KR20040077207A - Sampoo composition containing polymeric nanostructure - Google Patents

Abstract

PURPOSE: A shampoo composition containing polymeric nanostructure is provided to increase absorption of useful components of the composition into the hair, and improve adhesive property of the composition to the hair by stimulating the formation of coacervate phase. CONSTITUTION: The shampoo composition contains 0.1 to 10.0 wt.% of polymeric nanostructure; 0.01 to 5 wt.% of cationic polymer; 1 to 50 wt.% of anionic surfactant; and 10 wt.% or less of bipolar surfactant or zwitter ionic surfactant, wherein the polymeric nanostructure is prepared by preparing a hydrophilic block using both polyethylene imine and polyethylene oxide and preparing a hydrophobic block using poly(ε-caprolactone); the particle size of the polymeric nanostructure is 50 to 300 nm; the anionic surfactant is selected from ammonium lauryl sulfate, ammonium laureth sulfate, sodium lauryl sulfate and sodium laureth; the bipolar surfactant is selected from lauroamphoacetate, lauroamphodiacetate, cocoamphoacetate and cocoamphodiacetate; and the zwitter ionic surfactant is betaine surfactant.

Description

Shampoo composition containing polymeric nanostructure

The present invention relates to a shampoo composition containing a polymer nanostructure, and more particularly to a nanostructure, anionic surfactants, amphoteric surfactants or tsu containing hair nutrients to improve the hair adsorption, penetration performance of the hair nutrients A shampoo composition containing a bitter ionic surfactant and at least one cationic polymer.

Shampoo is a hair cosmetic that is used to decontaminate the scalp and hair and keep the hair clean and beautiful.In addition to the purpose of cleaning, shampoo is easy to comb, softness, smoothness, shine and deterioration of the surface of the hair, antistatic, It is used for additional purposes such as hair protection. With the recent increase in the population of hair and scalp damaged by frequent perming, dyeing, hair dry, ultraviolet rays, etc., it is expected to provide effective ingredients to damaged hair to restore damaged hair, and to expect the effect on shampoo. Is increasing. Compositions of these shampoos are generally mixed with conditioning agents such as silicones, hydrocarbon oils, fatty esters or mixtures thereof and include anionic detergent surfactants.

However, many conditioning shampoos do not provide sufficient deposition on the hair during shampooing. Detergent surfactants are designed to remove oil and dirt on the hair and scalp and therefore may interfere with the deposition of the conditioning components and may leave the deposited conditioning agent during cleaning. The large amount of conditioning agent which prevented this from being deposited would be rinsed during shampooing, thereby reducing the hair conditioning performance.

Therefore, the present invention is to provide a shampoo composition to provide improved hair deposition of the active ingredient of the hair as well as the cleaning power of the original function of the shampoo, and to have an improved conditioning function when used at the same concentration.

The present inventors use the amphiphilic polymer nanostructure having a core-shell form as a hair active ingredient in the shampoo composition, whereby the polymer nanostructure is safely present in the colloidal form in the shampoo composition, and contains the hair nutrients therein. As a result of studying various materials to have excellent hair adsorption ability, polymers using poly (ε-caprolactone), a biodegradable and biocompatible polymer, as hydrophobic blocks while simultaneously using polyethyleneimine and polyethylene oxide as hydrophilic blocks It has been found that nanostructures can contain a variety of hair nutrients very effectively, and found that these nanostructures can supply hair nutrients more efficiently when adsorbed to hair.

In addition, the present inventors have improved the hair conditioning performance, especially in wet hair during rinsing by giving a cationic polymer, such as a cellulosic or guar polymer modified with a cationic substituent to improve the hair adhesion of such polymer nanostructures, anion The present invention has been found to be particularly effective in improving the deposition of nanostructures on hair when used in combination with a sexual surfactant component. However, such cationic polymers, when used at high concentrations or at relatively high cationic charge densities, can cause compatibility problems with other materials in the formulation, create undesirable greasy hair feel, and can cause hair to feel dirty when dried. Therefore, proper mixing ratio with detergent was required.

