JP5663320B2 - Method for producing vesicle composition - Google Patents

Description

  The present invention relates to a method for producing a vesicle composition.

  In recent years, the use of perms, hair colors, bleaches, and the like has become common, but hair damage due to these chemical treatments has also become a problem. Conventionally, hair cosmetics such as rinses, conditioners and treatments have been used to improve the feel of hair after shampooing, but further performance improvements are desired from the viewpoint of reducing hair damage. Yes.

  Patent Documents 1 and 2 describe hair that can repair or inhibit damage or fatigue damage of hair caused by chemical treatment, dryer drying, and daily hair care behavior, and can impart good flexibility and a supple feel from wet to dry. Cosmetics are disclosed. The hair cosmetic described in Patent Document 1 contains a specific branched fatty acid or a salt thereof, a specific amidoamine or a salt thereof, and silicones, and optionally an amphiphilic amide lipid, and the hair described in Patent Document 2 The cosmetic contains a specific branched fatty acid or a salt thereof, a specific aromatic alcohol, and a specific amidoamine or a salt thereof. As a result, it is described that this hair cosmetic can repair or suppress hair damage and fatigue destruction, and can impart good flexibility and a supple feel from wet to dry.

  Patent Document 3 discloses a hair treatment composition comprising a multilayer vesicle dispersion stabilized with cholesterol, a basic amino acid, a fatty acid and a nonionic active agent for the purpose of repairing and preventing hair damage, and a multilayer vesicle. Hair treatment compositions such as shampoos and conditioners containing the dispersion are disclosed. This treatment composition is described as specifically promoting the penetration of some hair active substances into hair fibers.

On the other hand, a phase inversion emulsification method and a liquid crystal emulsification method are known as one of methods for producing an emulsified composition. The phase inversion emulsification method is a method of emulsifying while adding an aqueous phase to an oil phase. The liquid crystal emulsification method is a method of emulsifying while adding an aqueous phase to the liquid crystal phase. For example, in Non-Patent Document 1, emulsification is performed while adding an aqueous phase to the oil phase, and a fine emulsion having an average particle size of 1 μm or less is formed by utilizing the fact that the oil-water interface tension is remarkably reduced near the phase inversion point. Yes.
Further, for example, Patent Document 4 discloses a method for producing an oil-in-water emulsion containing a quaternary ammonium salt, which has good fragrance long-lasting and diffusibility and good stability over time.

JP 2008-297262 A JP 2007-176924 A JP 2002-516831 A JP 2008-094980 A

Optimization of Nano-emulsion Preparation by Low-Energy Methods in an Ionic Surfactant System, Langmuir 2006,22,8326-8332

  However, the techniques described in Patent Documents 1 and 2 may not be sufficiently effective with respect to the feeling of familiarity when applying hair cosmetics or the smoothness at the time of excessive application, and the content of further active ingredients There is also a need for optimization of formulation. Moreover, the conventional method is implemented about the manufacturing method.

  In the technique described in Patent Document 3, multi-layer vesicles are formed by mixing cholesterol as an essential component. That is, a vesicle structure is formed by the presence of specific lipids such as sterols. However, sterols, which are not components of ordinary treatment agents, are essential, and no mention is made of any change or modification of hair surface properties.

  Furthermore, phase inversion emulsification as described in Non-Patent Document 1 and Patent Document 4 is generally performed for stabilization of the emulsion, but no mention is made of forming a vesicle structure. Moreover, it is not disclosed about the change of the surface property of hair and modification | reformation by making the vesicle with the large volume obtained and applying this.

  The present inventors have found that vesicles can be constituted in water by using a specific organic acid in combination with a specific tertiary amine and a specific branched fatty acid. Moreover, when the hair cosmetics using the said vesicle composition were content of the branched fatty acid comparable as the past, it discovered that the effect more than the conventional hair cosmetics was exhibited.

Furthermore, the present inventors, hair cosmetics using a composition in which vesicles occupy a large volume in this way, a feeling of familiarity at the time of application, smoothness at the time of rinsing, smoothness at the time of application, good finger, It has been found that the unity during drying is maintained or improved.
Such vesicle compositions are specifically formed from components (A), (B), (C) and water, and vesicle compositions having sufficient vesicle volume concentration are specific tertiary amines and specific vesicle compositions. The present invention was completed by finding that it can be produced by adding an aqueous phase to an oil phase containing a branched fatty acid and a specific organic acid while mixing and having a sufficient vesicle volume concentration.

That is, according to the vesicle composition of the present invention, the vesicle composition in which the continuous phase formed from the components (A), (B), (C) and water is an aqueous phase, and the component in the vesicle composition The total of (A), (B) and (C) is 1 to 20% by mass, and the vesicle composition contains vesicles at least 5 times by volume with respect to the volume of the component (A) in the vesicle composition. object:
(A) Branched fatty acid represented by the general formula (1)

(Wherein R ¹ represents a methyl group or an ethyl group, and n represents an integer of 5 to 36);
(B) At least one tertiary amine selected from the group represented by formula (2) or (3)

(Wherein R ¹¹ represents an aliphatic hydrocarbon having 12 to 24 carbon atoms, and R ¹² independently represents H or an alkyl group having 1 to 4 carbon atoms),

(In the formula, R ²³ represents an aliphatic hydrocarbon group having 11 to ²³ carbon atoms, R ²⁴ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a number of 2 to 4). And (C) an organic acid having 1 to 8 carbon atoms,
Is provided.

