KR100350608B1 - Composition of hair-care products containing thermo-sensitive cationic liposome - Google Patents

Abstract

The present invention relates to a method for producing a heat sensitive cationic liposome and a hair care composition containing the liposome.

In order to achieve the above object, the present invention provides a method for preparing a cationic liposome for a hair care composition comprising the step of dispersing a hair setting polymer and a cationic long chain alkyl hydrocarbon in water to prepare a suspension. A hair care composition is provided comprising a shampoo, rinse, hair spray, hair mousse, hair gel, hair cream, or hair tonic comprising a cationic liposome.

The cationic liposomes prepared by the method of the present invention have excellent phase stability at a certain temperature and have an even particle size distribution, and the hair care composition containing the prepared liposomes has a long chain alkyl when heat is applied by using a hair dryer or curling iron. It is a hair product in which a hydrocarbon is melted and a hair setting polymer in it flows out to the hair and has an effect on styling formation.

Description

Hair care composition containing heat-sensitive cationic liposomes TECHNICAL FIELD

[Industrial use]

The present invention relates to a method for producing a thermally sensitive cationic liposome and to a hair care composition containing the liposome, in particular a cationic liposome is prepared by coating a hair setting polymer with a long chain alkyl hydrocarbon, and the prepared liposome is applied to the hair care product. Method of producing a cationic liposome for hair care composition which contains long chain alkyl hydrocarbon and melts the hair setting polymer in the hair and applies it to styling by applying heat using hair dryer or iron when applied after application. One hair care composition relates.

[Prior art]

For busy modern people, how to style hair easily and quickly has been a major concern for hair products since ancient times. U.S. Patent No. 5,391,368 and European Patent No. 437,114 A1 said that the hair setting polymer used in hair mousse or spray can be applied directly to shampoo and rinse to help hair style after hair washing. The disadvantage of making hair setting polymers sticky or stiff when wet is virtually difficult to apply directly to shampoos or rinses.

Complementing this, U.S. Patent No. 5,656,280 discloses a method for preparing a hair setting polymer into a multiple emulsion using volatile silicone oil or hydrocarbon, or nonvolatile silicone oil and hydrocarbon, surfactant, which is generally a multiple emulsion Silver is difficult to manufacture and difficult to produce on an industrial scale as well as unstable in long-term storage stability. In addition, since the multiple emulsion is not cationic and nonionic, there is a disadvantage that the emulsion does not remain much when rinsed with water after application to the hair. In addition, the particle size of the multiple emulsions is not prepared with uniform particle sizes of 5 to 1000 μm or 10 to 500 μm.

US Patent No. 5,874,105 discloses a method for preparing liposomes with long chain alkylammonium fatty acid salts and commercialized under the trade name Catate. However, this patent discloses a technique for forming liposomes with long chain alkyl ammonium fatty acid salts, but there are products using silicone, panthenol, sunscreen, etc. as core materials, but heat sensitive styling such as liposome formulations containing hair setting polymers. The composition has not been disclosed.

In view of the above problems, the present invention uses liposome vesicles coated with a material capable of dissolving the hair setting polymer to heat and applies the vesicle to the hair article in order not to apply the setting polymer directly to the hair. The purpose of the present invention is to provide a hair care composition that can be used to help styling by applying a heat to a hair dryer or curling iron to produce a hair style without affecting the hair.

Another object of the present invention is to find a relationship between the particle size of the cationic liposomes and the amount of hair adsorption, and to provide a method for producing a cationic liposome for a hair care composition having excellent phase stability and uniform particle size distribution at a predetermined temperature during liposome preparation. To provide.

1 is a schematic view showing a liposome having a double-worm structure of Example 1.

FIG. 2 illustrates a hydrophilic group and a hydrophobic group forming the double layer structure of FIG. 1.

Reference numeral 1 is a hydrophilic group, and 2 is a hydrophobic group.

[Means for solving the problem]

The present invention to achieve the above object,

A method of preparing a cationic liposome for a hair care composition comprising dispersing a hair setting polymer and a cationic long chain alkyl hydrocarbon in water to prepare a suspension.

The particle size of the liposome is preferably 0.1 to 3 μm, more preferably 0.1 to 1 μm.

In the above production method, it is possible to further include the step of circulating the suspension prepared by dispersing the hair setting polymer and the cationic long chain alkyl hydrocarbon in water in a microfludizer in a temperature range of 40 to 70 ℃. Do.

The present invention provides a hair care composition of a shampoo, rinse, hair spray, hair mousse, hair gel, hair cream, or hair tonic comprising a cationic liposome prepared by the above production method.

