KR101069082B1 - Skin Cleansing compositions containing cationic surfactant with glyceryl moiety - Google Patents

Abstract

The present invention relates to a skin cleanser composition, and includes an anionic surfactant and a quaternary ammonium cationic surfactant represented by the following formula (1). Quaternary ammonium cationic surfactants include glyceryl groups, which are hydrophilic groups, to form neutral complexes with excellent solubility in water when combined with anionic surfactants, which are cleansing ingredients, and when adsorbed into skin oils, to improve skin adsorption. Since the effect of the useful agent can be effectively exerted, the skin cleanser composition containing the same has little irritation to the skin, and has excellent initial bubble, bubble retention, and moisturizing properties.

<Formula 1>

Quaternary Ammonium, Cationic Surfactant, Skin Cleanser

Description

Skin cleansing compositions containing cationic surfactant with glyceryl moiety

The present invention relates to a skin cleanser composition containing a cationic surfactant having a glyceryl group introduced therein.

Conventionally, a skin cleaner having an excellent cleaning action has been used to remove skin contaminants. However, in order to maintain a moist and glossy skin condition, the skin must contain an appropriate amount of moisture, so researches on skin cleaners that not only maintain the cleanliness of the skin by cleaning action but also protect and moisturize the skin Has been.

As such skin cleaners, skin cleaners have been added to which the skin useful ingredient exhibits conditioning and moisturizing effects have been developed. Examples of such skin benefit ingredients include various polymer compounds, polyols, ester oils, fats and oils, silicone compounds and the like. come.

By the way, in the case of the aforementioned polymer compound, it is widely used as a product for enhancing the stability of the product and as a moisturizer, but it is slippery when rinsing and sticky after drying, and in the case of water-soluble polyol, a large part is lost during rinsing, and the amount of foam is reduced. In the / W formulation, the viscosity is lowered, which affects the stability of the content. In addition, ester oils, silicones and fats and oils have a drawback of reducing the amount of bubbles, poor rinsing, and affects the color, odor and property stability of the contents of the product, causing a limitation in the content.

In particular, when a detergent containing a large amount of anionic surfactant generally contains a smaller amount of lipophilic skin oil, there was a problem that the lipophilic component is removed by the surfactant to be effectively delivered to the skin.

On the other hand, cationic surfactants generally exhibit excellent conditioning effects. These cationic surfactants generally form complexes with anionic surfactants used in detergents to form precipitates and have high skin irritation and have been refrained from use in skin cleaners. .

However, recently dissolving anionic surfactants and cationic surfactants with different ionic ions simultaneously in an aqueous solution combines the anionic and cationic surfactants to form a neutral complex called a pseudo pseudo-nonionic complex surfactant. In some cases, it is known that the neutral complex may increase the solubility in water as the hydrophilic group has more hydrophilic groups such as a nonionic surfactant.

These neutral complexes are known to have a stable dispersion of surfactants according to the content ratio of cationic and anionic surfactants ("Anionic and Cationic compounds in Mixed system", Cosmetics & Toiltries, Vol. 106, April 1991, PP49-). 54) It has been reported that the neutral complex of dispersed surfactant effectively adsorbs and delivers skin useful components during cleaning and rinsing as compared to systems containing only free surfactant. (Korean Patent Publication Nos. 10-2000-65184 and 10-2000-65185). However, in these systems, it is difficult to form stable surfactant neutral complexes due to the formation of precipitates above a certain amount of the cationic surfactant, and there is a problem in that the initial bubble power and the bubble holding power are not satisfactory when the oil is contained. .

Accordingly, the technical problem to be achieved by the present invention is to solve the above problems, to provide a skin cleansing composition having a low irritation to the skin, excellent initial foaming power, bubble holding power and moisturizing power.

In addition, another technical problem to be achieved by the present invention is to provide a skin cleansing composition that can effectively exert the efficacy of the skin oils by improving the adsorption of the skin oils to the skin when the skin oils are contained in addition to the above object. It is.

In order to achieve the above technical problem, the present invention provides a skin cleanser composition comprising an anionic surfactant and a quaternary ammonium cation surfactant represented by the following formula (1).                     

<Formula 1>

In Formula 1, R ₁ is any one selected from the group consisting of a straight alkyl group having 12 to 18 carbon atoms, a branched alkyl group and an alkenyl group, R ₂ and R ₃ are independently an alkyl group having 1 to 3 carbon atoms, n is 1 to 10, and X is any one selected from the group consisting of a halogen group element, a sulfate group and an acetate group.

Hereinafter, the composition of the present invention will be described in detail.

The skin cleanser composition according to the present invention includes a cationic surfactant into which a glyceryl group represented by Chemical Formula 1 is introduced. Referring to Formula 1, the cationic surfactant used in the present invention has one or more hydrophilic groups in the substituent as a structure of the quaternary ammonium compound, and the hydrophilic group is a structure in which one or more glyceryl groups are condensed and repeated, and the number of repeating units is 1 to 10.

As described above, conventional cationic surfactants not only have high skin irritation despite excellent conditioning effects, but also form precipitates when anionic surfactants are used as cleaning ingredients, and thus, of course, Since the washing | cleaning power also falls and the stability of a composition also falls, the usage-amount had a limit.