  According to the vesicle composition of the present invention, when the content of the branched fatty acid is the same as that of the hair cosmetic used in the conventional “washing form”, the application realized by the conventional hair cosmetic You can dramatically improve the familiarity of time and the smoothness of rinsing.

  Further, even when used as a hair cosmetic used in a “non-washing form”, it is possible to maintain or improve the smoothness at the time of application, the goodness of fingering, and the unity at the time of drying.

In the vesicle composition of the present invention, the continuous phase formed from the following components (A), (B), (C) and water is an aqueous phase. Hereinafter, each component will be specifically described.
(A) Branched fatty acid (B) Tertiary amine (C) Organic acid having 1 to 8 carbon atoms

First, the component (A) will be described.
The component (A) used in the present invention is a branched fatty acid represented by the general formula (1).

(In the formula, R ¹ represents a methyl group or an ethyl group, and n represents an integer of 5 to 36.)
Among such branched fatty acids, n is preferably 5 to 35 (total carbon number of branched fatty acid 9 to 40), more preferably 6 to 35 (total carbon number of branched fatty acid 10 to 40), particularly 6 to 19 (branched). The total carbon number of fatty acids is 10-24).

  Specifically, 18-methyleicosanoic acid, 18-methylnonadecanoic acid, 14-methylpentadecanoic acid, 14-methylhexadecanoic acid, 15-methylhexadecanoic acid, 15-methylheptadecanoic acid, 16-methylheptadecanoic acid, 16 -Methyloctadecanoic acid, 17-methyloctadecanoic acid, 17-methylnonadecanoic acid.

  The branched fatty acid of component (A) can also be separated and extracted from hair or the like according to the description of LIPIDS, vol.23, No.9, 878-881 (1988), WO 98/30532 pamphlet, for example. However, it can also be synthesized according to the description in JP-A-4-173719.

  Examples of the extract include an extract from lanolin, that is, a lanolin fatty acid and a salt thereof. Commercially available lanolin fatty acids contain about 50% by mass of methyl branched long chain fatty acids called isofatty acids and anteisofatty acids. Specific examples include 18-MEA (manufactured by Croda Japan Co., Ltd.), Scrairo (manufactured by Croda Japan Co., Ltd.), and FA-NH (manufactured by Nippon Seika Co., Ltd.).

  Two or more kinds of the branched fatty acid of component (A) may be used in combination. Moreover, you may use combining a synthetic product and an extract. The content of the component (A) in the vesicle composition is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. Moreover, 15 mass% or less is preferable and 10 mass% or less is more preferable.

  The component (B) used in the present invention is a tertiary amine represented by the general formula (2) or (3).

^{(Wherein, R 11} is the number 12 to 24 aliphatic hydrocarbon atoms, preferably aliphatic hydrocarbons 14-24 carbon atoms, more preferably represents an aliphatic hydrocarbon 18-24 carbon ^{atoms, R 12} Are each independently H or an alkyl group having 1 to 4 carbon atoms, preferably H or an alkyl group having 1 to 3 carbon atoms.)
Specific examples include N, N-dimethyltetradecylamine, N, N-dimethylhexadecylamine, N, N-dimethylbehenylamine, and N, N-dimethyl-n-octadecylamine.

^{(Wherein, R 23} is an aliphatic hydrocarbon group having 11 to 23 carbon atoms, preferably an aliphatic hydrocarbon of 13-23 carbon atoms, more preferably represents an aliphatic hydrocarbon 17-23 carbon ^{atoms, R 24} Are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents a number of 2 to 4).
Specific examples include N- (3- (dimethylamino) propyl) docosanamide and N- (3- (dimethylamino) propyl) stearamide.

  Two or more types of tertiary amines as component (B) may be used in combination.

Component (C) used in the present invention is an organic acid having 1 to 8 carbon atoms.
Specifically, monocarboxylic acids such as acetic acid, propionic acid and caprylic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid and fumaric acid; glycolic acid, lactic acid, hydroxyacrylic acid and glycerin Hydroxycarboxylic acids such as acid, malic acid, tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid, salicylic acid and phthalic acid; acidic amino acids such as glutamic acid and aspartic acid. Of these, hydroxycarboxylic acids and acidic amino acids are preferred. As the hydroxycarboxylic acid, glycolic acid, citric acid, lactic acid, and malic acid are more preferable, and glycolic acid, lactic acid, and malic acid are particularly preferable. As the acidic amino acid, glutamic acid is particularly preferable.

  The hair cosmetic composition of the present invention contains water. As the water, purified water is preferably used. The content of water is not particularly limited, and can be appropriately adjusted according to the purpose of use.

A vesicle composition in which a vesicle is formed by component (A), component (B), component (C) and water, and in particular, a multilayer lamella vesicle (so-called onion vesicle) composed of several double membranes is dispersed in water. Easy to form. In addition, the vesicle generally refers to a vesicle having an inner layer that is hollow or an aqueous phase, but the multilayer lamella vesicle formed here includes those having a structure in which part or all of the inner layer is an oil phase. In the present application, “vesicles” include multilayer lamella vesicles.
The multilayer lamella vesicle and the lamellar lamella are different, and the lamellar lamella in this specification is a so-called plate-like lamellar structure in which the bimolecular film has a plate shape without a curvature, The lamella vesicle and the lamellar lamella can be discriminated by a cross image (Maltes Cross) observed when crossed Nicols are used under a polarizing microscope.