[Action]

Hereinafter, the present invention will be described in detail.

The present invention is applied to the cationic liposomes shampoo, rinse, hair spray, hair mousse, hair gel, hair cream, hair tonic type of hair products, and then using a hot air balloon such as a hair dryer or curling agent, that is, cationic Applying heat above the melting point of the long chain alkyl hydrocarbons causes cationic long chain alkyl hydrocarbons to melt away by heat, and the hair setting polymers surrounded by the cationic long chain alkyl hydrocarbons are eluted to the hair to provide a hair care composition. To provide.

In the present invention, the focus was on finding a suitable material for coating the hair setting polymer, but the formed liposomes were applied to the hair products, so that the phase stability was maintained even when stored for a long time, and the material which acted as a disadvantage in feeling was excluded.

In addition, a device capable of heating the hair, that is, having a melting point in a temperature range of 60 to 200 ° C., which is an application temperature for hair styling of a hair dryer or a curling iron, has become an important requirement of the material search.

The materials having the above requirements were largely divided into three types.

That is, waxes, solid oils, long chain hydrocarbons, and the like are the specific examples of each.

Waxes include biswax, paraffin wax, carnauba wax, jujuba wax, shellac wax, and silicone wax. Solid oils include tribehenin (triester of glycerin / behenic acid). It can be divided into nonionic and cationic.

Nonionic hydrocarbons are saturated or unsaturated hydrocarbons having 12 to 24 carbon atoms, and cationic long chain hydrocarbons are N _n , N _n -dimethyl-1, n-diaminoalkyl (hereinafter referred to as fatty acids having 10 to 32 carbon atoms) The acyl N _n , N _n -dimethyl-1, n-diaminoalkyl (hereinafter referred to as ADDA) prepared by reacting with the primary amino group of the DDA) chain and the fatty acid having 10 to 32 carbons in the same molar number Cationic long chain alkyl fatty acid ammonium salt represented by the following formula (3) having a salt bridge (hereinafter referred to as A-ADDA), behenintrimethylammonium chloride, distearyldimonium chloride, cetyltrimethylammonium chloride, and dipalmitoyl Phosphatidichlorine etc. are mentioned.

NH ₂ (CH ₂ ) _n N (CH ₃ ) ₂

(Wherein n is an integer of 2 to 10)

(Wherein n 'is an integer of 8 to 30, n is an integer of 2 to 10)

(Wherein m and n 'are integers of 8 to 30, n is integer of 2 to 10)

As a result of experimenting with these materials, except for cationic long chain hydrocarbons, there is a disadvantage in that a separate emulsifier is required to coat or emulsify the hair setting polymer, and in terms of usability, the hair becomes sticky or stiff. The choice of cationic long-chain hydrocarbons, which are both comfortable to use and can be spontaneously coated in the preparation of liposomes.

And beheninetrimethylammonium chloride, distearyldimonium chloride, cetyltrimethylchloride and dipalmitoylphosphatidylchlorine in cationic long-chain hydrocarbons have a high cationic charge, so there is no problem in forming liposome formulations, but like shampoos. Anionic surfactants, such as sodium lauryl sulfate, sodium lauroyl ether sulfate, ammonium lauryl sulfate, ammonium lauroyl, which are one of the shampoo components when applied to hair products to which relatively high anionic surfactant is applied There was a problem in the phase stability of the shampoo product due to the complexes such as ether sulfate.

However, other hair products, such as rinses, hair sprays, hair mousses, hair gels, hair creams, hair tonics, etc., containing relatively less anionic surfactants, showed relatively good phase stability.

Thus, all of the above mentioned coating materials can be used for liposome preparation and can be applied to any one of hair products, ie shampoo, rinse, hair mousse, gel, hair spray. Therefore, it is easy to prepare liposomes, and when the prepared liposomes are applied to hair products, the cationic long chain hydrocarbons are also excellent.

One of the above-mentioned materials, ADDA, is already commercialized as a cationic surfactant and has excellent phase stability when preparing liposomes, n-16 stearylamidopropyldimethylamine and n'20 behenylamidopropyldimethyl. Amine is a representative example.

Stearylamidopropyldimethylamine with n '16 is commercialized under the name' Lexamine S-13 (Inolex) ', and behenylamidopropyldimethylamine with n' 20 is' Incromine BB (Croda) Is named.

In addition, the fatty acids having 10 to 32 carbon atoms may typically include palmitoyl acid having 16 carbon atoms, stearyl acid having 18 carbon atoms, and behenyl acid having 22 carbon atoms.