Accordingly, it is an object of the present invention to provide a shampoo composition containing amphiphilic polymer nanostructures that can contain various hair nutrients and are excellent in hair adsorption performance.

Another object of the present invention is a shampoo composition containing a cationic adhesive polymer, which contains an anionic surfactant and an amphoteric surfactant in the shampoo composition at the same time so as to advantageously form a coacervate phase, so that the nanoparticles on the hair surface during shampoo application or rinsing To improve the adhesion of the structure to provide a conditioning shampoo composition with improved ability to supply nutrients to the hair.

1 is a graph showing the particle size distribution of polymer nanostructures containing tocopherol acetate.

Figure 2 is a graph showing the hair adsorption amount of tocopherol acetate.

3 is a result of measuring the tensile strength of the hair (A: Comparative Example 1, B: Example 1, C: Example 2, D: Example 3).

The present invention relates to a shampoo composition containing a polymer nanostructure, and more particularly to a nanostructure, anionic surfactants, amphoteric surfactants or tsu containing hair nutrients to improve the hair adsorption, penetration performance of the hair nutrients A shampoo composition is provided that contains a bitter ionic surfactant and at least one cationic polymer.

Shampoo compositions according to the invention comprise 0.1 to 10.0% by weight of polymeric nanostructures, 0.01 to 5% by weight of cationic polymers, 1 to 50% by weight of anionic surfactants and less than 10% by weight of amphoteric surfactants, based on the total weight of the composition. Or Zwitterionic surfactants.

In addition, the shampoo composition provided in the present invention can be used by adding the appropriate components according to the kind as well as the essential elements and limitations of the invention described herein, for example, foaming agent, cleaning agent, conditioning agent, pH adjusting agent, pearling agent , Preservatives, flavors, viscosity modifiers and the like.

Amphiphilic polymer nanostructures containing the active ingredient according to the present invention is preferably 0.01 to 20.0% by weight, preferably 0.1 to 10.0% by weight, based on the total weight of the shampoo composition.

The nanostructures used in the present invention are copolymers having a hydrophilic group containing polyethyleneimine, a cationic polymer, and a polyethylene oxide, a nonionic, hydrophilic polymer, as a hydrophobic block. .

It is common for the nanostructure to collect a physiologically active ingredient, and the particle size thereof is preferably 50 to 300 nm.

The organic solvent used in the preparation of the polymer nanostructure in the aqueous solution using the copolymer of the present invention is acetone, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, ethyl acetate, One or more selected from acetonitrile, methyl ethyl ketone, methylene chloride, chloroform, methanol, ethanol, ethyl ether, diethyl ether, hexane, and petroleum ether can be used.

Poly (ε-caprolactone) used in the present invention is a polymer having a linear structure having a chemical formula of-(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ COO) n- (where n is a positive integer), biodegradable and Widely used as a biocompatible polymer, it is a hydrophobic polymer that is insoluble in water. The molecular weight suitable for forming the polymer nanostructures depends on the structure and molecular weight of the hydrophilic polymer bound to poly (ε-caprolactone), and is preferably 1,000 to 100,000 Da.

Polyethyleneimine used in the present invention is a polymer having a chemical formula of-(CH ₂ CH ₂ NH) n-(where n is a positive integer), and linear and branched polymers However, the polymer assembly can be formed regardless of its structure, and the molecular weight of polyethyleneimine is determined depending on the molecular weight of the biodegradable poly (ε-caprolactone). It is preferable to use.

The polyethylene oxide used in the present invention is a polymer having a chemical formula of-(CH ₂ CH ₂ O) n-, where n is a positive integer, and is water-soluble and nonionic. Due to its excellent biocompatibility, it has been widely used as a medical polymer. In the present invention, it was used for the purpose of further improving the phase stability of the polymer vesicle. Since the range which can be used also depends on the molecular weight of a biodegradable poly ((epsilon) -caprolactone), it is preferable to use the thing of 5,000 Da or less generally.