  From the viewpoint of increasing the vesicle volume concentration in the vesicle dispersion, the molar ratio (A) / (C) of the component (A) to the component (C) is 5/5 or more, preferably 7/3 or more. And 9/1 or less, preferably 8/2 or less.

  In addition, from the viewpoint of efficiently contributing component (A), component (B), and component (C) to vesicle formation, the acid equivalent of all fatty acids including component (A) and component (C) in the vesicle composition The ratio of the base equivalent of component (B) is preferably 0.25 or more, more preferably 0.5 or more, and particularly preferably 0.6 or more. And 4 or less is preferable, 2 or less is more preferable, More preferably, it is 1.8 or less.

  Furthermore, from the viewpoint of storage stability and handling properties of the vesicle dispersion, the total of the component (A), the component (B) and the component (C) in the vesicle dispersion is 1 to 20% by mass, preferably 1 ˜15 mass%.

The volume of the vesicles produced in the vesicle dispersion is relative to the volume of the component (A) in the vesicle composition from the viewpoint of familiarity at the time of application of the hair cosmetic containing vesicles and improvement of smoothness at the time of rinsing. 5 volume times or more, preferably 6 volume times or more, more preferably 8 volume times or more.
The preferred vesicle dispersion is preferably 20 to 95% by volume, more preferably 30 to 95% by volume, particularly preferably 30 to 80% by volume. . This is because, within this range, the storage stability of the vesicle dispersion, the handling and familiarity, and the smoothness during rinsing are most excellent.

The vesicle composition of the present invention preferably takes the form of a vesicle dispersion (premix). This vesicle dispersion has the following steps:
(I) a step of dissolving the oil phase containing the component (A), the component (B), and the component (C) at a temperature equal to or higher than the melting point of the oil phase;
(Ii) a step of mixing while adding an aqueous phase to the obtained oil phase;
Can be suitably manufactured. According to such a procedure, a vesicle composition in which the continuous phase is an aqueous phase is obtained.

In step (i), the oil phase is preferably completely dissolved from the viewpoint of stable production. Here, “completely dissolved” refers to a state in which the oil phase is dissolved to a state where there is no solid matter. For this reason, it is preferable to melt | dissolve at the temperature more than melting | fusing point of an oil phase, and also melt | dissolve at the temperature higher 5 degreeC or more than the melting | fusing point of an oil phase, and it is preferable to melt | dissolve especially 10 degreeC or more higher than the melting point of an oil phase.
The oil phase is preferably in a uniformly mixed state. Therefore, in this step, it is preferable to dissolve the oil phase while mixing. The mixing method is not particularly limited, but it is preferable to mix by, for example, stirring.

  In step (ii), the temperature at the time of dropping the aqueous phase can be appropriately determined by the oil phase temperature, the temperature of the dropped water phase, and heating or cooling in a mixing device. Here, purified water such as ion-exchanged water or distilled water is used for the “aqueous phase”, but it is also possible to contain a polyhydric alcohol which is a component (D) dissolved in water, such as glycerin or dipropylene glycol. it can. Further, from the viewpoint of efficiently producing vesicles, it is preferable that the oil phase temperature and the temperature of the water phase to be dropped be equal to or higher than the gel transition temperature of the vesicle to be formed.

The volume concentration of vesicles in the vesicle dispersion can be adjusted by the dropping speed of the aqueous phase to the oil phase and the stirring speed when dropping the aqueous phase, and the particle size of the vesicle can be adjusted by the stirring speed (shearing speed) after the start of dropping of the aqueous phase. It is. The optimum value of the dropping speed of the aqueous phase to the oil phase and the stirring speed at the time of dropping varies depending on the formulation of the vesicle composition, the component ratio, the size and shape of the mixing tank, but the viscosity rises most during the dropping of the aqueous phase. Conditions that allow uniform mixing in the state are preferred. As the aqueous phase is further dropped, the viscosity of the vesicle dispersion decreases and the vesicle volume concentration decreases. The amount of the aqueous phase to be dropped can be appropriately adjusted in consideration of the storage stability and handling properties of the vesicle dispersion.
Although the dropping speed of the water phase to the oil phase can be appropriately selected as described above, it is desirable to drop over 10 minutes or more for the purpose of increasing the volume concentration of the vesicle in the vesicle dispersion. Although the dropping speed is not particularly limited, for example, when the total amount of the water phase to be dropped is 600 g, it is preferably dropped at 5 to 20 g / min.

In addition, from the viewpoint of the stability of the vesicle composition, it is a method for producing a vesicle composition comprising a step of (iii) cooling to the temperature of the vesicle immediately after the completion of dropping of the aqueous phase after step (ii). Is preferred.

The vesicle volume concentration in the vesicle composition is set across the aperture when the vesicle composition is dispersed in the electrolyte solution and the vesicle floating in the electrolyte solution passes through a region defined by pores called apertures. By measuring the change in electrical resistance or voltage or current between the two electrodes, the exact volume of the vesicle passing through the aperture can be determined. The particle size distribution can be measured using a particle size distribution measuring apparatus having such a principle, for example, Multisizer ^™ 4 manufactured by Beckman Coulter, Inc. or CDA-1000X manufactured by Sysmex Corporation.