The hair setting polymer in the liposome can be applied to both hydrophilic and hydrophobic setting polymers and can be cationic, nonionic, amphoteric polymers except anionic. The hair setting polymer used here corresponds to a conventional hair setting polymer.

When the anionic polymer is prepared with liposomes using A-ADDA, an ion-ion complex with the fatty acid salt of A-ADDA is formed so that the polymer is precipitated or dissolved in water rather than liposomes.

When a hydrophilic polymer is applied to liposomes, it is present in a solubilized state in the liposome core portion of the aqueous phase, and when a hydrophobic polymer is applied, it is present in a bi-layer acylalkyl group.

Examples of hydrophilic polymers include vinylpinolidon-vinylacetate copolymers, vinylpinolidon polymers, dimethyldiallylammonium chloride-acrylamide copolymers, and, in the case of hydrophobic polymers, vinylacetate-butylmaleate-iso. A carbonyl acrylate copolymer, a methacroyl ethyl betaine- methacrylate copolymer, a vinyl caprolactam- vinylpinolidon- dimethylamino ethyl methacrylate, etc. are mentioned.

The present invention is not limited to only the setting polymers mentioned above.

The present invention has found that the particle size of the cationic liposomes prepared with the above-mentioned materials is increased to the maximum in the range of 0.1 to 1.0 μm, and the microfluidizer at 40 to 70 ° C. during liposome preparation It can be seen that the cationic liposomes having an excellent phase stability and an even particle size distribution can be prepared by applying.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the examples are only for illustrating the present invention and not for limiting the present invention.

EXAMPLE

Examples 1-8

(Production of Cationic Liposomes)

In the present invention, cationic long-chain hydrocarbons, i.e. cationic fatty acid ammonium salt (A-ADDA) and behenintrimethylammonium chloride, distearyldimonium chloride, cetyl trimethylammonium chloride, dipalmitoylphosphatidichlorine are all cationic liposomes. An example in which cationic liposomes are prepared using a cationic fatty acid ammonium salt (A-ADDA) as a coating material which can be prepared but applicable to the most representative shampoos of hair products is described.

When the cationic fatty acid ammonium salt (A-ADDA) is dispersed in water, liposomes having superior phase stability in the quaternized form can be prepared at ionic strengths of 5 to 10 and pH of 1 mol or less of sodium chloride. The quaternary amine group, which is a hydrophilic group in A-ADDA, can be hydrogenated at a hydrogen ion concentration of 10 or less and become a quaternized amine.A fatty acid such as behenyl acid is dehydrogenated at a hydrogen ion concentration of 5 or higher because its hydrogen equilibrium constant (pKa) This is because it can be a negatively charged carboxyl group. Among the A-ADDAs formed in this way, the hydrophilic fatty acid salt forms a salt bridge, and when dispersed in water, the molecular structure is oriented toward water, and the acyl alkyl group, which is a hydrophobic group, is oriented in the opposite direction due to the dislike of water. Form liposomes with a bi-layer.

Representative examples of A-ADDA are as follows. PalmitoylN ₁ -palmitoylamido-N _2, N ₂ -dimethylpropyl-1,3-diamine (hereinafter referred to as P-PDDP) represented by formula (4) wherein m and n 'are 14, and m and n' are 14 Stearyl N ₁ -stearoylamido-N ₂ , N ₂ -dimethylpropyl-1,3-diamine (hereinafter referred to as S-SDDP) represented by 5 and behenyl N ₁ represented by Formula 6 wherein m and n 'are 20 -Behenamido-N ₂ , N ₂ -dimethylpropyl-1,3-diamine (hereinafter B-BDDP) and the like.

Since their melting point is in the range of 60 to 200 ° C. during measurement, heat may be melted when heated with a hair dryer or curling iron. Also, as mentioned above, A-ADDA is cationic, so it can remain a lot when used in rinse-off products such as shampoo or rinse. Has an advantage.

When preparing cationic liposomes, A-ADDA and hair setting polymers are first dispersed by heating and stirring in a phosphate buffer solution (20 mM phosphate buffer solution with 140 mM sodium chloride, pH = 7.2) to a temperature of 70 ° C. The suspension is circulated five times in a microfluidizer (manufactured by Newton Co., Ltd.) at room temperature, at 45 ° C and 70 ° C, and at a pressure of 10,000 psi, thereby obtaining a liposome of white turbidity.