There is no particular limitation as to the physiologically active ingredient which can be collected and used within the nanostructures provided by the present invention, except that it should be a soluble component that can be solubilized in a polymer, and the type of physiologically active ingredient to be trapped inside the nanoparticles and The content can be used to be adjusted depending on the purpose and case. Bioactive active ingredients that can be used in the present invention include rhubarb, genesistine, hesperidin, hesperidin, catechin, isoflavone, danazol, haloperidol, furosemid, isosorbide dinitrate (isosorbide dinitrate), chloramfenicol, sulfamethoxazole, caffeine, cimethidine, sodium diclofenac Na, coenzyme Q10, vitamin E and its derivatives, vitamin A and its Derivatives thereof, provitamin D3 and derivatives thereof, ursolic acid, oleanolic acid, rosmarinic acid, 18 beta-glycyrrhetinic acid, glabridin ), Aleuritic acid, polyphenol, esculin, epigallocatechin gallate [(-) epigallocatechin gallate], turmeric acid, ginsenosides, Tetra high Tetra hydrocurcuminoids, centella asiatica, beta-carotene, asiaticoside, farnesol, beta-sitosterol, linoleic acid ( linoleic acid, gamma linolenic acid, resveratrol, vineatrol, ginkgo biloba, triclosan, minoxidil, natural essential oils, ceramides, sphingosines, etc. Can be mentioned.

Cationic polymers used in the present invention contain cationic nitrogen containing moieties such as quaternary ammonium or amino moieties to which cationic protons have been added. The average molecular weight of the cationic polymer is 10,000,000 to 5000 Da, preferably about 100,000 Da or more and 1,500,000 Da or less. In addition, the cationic charge density of the polymer is generally 0.2-7 meq / gm, more preferably 0.5 meq / gm or more and less than 2 meq / gm in the shampoo composition having a pH of 3-9, preferably pH 4-7.

Examples of cationic polymers used in the present invention include acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates, vinyl caprolactone and vinyl pyrrolidone, and the like. Water soluble spacing monomers; And copolymers of vinyl monomers having amines or quaternary ammonium functional groups to which cationic protons are added. Cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and cationic cellulose derivatives can also be used.

In order to provide bubbles and cleaning functions in the present invention, a cleaning surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof is preferably used. It can mix and use 1 or more types, or can mix and use 1 or more types of anionic and zwitterionic surfactant. At this time, the amphoteric surfactant and the zwitterionic surfactant have a bonding group that is anionic at the pH of the composition.

The anionic surfactant used in the present invention may be used alone or in combination of two or more kinds of ammonium lauryl sulfate, ammonium laureth sulfate, sodium lauryl sulfate and sodium laureth sulfate, the content is based on the total weight of the total composition It is preferable to use 1 to 25% by weight, preferably 5 to 20% by weight.

The amphoteric surfactant used in the present invention is preferably selected from the group consisting of coco ampoacetate, coco ampodiacetate, lauro ampoacetate, lauro ampo diacetate and mixtures thereof, and the content thereof. It is preferable to use less than 10% by weight of the total amount of silver in the total composition.

Zwitter ionic surfactants used in the present invention are aliphatic radicals are linear or branched, wherein one of the aliphatic substituents is about 8 to 18 carbon atoms, one is an anionic water-soluble group, for example, carboxy, sulfonate, Surfactants widely disclosed as derivatives of aliphatic quaternary ammonium, phosphonium, sulfonium compounds containing phosphates or phosphonates. In this invention, it is preferable to use cocamidopophile betaine.

As the conditioning agent used in the present invention, dimethicone base, hydrogenated polydecene, cationic polymer, etc. may be used alone or in combination of two or more thereof, and the content thereof is 0.1 to 10% by weight, preferably based on the total weight of the composition. It is preferable to use 0.5 to 5% by weight.

Examples of the pH adjuster used in the present invention include sodium phosphate, disodium phosphate, citric acid, sodium citrate and the like.