  In addition, the average particle diameter when the vesicle is spherical is 2 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and 20 μm or less, preferably 18 μm from the viewpoint of further improving the feeling of familiarity when applying hair. Hereinafter, it is more preferably 15 μm or less. Here, the average particle size is a particle size distribution measuring device used in the measurement of the vesicle volume concentration, for example, MultisizerTM4 manufactured by Beckman Coulter, Inc. or CDA-1000X manufactured by Sysmex Corporation, or a laser diffraction particle size distribution measuring device, For example, using SALD2100 manufactured by Shimadzu Corporation or LA-920 manufactured by Horiba, Ltd., the intensity distribution of the scattered light obtained by irradiating the vesicle moving in the flow cell in the circulation system with laser light is measured, The average particle diameter can be measured by the volume distribution obtained by converting from the intensity distribution. The measurement is desirably performed at room temperature (15 to 30 ° C.).

The vesicle composition of the present invention may further contain (D) a polyhydric alcohol.
Specific examples of the component (D) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and glycerin.

  The content of the component (D) is preferably 0.5 to 60% by mass and more preferably 1 to 50% by mass with respect to the entire vesicle composition from the viewpoint of storage stability of the vesicle composition.

  In the addition of the component (D), after the oil phase containing the component (A), the component (B), and the component (C) is dissolved at a temperature equal to or higher than the melting point of the oil phase in the step (i). The component (D) can be added to the oil phase. Alternatively, in the stage (i), the oil phase containing the component (A), the component (B), the component (C), and the component (D) is dissolved at a temperature equal to or higher than the melting point of the oil phase until there is no solid matter An oil phase that has been allowed to flow may be obtained. After the step (i), a vesicle dispersion having a high vesicle volume concentration and high storage stability can be obtained by passing through the step (ii) of mixing while adding an aqueous phase to the obtained oil phase. . Further, from the viewpoint of storage stability of the vesicle, it is preferable to pass through the step (iii) of quickly cooling the vesicle to the phase transition temperature or lower after the completion of dropping of the aqueous phase.

Moreover, an arbitrary component can be put in the oil phase in the range which does not inhibit manufacture of the vesicle of this invention. Examples of the optional component include various extracts and antioxidants, but are not limited thereto. The optional component that can be added to the oil phase is 1% by mass or less of the oil phase from the viewpoint of producing a stable vesicle composition.
Arbitrary components can be added to the aqueous phase as long as the production of the vesicle of the present invention is not inhibited. Examples of optional components that can be added include various extracts and preservatives, but are not limited thereto. The optional component that can be added to the aqueous phase is 0.1% by mass or less of the aqueous phase from the viewpoint of producing a stable vesicle composition.

  In addition, in the prescription including the component A) component B) component C) of the present application, the higher alcohol is 1/10 or less of the total mass of the oil phase from the viewpoint of increasing the volume ratio of vesicles contained in the composition. It is more preferable that it is substantially not contained in the vesicle composition, and it is particularly preferred that it is not contained in the vesicle composition.

  When producing a vesicle composition, an aqueous phase is dropped into an oil phase in a shear mixed state. The mixing apparatus is not particularly limited as long as shear mixing can be performed. However, when the viscosity becomes high during the addition of the aqueous phase, an apparatus capable of mixing a high-viscosity product, for example, ADI homomixer manufactured by Primemix Co., Ltd. K. A combination mix, a vacuum emulsification stirrer manufactured by Mizuho Industry Co., Ltd., a Max blend stirrer manufactured by Sumitomo Heavy Industries, Ltd., a supermix stirrer manufactured by Satake Chemical Machinery Co., Ltd., and the like are preferable. Although it does not specifically limit about stirring speed, For example, if it is a 300 ml mixing tank, it is preferable to stir at 100-600 rpm.

Although there is no confirmation, in the vesicle obtained by such a production method of the present invention, the structure on the hair surface can be suitably changed by easily changing the structure from the vesicle to a film shape when applied to the hair. It is considered possible.
Moreover, the conventional vesicle structure is comprised by interposing specific lipids, such as sterols and phospholipids, as described in Patent Document 3. In contrast, the present invention can form a vesicle composition without containing sterols or phospholipids. That is, it can be said that the vesicle structure can be constituted by components conventionally used in hair cosmetics such as rinses and conditioners. Accordingly, the present invention provides a novel pharmaceutical formulation in the art.

The hair cosmetic composition of the present invention contains one or more surfactants and an aliphatic alcohol, and further contains the vesicle composition described above.
When the content of the vesicle composition in the hair cosmetic is given as a feeling of familiarity at the time of application and smoothness at the time of rinsing, when viewed as the amount of the branched fatty acid that is the component (A) constituting the vesicle, The amount is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass. Such hair cosmetics maintain the flexibility, smoothness, moist feeling, and suppleness achieved by conventional hair cosmetics even if the content of the active ingredient is reduced as compared with conventional hair cosmetics. Can be improved.
Examples of such hair cosmetics include conditioners, rinses, treatments, and shampoos. Conditioners, rinses and treatments are preferred as particularly effective hair cosmetics. These hair cosmetics may be used after washing hair cosmetic or after use.

  A hair cosmetic containing the vesicle composition can be obtained by separately mixing the vesicle composition of the present invention into a hair cosmetic base prepared by a usual method. The hair cosmetic base prepared by an ordinary method refers to a general hair cosmetic containing, for example, a surfactant and an aliphatic alcohol, and blending silicone, oily components and the like as necessary. This can be adjusted in any way.

  Cationic surfactants used as a hair cosmetic base include quaternary ammonium and tertiary amine compounds, with tertiary amine compounds being particularly preferred. The tertiary amine compound is selected from the compounds listed in Component (C). In particular, it is preferable to use the same component as the tertiary amine compound used in the vesicle composition.