In Examples 1 to 8, liposomes were prepared according to each component, its content, and liposome preparation conditions, and the particle size of the initial liposomes was measured by a particle size analyzer (mastersizer, manufactured by Malvern Instrument), and the particles of liposomes by an optical microscope The state was observed. The rate of change according to Equation 1 was calculated by measuring the size of liposomes under severe conditions (storage at 50 ° C. for 1 month). The results are shown in Table 1.

The proportion of each component was calculated as the weight ratio to the total content.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Vinylpinolidone-dimethylaminoethyl methacrylate 2 2 2 2 2 10 11 - Butenedionic acid-monobutyl methacrylate - - - - - - - 2 B-BDDP 18 18 18 - - 10 11 18 S-SDDP - - - 18 - - - - P-PDDP - - - - 18 - - - Application temperature (℃) when applying microfluidizer 25 45 70 45 45 45 45 45 Initial particle size (㎛) 0.8 0.1 0.5 1.0 1.5 2.5 3.0 × Particle size distribution (%) +60 +20 +23 +30 +70 +90 +200 × % Change 30 10 15 40 50 30 × ×

In the table above,

As the vinylpinolidon-dimethylaminoethyl methacrylate, polyquaternium 11 (Gapgat 755 N manufactured by ISP) was used.

Butenedioic acid-monobutyl methacrylate was used Gantzrez A-425 (manufactured by National starch),

× indicates that liposomes are not formed or phase stability is very unstable.

As shown in Table 1, the liposome of Example 2, which has a heating temperature of 45 ° C. when the solution of the setting polymer and A-ADDA dissolved in the microfluidizer, is the smallest in particle size. It was also found that the particle size distribution was uniform. It is believed that this result was obtained because the association with the setting polymer was easy because the fluidity of A-ADDA was increased in the temperature range of 40 to 70 ° C.

And it can be applied at a temperature of 70 ℃ or more, but it is excluded because there are some risk factors in the process of the microfluidizer. In addition, as the alkyl length of A-ADDA increases, the interaction rate of the acylalkyl group increases, and thus the particle size change rate decreases, and thus the phase stability is excellent. And when using B-BDDP, it was found that the reformed cotton was formed until the ratio of B-BDDP to the hair setting polymer vinylpynolidone-dimethylaminoethyl methacrylate was 1: 1.

Butenedionic acid-monobutyl methacrylate, an anionic setting polymer, did not form a liposome due to the formation of a salt bridge due to complex formation with a hydrophilic group of fatty acid salt of A-ADDA.

Hair adsorption capacity of the liposomes prepared as in Table 1 was evaluated and the results are shown in Table 2. Evaluation of hair adsorption capacity of the cationic liposome was carried out in the following manner.

(Evaluation of adsorption of liposomes on hair)

The woolen cloth was cut to a size of 4 cm x 4 cm, soaked in 300 g of a 10% solution of the product, and stirred for 5 minutes. Rinse twice with 300 ml of ion-exchanged water for 1 minute. This rinsed wool is immersed and stirred in 300 g of 0.5% by weight dye solution (Red 80) for 5 minutes. This dyed wool rinse was repeatedly rinsed twice in 300 ml of ion-exchanged water for 1 minute. The rinsed wool was naturally dried and the color difference (ΔE) was measured using a colorimeter to evaluate the degree of adsorption of liposomes.

Adsorption evaluation results for the hair of liposomes prepared in Table 1 division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 ΔE 55 70 69 52 40 35 30

As shown in Table 2, Example 1 to Example 4 having an initial particle size of 0.1 to 1.0 μm showed the best adsorption degree. The smaller the particle size to the appropriate particle size of the liposome, the smaller the surface area of the liposome. This increases the probability of contact with the hair, and the hair with an isoelectric pH of 3.5 to 4.5 is anionic at higher hydrogen ion concentrations. It is believed that the amount adsorbed on the carbon dioxide is high.

Examples 9-12, Comparative Example 1

In Examples 9 to 12 and Comparative Example 1, liposomes of Example 2, which were relatively superior in phase stability and showed uniform and fine particle sizes, were applied to the shampoos by content, and the results are shown in Table 3.

Example of a shampoo to which the liposome of Example 2 is applied division Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Sodium Laureth Sulfate 40 40 40 40 40 Cocamido Profile Betaine 5 5 5 5 5 Decyl glucoside 5 5 5 5 5 Silicone oil One One One One One antiseptic 0.05 0.05 0.05 0.05 0.05 Sitrick Mountain 0.1 0.1 0.1 0.1 0.1 Liposomes of Example 2 0.5 1.0 5.0 10.0 0 water Remainder Remainder Remainder Remainder Remainder

In the above table, silicone oil was used as silicone oil emulsion (Dow Corning, 2-1691 emulsion).

