results are shown by calculating the average score of 10 people.

Example 7-9
In the same manner as in Example 1 or 2, an emulsion composition having the composition shown in Table 5 was produced, the presence or absence of an endothermic peak in DSC was measured, and the skin care effect was evaluated. The results are also shown in Table 5.

It is a figure which shows the result of the differential calorimetry of Example 1 and Comparative Example 1.

Claims (5)

The following components (A), (B), (C) and (D):
(A) Nonionic surfactant or ionic surfactant having HLB of 9 or more
0.01-7% by mass,
(B) 0.11 to 77% by mass of an amphiphilic substance that is solid at 25 ° C.
(C) 4 to 40% by mass of an oily component which is liquid at 25 ° C.
(D) Water 16-99 mass%
The mass ratio of components (A) and (B) is (A) :( B) = 1: 11.7 to 1:15, and is obtained by emulsification at a processing pressure of 50 MPa or more, An emulsified composition having no endothermic peak at room temperature or higher in calorimetry. The following components (A), (B), (C) and (D):
(A) Nonionic surfactant or ionic surfactant having HLB of 9 or more
0.01-7% by mass,
(B) 0.11 to 77% by mass of an amphiphilic substance that is solid at 25 ° C.
(C) 4 to 40% by mass of an oily component which is liquid at 25 ° C.
(D) Water 16-99 mass%
The mass ratio of components (A) and (B) is (A) :( B) = 1: 11.7 to 1:15, and is obtained by emulsification at a processing pressure of 50 MPa or more, In the calorimetric measurement, the emulsion composition is composed of an emulsion composition having no endothermic peak at room temperature or higher, and (B) an emulsified composition for allowing the solid amphiphile to penetrate into the skin at 25 ° C. by applying to the skin.   The component (A) is selected from polyoxyethylene alkyl ethers having an alkyl group having 10 to 24 carbon atoms, alkyl sulfate esters, higher fatty acid amide sulfonates and long-chain N-acyl glutamates. Or the emulsion composition of 2. Component (B) is a saturated fatty acid having 12 to 24 carbon atoms, a saturated aliphatic alcohol having 12 to 24 carbon atoms, cholesterol, a cholesterol ester having a higher fatty acid residue having 12 to 24 carbon atoms, general formula (1)

(Wherein R ¹ represents a hydrocarbon group having 12 to 32 carbon atoms, R ² represents a hydrocarbon group having 10 to 26 carbon atoms, X is a single bond, —CH (OR ³ ) —, —CH═ CH— or —OCH ₂ — is represented (R ³ represents a hydrogen atom or —COCH (OH) —R ¹ , and n represents 0 or 1).
Ceramides represented by the general formula (2)

(In the formula, R ⁴ represents a hydrocarbon group having 10 to 26 carbon atoms, R ⁵ represents a hydrocarbon group having 9 to 25 carbon atoms, and Y represents — (CH ₂ ) _m — (m represents 2 to 6 carbon atoms). Indicates an integer)
Synthetic ceramides, sphingosines represented by the general formula (3)

(In the formula, R ¹¹ represents a hydrocarbon group having 4 to 40 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ are each a hydrogen atom or a carbon atom 1 optionally substituted by a hydroxyl group. To 10 hydrocarbon groups)
The emulsified composition according to any one of claims 1 to 3, which is selected from amine compounds represented by the formula (1) or acid addition salts thereof.   The emulsified composition according to any one of claims 1 to 4, wherein the component (C) is selected from hydrocarbon oil and silicone oil.

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