  The aliphatic alcohol used as the hair cosmetic base is preferably an aliphatic alcohol having 12 to 26 carbon atoms. Thereby, the hair at the time of application to hair can be made smooth. An aliphatic alcohol having a linear or branched alkyl group or alkenyl group is preferable, and an aliphatic alcohol having a linear or branched alkyl group or alkenyl group having 16 to 22 carbon atoms is particularly preferable. In particular, aliphatic alcohols having a linear or branched alkyl group or alkenyl group having 16 to 18 carbon atoms are more preferred. Specifically, cetyl alcohol and stearyl alcohol are preferable.

The hair cosmetic base formulation and production method are not particularly limited. For example, it can be obtained by adding and emulsifying an oil phase containing a cationic surfactant and a higher alcohol to a heated and stirred aqueous phase.
The method for blending the present vesicle composition into a normal hair cosmetic base is not particularly limited, but it is desirable to blend at a temperature not higher than the gel transition temperature of the vesicle from the viewpoint of vesicle stability. As a result, a hair cosmetic that maintains the structure of the vesicle composition can be obtained.

Example 1
18.50 g of 18-MEA (fatty acid and branched fatty acid mixture containing 18-methyleicosanoic acid, average molecular weight: 364.3, melting point 35 to 55 ° C., manufactured by Croda Japan Co., Ltd.), Musashino lactic acid 90 (lactic acid, purity 90%) , Molecular weight: 90.08, melting point 18 ° C., 0.72 g, manufactured by Musashino Chemical Laboratory, Pharmin DM 8098 (N, N-dimethyl-n-octadecylamine, purity 98%, molecular weight 297.56, melting point 23 ° C. , Kao Co., Ltd.) 10.92 g and DPG-RF (dipropylene glycol, melting point −40 ° C., ADEKA Co., Ltd.) 31.50 g are placed in a 300 ml beaker and heated to 80 ° C. with stirring to dissolve the raw materials. did. In this oil phase, 246.36 g of ion-exchanged water heated to 80 ° C. as an aqueous phase was dropped at a constant rate over 10 minutes and emulsified at 80 ° C. Then, it cooled to 30 degrees C or less using a 5 degreeC refrigerant | coolant. The vesicle composition thus obtained was used as a premix. The volume of 18-MEA in this premix is 3.5% by volume when the specific gravity of 18-MEA is calculated as 1 g / cm ³ . The emulsification method in which the aqueous phase is dropped while stirring the oil phase is generally referred to as phase inversion emulsification. It was 53.8 degreeC when the gel transition temperature of this vesicle composition was measured with the differential scanning calorimeter (DSC). The gel transition temperature was measured using a SETARAM INSTRUMENTATION μDSC7 evo from 5 ° C. to 90 ° C. at a heating rate of 0.5 ° C./min. Table 1 shows the premix production conditions and the amount (g) of each component converted to 10.00 g of the premix.

  Here, the rinse was blended using the premix which is the prepared vesicle composition. The rinses prepared in Examples 1 to 14 and Comparative Examples 1 to 6 are hair cosmetics used in the form of washing away.

  In a 500 ml beaker, 301.40 g of ion-exchanged water and 2.36 g of Musashino lactic acid 90 are added as an aqueous phase, and heated to 55 ° C. with stirring with a propeller. Thereafter, an oil phase consisting of 9.29 g of Farmin DM E-80, 21.00 g of calcoal 8098 (stearyl alcohol, purity 98%, manufactured by Kao Corporation), and 5.95 g of DPG-RF (same as above) was averaged at 80 ° C. After dissolution, it was added to the aqueous phase and emulsified by stirring. After cooling to 30 ° C. or lower using a 5 ° C. refrigerant to prepare a base rinse, the aforementioned premix (10,000 g) was added to form a rinse.

(Comparative Example 1)
18.50 g of 18-MEA (fatty acid and branched fatty acid mixture containing 18-methyleicosanoic acid, average molecular weight: 364.3, melting point 35 to 55 ° C., manufactured by Croda Japan Co., Ltd.), Farmin DM 8098 (N, N-dimethyl) -N-octadecylamine, purity 98%, molecular weight 297.56, melting point 23 ° C., Kao Corporation) 10.92 g, and DPG-RF (dipropylene glycol, melting point −40 ° C., ADEKA Corporation) 31.50 g Was placed in a 300 ml beaker and heated to 80 ° C. with stirring with a propeller to completely dissolve the raw material. In this oil phase, 247.08 g of ion-exchanged water heated to 80 ° C. as an aqueous phase was dropped at a constant rate over 10 minutes and emulsified at 80 ° C. Then, it cooled to 30 degrees C or less using a 5 degreeC refrigerant | coolant, and obtained the premix.

(Comparative Example 2)
18.50 g of 18-MEA (fatty acid and branched fatty acid mixture containing 18-methyleicosanoic acid, average molecular weight: 364.3, melting point 35 to 55 ° C., manufactured by Croda Japan Co., Ltd.), Musashino lactic acid 90 (lactic acid, purity 90%) , Molecular weight: 90.08, melting point 18 ° C., Musashino Chemical Laboratory Co., Ltd. 0.72 g, and DPG-RF (dipropylene glycol, melting point −40 ° C., ADEKA Co., Ltd.) 31.50 g in a 300 ml beaker The mixture was heated to 80 ° C. with stirring with a propeller to completely dissolve the raw materials. In this oil phase, 257.28 g of ion-exchanged water heated to 80 ° C. as an aqueous phase was dropped at a constant rate over 10 minutes and emulsified at 80 ° C. It cooled to 30 degrees C or less using a 5 degreeC refrigerant | coolant, and obtained the premix.