Examples of the pulping agent used in the present invention include glycol distearate, glycol monostearate, fatty acids, and the like.

A preservative can be used individually or in mixture of 2 or more types of methyl paraoxybenzoate, propyl paraoxybenzoate, sodium benzoate, methylchloroisothiazolinone, and methyl isothiazolinone.

Examples of the viscosity modifier used in the present invention include coamide amide (CME), coamide amide (CDE), sodium chloride, and the like, which are amide based nonionic surfactants.

Hereinafter, the configuration and effect of the shampoo composition according to the present invention will be described in more detail with reference to Examples and Test Examples. However, these examples are intended to illustrate the present invention, it is obvious to those skilled in the art that the scope of the present invention is not limited to these examples.

Reference Example 1 Preparation of Polymer Nanostructure Containing Tocopherol Acetate

As an active ingredient, a macromolecular nanostructure containing tocophenol acetate, a vitamin E derivative, was prepared.

Poly (ε-caprolactone) / polyethyleneimine / polyethylene oxide copolymer was prepared through the condensation reaction after melting each polymer component at a high temperature. 60 g of poly (ε-caprolactone) (supplier: Aldrich, molecular weight 80,000 Da), 10 g of polyethyleneimine (supplier: Aldrich, branched, molecular weight 600 Da), 30 g of aminopropyl polypropylene glycol-block-polyethylene glycol-polypropylene glycol (supplier) : Fluka and molecular weight 1,900 Da) were heated to 100 ° C, melted, and reacted by stirring for 9 hours. Briefly, the reaction process is as follows. First, polyethyleneimine and aminopropyl polypropylene glycol-block-polyethylene glycol-polypropylene glycol were put in a reactor equipped with a stirrer and the temperature was raised to 100 ° C. Subsequently, homogenous stirring was enabled while slowly adding poly (ε-caprolactone) while stirring at a speed of 50-100 rpm. After the reaction, the polymer was injected into a storage container in a molten state and cooled to room temperature to obtain a wax-type solid product. Next, 9 g of the copolymer and 1 g of vitamin E acetate were uniformly dispersed in 50 ml of acetone, and then slowly added and stirred in 90 ml of tertiary distillation containing 50 mM HCl. Thereafter, acetone was removed by evaporation in a chemical hood for 12 hours to prepare a polymer nanostructure.

EXAMPLE

Table 1 puts together the composition ratio of each component of the hair shampoo composition by Examples 1-3 and Comparative Example 1 concerning this invention. The composition ratio of each composition is weight%.

Furtherance Comparative Example 1 Example 1 Example 2 Example 3 Ammonium laureth sulfate 10 10 10 10 Glycol distearate 2.0 2.0 2.0 2.0 Cetyl alcohol 0.6 0.6 0.6 0.6 Cocamide MEA 0.5 0.5 0.5 0.5 Ammonium Lauryl Sulfate 6 6 3 3 Guar hydroxypropyltrimonium chloride - 0.15 0.15 0.15 Polyquaternium-10 0.1 0.15 0.15 0.15 silicon 0.5 0.5 0.5 0.5 Distearyl dimethylammonium chloride 0.2 0.2 1.0 1.0 Sodium coco ampoacetate - - 4.0 4.0 Spices 1.0 1.0 1.0 1.0 antiseptic 0.03 0.03 0.03 0.03 Citric acid 1.0 10 1.0 1.0 Tocopherol Acetate 0.2 - 0.2 - Tocopherol acetate nanostructure (contains 10% tocopherol acetate) - 2.0 - 2.0 Dilution water to 100 to 100 to 100 to 100

To prepare a shampoo composition in which the polymer nanostructures containing tocopherol acetate as an active ingredient were mixed, the shampoo was prepared according to a conventional shampoo preparation method using the composition of Table 1 above.