The long-term storage stability of the liposomes of Example 2 applied to the shampoo was measured according to the following equation 1 after measuring the initial particle size of the liposomes as described in Table 1, and then storing them in an oven at 50 ° C. for one month. The change rate was measured and the results are shown in Table 4.

Where

I is the particle size (μm) of the liposome measured after one month storage at 50 ℃,

I ₀ is the particle size (μm) of the liposome measured initially.

Phase Stability of Liposomes Applied to Shampoos division Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Initial particle size (㎛) 0.8 0.8 0.8 0.8 - % Change 9 10 12 13 -

Even under severe conditions (storage for one month at 50 ℃), the particle size increased to about 10%, showing stable dispersion.

(Sensory evaluation on hair feel and hair setting force)

The shampoo compositions of Examples 9-12 and Comparative Example 1 were applied to 10 women for evaluation.

When the experienced hair evaluator wound the hair with each shampoo composition, dried the hair dryer, and produced the hair style, the hair texture and the force felt in the hair were evaluated on a five-point scale as follows.

The evaluation results were evaluated with a 90 percent reliability. The results are shown in Table 5.

Sensory evaluation result division Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Feeling dry hair 3.0 3.4 3.6 4.0 3.0 Feeling power on dry hair 3.0 3.5 4.0 4.5 3.0

In the table above,

Feel on dry hair is 1: not smooth at all; 2: not very smooth; 3: normal; 4: smooth; 5: scored very smooth,

Feel on dry hair 1: No strength at all; 2: I don't feel much power; 3: normal; 4: I feel strength; 5: expressed as a score of very powerful.

As shown in Table 5, as the application content of the liposome of Example 2 was increased, it was found that the texture and strength of the dry hair were excellent. As a result, when the hair was dried with a hair dryer, B-BDDP was melted by heat, and it was found that vinylpinolidon-dimethylaminoethyl methacrylate, a hair setting polymer, was eluted to the hair.

The cationic liposomes prepared by the method of the present invention have excellent phase stability at a certain temperature and have an even particle size distribution, and the hair care composition containing the prepared liposomes has a long chain alkyl when heat is applied by using a hair dryer or curling iron. It is a hair product in which a hydrocarbon is melted and a hair setting polymer in it flows out to the hair and has an effect on styling formation.

Claims (8)

(correction) a) hair setting polymer with core material; And b) Cationic long chain alkyl hydrocarbons as coating material A heat-sensitive hair care composition in which the hair setting polymer flows out and functions by heat including a cationic liposome containing. (correction) The method of claim 1, The cationic long chain alkyl hydrocarbon of b) is cationic long chain alkyl fatty acid ammonium salt (A-ADDA), behenintrimethylammonium chloride, distearyldimonium chloride, cetyltrimethylammonium chloride, and dipalmi represented by the following Chemical Formula 3 A heat sensitive hair care composition in which the hair setting polymer is leaked and acted upon by heat selected from the group consisting of toilphosphatidylchlorine: [Formula 3] Where m and n 'are integers from 8 to 30 n is an integer from 2 to 10. (correction) The method of claim 1, A heat-sensitive hair care composition in which the hair setting polymer is released by the heat of the liposome having a particle size of 0.1 to 3 μm. The method of claim 3, wherein A heat sensitive hair product composition in which the hair setting polymer flows out by a heat having a particle size of 0.1 to 1 μm of the liposome. (delete) (correction) The method of claim 2, Cationic long-chain alkyl fatty acid salt (A-ADDA) represented by the formula (3) is a primary of the Nn, Nn-dimethyl-1, n-diaminoalkyl (DDA) chain to represent a fatty acid of 10 to 32 carbon By reacting with an amino group to prepare acyl Nn, Nn-dimethyl-1, n-diaminoalkyl (ADDA) represented by the following formula (2), and the prepared acyl Nn, Nn-dimethyl-1, n-diaminoalkyl (ADDA) A heat-sensitive hair care composition prepared by reacting with a molar number, such as fatty acids of 10 to 32 carbons, and having a melting point of 60 to 200 ° C. in which the hair setting polymer flows out. [Formula 1] NH ₂ (CH ₂ ) _n N (CH ₃ ) ₂ Where n is an integer from 2 to 10; [Formula 2] Where n 'is 8-30, n is 2-10. (delete) (correction) The method of claim 1, A heat sensitive hair product composition in which the hair setting polymer is released by heat, wherein the heat sensitive hair product composition is a shampoo, rinse, hair spray, hair mousse, hair gel, hair cream, or hair tonic.