(Comparative Example 3)
18.50 g of 18-MEA (fatty acid mixture containing 18-methyleicosanoic acid and branched fatty acid, average molecular weight: 364.3, melting point 35-55 ° C., manufactured by Croda Japan Co., Ltd.), Cotamine 86W (trimethylstearyl ammonium chloride, purity) 28%, molecular weight: 348.05, melting point −5 ° C., manufactured by Kao Corporation) 35.79 g, and DPG-RF (dipropylene glycol, melting point −40 ° C., manufactured by ADEKA Corporation) 31.50 g in a 300 ml beaker The mixture was heated to 80 ° C. with stirring with a propeller to completely dissolve the raw materials. In this oil phase, 222.21 g of ion-exchanged water heated to 80 ° C. as an aqueous phase was dropped at a constant rate over 10 minutes and emulsified at 80 ° C. Then, it cooled to 30 degrees C or less using a 5 degreeC refrigerant | coolant, and obtained the premix. Then, the rinse was adjusted by the same method as Example 1.

(Example 2)
Farmin DM8098 (0.36 g) in 10.00 g of the premix described in Example 1 was added to Farmin DM4098 (N, N-dimethyltetradecylamine, purity 97%, molecular weight 241.46, manufactured by Kao Corporation) 0.30 g The premix and rinse were adjusted in the same manner as in Example 1 except that the ion exchange water was 8.28 g.

Example 3
Pharmin DM8098 (0.36 g) in 10.00 g of the premix described in Example 1 was added to Farmin DM2285 (N, N-dimethylbehenylamine, purity 85%, molecular weight 269.51, melting point 44 ° C., manufactured by Kao Corporation). The premix and rinse were adjusted in the same manner as in Example 1 except that the amount was 0.38 g and the ion-exchanged water was 8.20 g.

Example 4
Farmin DM8098 (0.36 g) in 10.00 g of the premix described in Example 1 was added to AMIDET APA-22 (N- [3- (dimethylamino) propyl] docosanamide, purity 99%, molecular weight 424.75, melting point 76 The premix and rinse were adjusted in the same manner as in Example 1 except that 0.51 g and the ion-exchanged water was 8.07 g.

(Example 5)
Example 1 except that 0.02 g of lactic acid in 10.00 g of the premix described in Example 1 was 0.03 g of benzoic acid (Sigma Aldrich Japan Co., Ltd. first grade reagent) and ion-exchanged water was 8.21 g. The premix and rinse were adjusted in the same way.

(Example 6)
Example 2 except that 0.02 g of lactic acid in 10.00 g of the premix described in Example 1 was 0.04 g of caprylic acid (Wako Pure Chemical Industries, Ltd.) and ion-exchanged water was 8.20 g. The premix and rinse were adjusted as in 1.

(Comparative Example 4)
Except that 0.02 g of lactic acid in 10.00 g of the premix described in Example 1 was 0.04 g of capric acid (Wako Pure Chemical Industries, Ltd. reagent) and ion-exchanged water was 8.20 g. The premix and rinse were adjusted as in 1.

(Example 7)
0.001 g of DPG-RF and 9.27 g of ion exchange water in 10.00 g of the premix described in Example 1, 16.45 g of DPG-RF at the time of base rinse adjustment, and 290.90 g of ion exchange water Except that, premix and rinse were adjusted in the same manner as in Example 1.

(Example 8)
The premix and rinse were the same as in Example 1 except that Pharmin DM8098 (0.36 g) in the premix 10.00 g described in Example 1 was 0.09 g and ion-exchanged water was 8.49 g. It was adjusted.

Example 9
The premix and rinse were the same as in Example 1 except that Pharmin DM8098 (0.36 g) in the premix 10.00 g described in Example 1 was 0.18 g and ion-exchanged water was 8.40 g. It was adjusted.

(Example 10)
Premix and rinse in the same manner as in Example 1 except that Pharmin DM8098 (0.36 g) in Premix 10.00 g described in Example 1 was 0.73 g and ion-exchanged water was 7.85 g. It was adjusted.

(Example 11)
Premix and rinse in the same manner as in Example 1 except that Farmin DM8098 (0.36 g) in 10.00 g of the premix described in Example 1 is 1.46 g and ion-exchanged water is 7.12 g. It was adjusted.

(Example 12)
Example 1 except that 0.02 g of lactic acid in 10.00 g of the premix described in Example 1 was 0.10 g, Farmin DM8098 (0.36 g) was 0.57 g, and ion-exchanged water was 7.93 g. The premix and rinse were adjusted as in 1.

(Comparative Example 5)
In a 500 ml beaker, 309.62 g of ion-exchanged water and 2.38 g of Musashino lactic acid 90 are added as an aqueous phase and heated to 55 ° C. with stirring with a propeller. To this was added an oil phase consisting of 0.35 g of 18-MEA, 9.65 g of Farmin DM E-80, 7.00 g of DPG-RF, 21.00 g of Calcoal 8098 previously dissolved uniformly at 80 ° C. The mixture was emulsified by stirring at 300 rpm for 10 minutes. Thereafter, it was cooled to 30 ° C. or lower using a 5 ° C. refrigerant to form a rinse.

(Comparative Example 6)
Rinse was prepared in the same manner as Comparative Example 5 except that ion-exchanged water was 308.22 g and benzyl alcohol (purity 99.9%, manufactured by Sun Chemical Co., Ltd.) 1.40 g was added to the oil phase. .