Test Example 1 Particle Size Measurement by Dynamic Light Scattering

25 mg of the copolymer obtained in Reference Example 1 was uniformly dispersed in 0.5 ml of acetone, and then slowly added and stirred in 10 ml of tertiary distillation. Then, acetone was removed by evaporation in the chemical hood for 12 hours, and the average particle diameter was measured using a dynamic light scattering method (Dynamic Light Scattering, DLS, Zetasizer 3000HS, Malvern, UK). At this time, the concentration of the polymer vesicle was measured by fixing at a scattering angle of 0.6 mg / ㎖, temperature 25 ℃, 90 °. The results are shown in FIG.

The particle size of the tocopherol acetate-containing polymer nanostructures according to the present invention showed a rather wide distribution of 50 to 250 nm.

Test Example 2 Measurement of Tocopherol Acetate Hair Adsorption

At the time of hair application, the hair adsorption amount of the shampoo compositions prepared in Examples 1 to 3 and Comparative Example 1 was measured. A tress of 20 cm in length and 2 g was immersed in a 5% sodium lauryl sulfate solution for 5 minutes, rinsed with running water, and left for 24 hours at 25 ° C. and a relative humidity of 50%. Thereafter, the tress was dipped in a 10% solution of the shampoo composition for 5 minutes and rinsed with running water for 30 seconds, and left for 24 hours at 25 ° C. and 40% relative humidity. 2 g of hair samples of each tress prepared in this way were cut out, dispersed in 30 ml of methanol, sonicated for 30 minutes, extracted with vitamin E acetate, filtered through a 0.45 µm syringe filter, and then tressed for 5 minutes. After immersion and rinsing in running water for 30 seconds, it was left for 24 hours at 25 ℃, 40% relative humidity conditions. 2 grams of hair samples of each tress thus prepared were cut out, dispersed in 30 ml of methanol, sonicated for 30 minutes, extracted with vitamin E acetate, filtered through a 0.45 μm syringe filter, and analyzed by HPLC. The measuring instrument used HP 1100 series, Hewlett-Packard, the results are shown in FIG.

As shown in FIG. 2, Comparative Example 3 prepared from 0.2 wt% of the polymer nanostructure containing tocopherol acetate, 0.3 wt% of the cationic polymer, and 4.0 wt% of the coco ampo acetate showed the adsorption amount of tocopherol acetate the most. Even with the same polymeric nanostructures, the samples without 0.1% by weight amphoteric surfactant showed much less adsorption.

It has a much better hair adsorption effect when used in polymer nanostructures than in shampoos, even if the same amount of tocopherol is used in the manufacture of shampoos. It was found that higher polymer content increases hair uptake.

Test Example 3 Measurement of Hair Tensile Strength

The tensile strength of the hair was measured using the polymer nanostructures and the shampoos prepared in Reference Example 1, Examples 1 to 3, and Comparative Example 1. First, normal hair tresses were prepared. 5 g of the shampoos of Examples 1 to 3 and Comparative Example 1 were applied to the hair tresses, and then washed 10 times with constant flowing ionized water. The washed hair tress was left to stand at least 24hr under constant temperature, constant humidity (relative humidity: 40%, temperature: 25 ° C) and dried sufficiently. Hairs with a thickness of 80 ± 10 μm were collected from a fully dried tress. Using Instron (model: 4443), the collected hair was measured for tensile strength and the breaking point of the hair was recorded. Figure 3 shows the breaking point of the average data after experimenting with 8 to 10 hairs.

Referring to FIG. 3, it can be seen that the shampoos containing the tocopherol acetate nanostructures (Examples 1 and 3) have an increased breaking point compared to the shampoos containing the tocopherol acetate (Comparative Examples 1 and 2). Can be. In addition, it can be seen that the shampoo (Examples 2 and 3) in which the amphoteric surfactant and the cationic polymer are mixed is increased in tensile strength than the shampoo (Example 1 and Comparative Example 1) using only the anionic surfactant. As a result, it was confirmed that the nanostructure containing tocopherol acetate contained hair surface adsorption as well as penetrating the hair to increase hair strength. It was also confirmed that the amphoteric surfactant and cationic polymer included in the shampoo formulation confer synergistic effects of promoting the absorption of the nanostructures.