(Comparative Example 7)
Into a 300 ml beaker, 246.36 g of ion-exchanged water was added as an aqueous phase and heated to 80 ° C. with stirring with a propeller. Moreover, 10.50 g of 18-MEA (fatty acid and branched fatty acid mixture containing 18-methyleicosanoic acid, average molecular weight: 364.3, melting point 35 to 55 ° C., manufactured by Claude Japan Co., Ltd.), Musashino lactic acid 90 (lactic acid, purity) 90%, molecular weight: 90.08, melting point 18 ° C., Musashino Chemical Laboratory Co., Ltd. 0.72 g, Farmin DM 8098 (N, N-dimethyl-n-octadecylamine, purity 98%, molecular weight 297.56, melting point 23.degree. C., Kao Co., Ltd.) 10.92 g and DPG-RF (dipropylene glycol, melting point-40.degree. C., ADEKA Co., Ltd.) 31.50 g were put in a beaker and completely dissolved in an 80.degree. C. water bath with stirring. To obtain an oil phase. This oil phase was added dropwise to the aqueous phase in a 300 ml beaker at a constant speed over 10 minutes with stirring, and emulsified at 80 ° C. Then, it cooled to 30 degrees C or less using a 5 degreeC refrigerant | coolant. The vesicle composition thus obtained was used as a premix. The emulsification method in which the oil phase is dropped while stirring the aqueous phase is generally referred to as normal phase emulsification.

  Subsequently, in order to evaluate the premix in the same manner as in Example 1, a rinse was blended. In a 500 ml beaker, 301.40 g of ion-exchanged water and 2.36 g of Musashino lactic acid 90 are added as an aqueous phase, and heated to 55 ° C. with stirring with a propeller. Thereafter, an oil phase consisting of 9.29 g of Farmin DM E-80, 21.00 g of calcoal 8098 (stearyl alcohol, purity 98%, manufactured by Kao Corporation), and 5.95 g of DPG-RF (same as above) was averaged at 80 ° C. After dissolution, it was added to the aqueous phase and emulsified by stirring at 300 rpm for 10 minutes. After cooling to 30 ° C. or lower using a 5 ° C. refrigerant to prepare a base rinse, 10.00 g of the aforementioned premix was added to form a rinse.

(Comparative Example 8)
The premix and rinse were adjusted by the method described in Example 1 except that the temperature in the 300 ml beaker was 45 ° C. and the oil phase components were dissolved, and the temperature of the ion exchange water to be dropped was 45 ° C.

(Example 13)
18-MEA (fatty acid and branched fatty acid mixture containing 18-methyleicosanoic acid, average molecular weight: 364.3, melting point 35 to 55 ° C., manufactured by Claude Japan Co., Ltd.) 28.00 g, Musashino lactic acid 90 (lactic acid, purity 90% , Molecular weight: 90.08, Melting point: 18 ° C., 1.92 g, manufactured by Musashino Chemical Laboratory Co., Ltd., Farmin DM 8098 (N, N-dimethyl-n-octadecylamine, purity: 98%, molecular weight: 297.56, melting point: 23 ° C. 29.12 g made by Kao Corporation) and 84.00 g DPG-RF (dipropylene glycol, melting point −40 ° C., made by ADEKA Co., Ltd.) are put in an emulsifying apparatus (TK Aji homomixer, made by Primix Co., Ltd.). Then, warm water is introduced into the jacket so that the temperature in the tank becomes 80 ° C, and the raw material is completely dissolved by stirring with a paddle blade (80 rpm). It was. In this oil phase, 656.96 g of ion-exchanged water heated to 80 ° C. as an aqueous phase was dropped at a constant rate over 60 minutes and emulsified at 80 ° C. Then, it cooled to 30 degrees C or less with a 5 degreeC refrigerant | coolant, and obtained the premix. Table 1 shows the amount (g) of each component converted to 10.00 g of the premix.

  Subsequently, in order to evaluate the premix in the same manner as in Example 1, a rinse was blended. In a 500 ml beaker, 301.40 g of ion-exchanged water and 2.36 g of Musashino lactic acid 90 are added as an aqueous phase, and heated to 55 ° C. with stirring with a propeller. Thereafter, an oil phase consisting of 9.29 g of Farmin DM E-80, 21.00 g of calcoal 8098 (stearyl alcohol, purity 98%, manufactured by Kao Corporation), and 5.95 g of DPG-RF (same as above) was averaged at 80 ° C. After dissolution, it was added to the aqueous phase and emulsified by stirring at 300 rpm for 10 minutes. After cooling to 30 ° C. or lower using a 5 ° C. refrigerant to prepare a base rinse, 10.00 g of the aforementioned premix was added to form a rinse.

(Example 14)
A premix and a rinse were prepared in the same manner as in Example 1 except that the premix described in Example 13 was sheared by homomixer at 7000 rpm for 30 minutes to control the particle size.

(Premix evaluation method)
(1) The emulsified state of the premix was evaluated one day after the premix adjustment was completed. When the oil phase and the aqueous phase are separated at the time of evaluation and two phases are formed, the emulsified state is “bad”, and when the oil phase and the water phase are not separated, one phase is formed, the emulsified state Was evaluated as “good”.
(2) The average particle diameter and volume concentration of the vesicles in the premix were measured at 25 ° C. using Multisizer ^™ 4 manufactured by Beckman Locolter Co., Ltd. The average particle diameter was the volume-based median diameter (D50), and the volume concentration was the vesicle volume per unit volume of the premix.
(3) The viscosity of the premix was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 30 ° C., rotor No. 2 and evaluated at 30 rpm.
The stability of the premix was evaluated by the change in viscosity before and after storage at room temperature for 1 month.

(Rinse evaluation method)
The hair of a Japanese woman that has been treated once with straight perm and twice with bleach is treated as damaged hair, and each 20 g (length 15-20 cm, average diameter 80 μm) of hair bundle is obtained using 2 g of standard shampoo with the following composition. Apply 2g of the rinse shown in Table 1 to the washed hair bundle, and after thoroughly acclimating the entire hair, rinse it under running water of about 40 ° C for about 30 seconds, then towel dry and dry thoroughly with a dryer. I let you.

・ Standard shampoo formulation (pH 7.0)
25% polyoxyethylene (2.5) lauryl ether sulfate sodium salt 62.0%
Lauric acid diethanolamide 2.3%
Edetate disodium 0.15%
Sodium benzoate 0.5%
Sodium chloride 0.8%
75% phosphoric acid appropriate amount Fragrance, methylparaben appropriate amount Purified water remaining

  The hair was evaluated for “familiar feeling during application” and “smoothness during rinsing”. The evaluation was performed by 5 people on a 5-level scale, and the average value was taken. If the average score was 3 points or more, it was regarded as a passing product.

(Evaluation criteria)
5: Excellent feeling at application and smoothness at rinsing 4: Excellent feeling at application and smoothness at rinsing 3: Good feeling at application or smoothness at rinsing 2: Either the familiarity at the time of application or the smoothness at the time of rinsing is inferior 1: Both the familiarity at the time of application and the smoothness at the time of rinsing are inferior

Claims (12)

A vesicle composition in which vesicles formed from components (A), (B), (C) and water are dispersed in water ,
The vesicle composition is produced by mixing an oil phase containing the components (A), (B), and (C) while adding an aqueous phase,
The content of the higher alcohol in the oil phase is 1/10 or less of the total mass of the oil phase,
The sum of the components (A), (B), and (C) in the vesicle composition is 1 to 20% by mass, and the volume of the component (A) in the vesicle composition is 5 times or more by volume. Vesicle compositions containing vesicles of:
(A) Branched fatty acid represented by the general formula (1)

(Wherein R ¹ represents a methyl group or an ethyl group, and n represents an integer of 5 to 36);
(B) Tertiary amine represented by the general formula (2) or (3)

^{(Wherein, R 11} represents an aliphatic hydrocarbon ^{C12-24, R 12} represent each independently an alkyl group having a carbon number of 1-4.)

^{(Wherein, R 23} represents an aliphatic hydrocarbon group having 11 to 23 carbon ^{atoms, R 24} are the same or different and each represents an alkyl group having a carbon number of 1 to 4, n is a number of 2-4. And component (C) an organic acid having 1 to 8 carbon atoms. The vesicle composition according to claim 1, wherein the vesicle has a spherical shape and an average particle diameter of 2 to 20 µm.   The vesicle composition according to claim 1 or 2, further comprising (D) a polyhydric alcohol. To claim 1 any one ratio of base equivalents is 0.25-4 component of the vesicle composition (A) and component (C) those acid of the total fatty acids amount and components comprising (B) The vesicle composition described.   A hair cosmetic comprising one or more surfactants, an aliphatic alcohol, and emulsified silicone particles, and obtained by adding the vesicle composition according to any one of claims 1 to 4. Component (A) Branched fatty acid represented by general formula (1)

(Wherein R ¹ represents a methyl group or an ethyl group, and n represents an integer of 5 to 36);
(B) Tertiary amine represented by the general formula (2) or (3)

^{(Wherein, R 11} represents an aliphatic hydrocarbon ^{C12-24, R 12} represent each independently an alkyl group having a carbon number of 1-4.)

^{(Wherein, R 23} represents an aliphatic hydrocarbon group having 11 to 23 carbon ^{atoms, R 24} are the same or different and each represents an alkyl group having a carbon number of 1 to 4, n is a number of 2-4. And (C) a step of dissolving an oil phase containing an organic acid having 1 to 8 carbon atoms at a temperature equal to or higher than the melting point of the oil phase, and a step of mixing the dissolved oil phase while adding an aqueous phase. See
A vesicle formed from the components (A), (B), (C) and water, and having a higher alcohol content in the oil phase of 1/10 or less of the total mass of the oil phase and dispersed in water. A method for producing a vesicle composition, wherein the composition is formed at least 5 times the volume of the component (A) in the vesicle composition. The method for producing a vesicle composition according to claim 6, wherein the oil phase further comprises (D) a polyhydric alcohol. The vesicle composition according to claim 6 or 7, wherein the ratio of the acid equivalent of all fatty acids including the components (A) and (C) in the vesicle composition to the base equivalent of the component (B) is 0.25-4. Manufacturing method.   The vesicle composition manufactured with the manufacturing method as described in any one of Claims 6-8. The components of the vesicle composition (A), (B) and the sum of (C) is Ru 1-20% by mass, the vesicle compositions produced by the method described in any one of claims 6-8 . The vesicle composition manufactured by the method according to any one of claims 6 to 8, wherein an average particle diameter when the vesicle is spherical is 2 to 20 µm.   Hair makeup obtained by adding a vesicle composition containing one or more surfactants, aliphatic alcohols and emulsified silicone particles and produced by the method according to any one of claims 6-8. Fee.