Test Example 4 Results of Use Quality Tests by Composition

Simple Mona, which was used for two weeks in a panel consisting of 50 women aged 20 to 30 for the shampoos prepared in Examples 1 to 3 and Comparative Example 1 and then answered the questionnaire on a 7-point scale The following results were obtained by evaluating the use quality through the simple monadic test.

Survey Item Comparative Example 1 Example 1 Example 2 Example 3 1. Air bubbles are good and air bubbles feel good 5.6 5.7 5.4 5.5 2. Feels good when rinsing and fingers pass well 4.8 3.9 5.0 4.9 3. Combing is easy and soft during semi-drying 5.5 5.6 5.5 5.6 4. Hair care is easy and soft after drying 5.2 5.4 5.2 5.4 5. Moisturizes hair after drying 4.8 5.2 4.9 5.5 6. The gloss of hair is felt after drying 4.0 4.2 4.0 4.5

The shampoo composition prepared by the present invention further enhances absorption of the active ingredient in the hair by containing a certain amount of the polymer nanostructure of 50-200 nm containing the active ingredient in the formulation, and anion of at least one cationic polymer and an amphoteric surfactant. When used in combination with a surfactant, it was found that it promotes and increases the formation of coacetate phase to increase the hair adhesion of the nanostructures, thereby increasing the adhesion amount of the hair active ingredient, thereby nourishing and protecting the hair.

Claims (7)

A shampoo composition comprising a polymer nanostructure in which a bioactive active ingredient is collected, the shampoo composition comprising: 0.1 to 10.0 wt% of a polymer nanostructure based on the total weight of the composition; 0.01-5% by weight of cationic polymer; 1-50% by weight of anionic surfactant; And less than 10% by weight of amphoteric surfactant or zwitterionic surfactant. The shampoo composition according to claim 1, wherein the nanostructures in which the physiologically active ingredients are collected are prepared by using hydrophilic blocks of polyethylenimine and polyethylene oxide at the same time and hydrophobic blocks of poly (ε-caprolactone). The shampoo composition of claim 1, wherein the nanostructure has a particle size of 50 nm to 300 nm. The method of claim 1, wherein the anionic surfactant is selected from the group consisting of ammonium lauryl sulfate, ammonium laureth sulfate, sodium lauryl sulfate, sodium laureth; The amphoteric surfactant is selected from the group consisting of lauro ampoacetate, lauro ampo diacetate, coco ampoacetate, coco ampo diacetate; Zwitter ionic surfactant is a shampoo composition, characterized in that the betaine surfactant. The shampoo composition of claim 1 wherein the cationic polymer is selected from the group consisting of cationic cellulose derivatives and cationic guar gum derivatives. The method of claim 1, wherein the bioactive active material collected in the nanostructures are rhubarb, genesistine, hesperidin, hesperidin, catechin, isoflavone, danazol, haloperidol, furosemid, iso Sorbide dinitrate, chloramfenicol, sulfamethoxazole, caffeine, cimethidine, sodium diclofenac Na, coenzyme Q10, vitamin E and its E Derivatives, vitamin A and its derivatives, provitamin D3 and its derivatives, ursolic acid, oleanolic acid, rosmarinic acid, 18-beta-glycyrrhetinic acid, Glabridin, aleuritic acid, polyphenols, esculin, epigallocatechin gallate [(-) epigallocatechin gallate], turmeric acid, ginseno Ginsenosides Tetra hydrocurcuminoids, centella asiatica, beta-carotene, asiaticoside, farnesol, beta-sitosterol, Linoleic acid, gamma linolenic acid, resveratrol, vineatrol, ginkgo biloba, triclosan, minoxidil, natural essential oils, ceramides, sphs Shampoo composition, characterized in that at least one selected from the group consisting of high. According to claim 1, wherein the composition is a shampoo composition, characterized in that to increase the hair adsorption of the polymer nanostructures containing the active ingredient in the hair or to enhance the hair tensile strength.