However, the quaternary ammonium cation surfactant may contain at least one glyceryl group, which is a hydrophilic group, and may form a mixed micelle that is soluble in an aqueous solution that is a neutral complex through interaction with the anionic surfactant. These neutral complexes are commonly known as pseudo-nonionic complex surfactants, and the formation of such neutral complexes improves the problems that occur when cationic and anionic surfactants are used simultaneously. Thus, the amount of the cationic surfactant can be increased even in the presence of the anionic surfactant. Such neutral composites can be prepared by controlling the conditions such as the structure and the mixing concentration of the anionic surfactant and the cationic surfactant in terms of surfactant activity, for example, solubilizing power, detergency, emulsifying power, dispersing power, surface tension reducing ability, and low cmc concentration. Excellent effect can be obtained.

As such, the quaternary ammonium cationic surfactant represented by Formula 1 includes a glyceryl group, which is a hydrophilic group, to increase the solubility of water in the resulting neutral complex to prevent precipitation formation, It increases initial bubble level and bubble retention, and increases the moisturizing power of the neutral complex itself.

Preferably, the content of the quaternary ammonium cationic surfactant included in the skin cleanser composition of the present invention is 0.1 to 30% by weight, more preferably 0.5 to 10% by weight, more preferably based on the total weight of the composition. Is 0.5 to 5% by weight.

The anionic surfactant which is a cleaning ingredient included in the skin cleanser composition according to the present invention may be generally applied to all widely used anionic surfactant compounds, for example, carboxylate compounds such as soap, higher alcohols, higher grades. Alkyl ethers, sulfate esters of sulfates of olefins, sulfate compounds including alkylbenzensulfonates, phosphate compounds phosphorylated with higher alcohols, and the like. Specifically, sodium lauryl sulfate (hereinafter referred to as 'SLS'), sodium lauryl ether sulfate (SLES), linear alkylbenzenesulfonate (LAS), monoalkyl phosphate (MAP), acyl isethionate (acyl isethionate, SCI), alkyl glyceryl ether sulfonate (AGES), acyl glutamate (acyl glutamate), acyl taurate, fatty acid metal salt (fatty acid metal salt), etc. It is preferable to use the above, and to use SLS, SLES, LAS, or SCI especially.

The content of such anionic surfactants is preferably 0.1 to 40% by weight, more preferably 0.5 to 20% by weight, still more preferably 0.5 to 15% by weight based on the total weight of the composition.

The present invention also provides a skin cleanser composition containing an anionic surfactant, a quaternary ammonium cationic surfactant represented by the formula (1) and a skin oil solvent. The skin oil component is effectively absorbed and delivered to the skin during washing and rinsing by the neutral complex of the quaternary ammonium cationic surfactant and anionic surfactant described above, thereby increasing its efficacy. As the skin oils, various skin oils commonly used in skin cleansing compositions may be used. For example, the skin oils may include one or more selected from polyols, ester oils, fats and oils, silicones, and various moisturizing agents. It may include ingredients such as skin soothing agents, skin treatments, skin protectants, sunscreens, vitamins and vitamin derivatives. The amount of such dermatological agents is preferably 0.0001 to 30% by weight, more preferably 0.01 to 20% by weight, even more preferably 0.01 to 15% by weight based on the total weight of the composition, and anionic surfactant and formula (1). The preferred content of quaternary ammonium cationic surfactant is as described above.

Meanwhile, the skin cleanser composition according to the present invention may further include a nonionic surfactant, the content of which is preferably 0.1 to 40% by weight, more preferably 0.2 to 15% by weight, further based on the total weight of the composition, respectively. Preferably it is 0.5 to 10 weight%. Examples of suitable nonionic surfactants for cleaning components included in skin cleanser compositions include fatty acid alkanol amides (cocamide diethanol amides), alkyl polyglucosides, fatty alcohol ethoxylates, alkylphenol-polyethylene glycols, alkylated-polyethylene glycols. And fatty amine ethoxylates, fatty acid ethoxylates, polypropylene glycol ethoxylates, sorbitol esters and polyglycol ethers. In addition, amphoteric surfactants may be used alone or in combination with the aforementioned nonionic surfactants, with the preferred content being the same as the nonionic surfactants.

In addition, as an additive commonly used in skin cleanser compositions, stabilizers, flavors, preservatives, antioxidants and the like may be further used.

The skin cleanser composition of the present invention can be suitably prepared in a formulation such as liquid, gel, powder, emulsion, cream, non-foam, paste or sheet depending on the use thereof.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Synthetic example

As a cationic surfactant in the form of quaternary ammonium, a monotype containing one quaternary ammonium group was synthesized in the following manner. The following examples are intended to illustrate the invention in detail, but these examples do not limit the technical scope of the invention.

Synthesis of N, N-Dimethyl-N-Monoglyceryl Stearyl Ammonium Chloride

In Scheme 1, R is C ₁₈ H ₃₇ .

Isopropyl alcohol (IPA; 120 g), dimethyloctadecylamine (397 g, 1.4 mol), 1-chloro-2,3-propanediol (166 g, 1.47 mol) were added to a three-necked flask, and sodium iodide was used as a catalyst. (sodium iodide) (2.4 g) was added followed by reflux. The reaction progress was checked by measuring the amine%. The reaction proceeded for 95 hours after raising the temperature of the reactor to 120 ° C. The reaction product was poured into acetone, cooled and recrystallized. The result was hygroscopic, and the result obtained through the manure after recrystallization was immediately dried in vacuo.

Synthesis of N, N-Dimethyl-N-Diglyceryl Stearyl Ammonium Chloride

In Scheme 1, R is C ₁₈ H ₃₇ .

In order to synthesize the diglyceryl compound in which two glyceryl groups were substituted, the glyceryl group was further introduced in the monoglyceryl compound.

Isopropyl alcohol (IPA; 140 g), a monoglyceryl compound (286 g, 0.7 mol), and glycidol (61 g, 96%, 0.7 mol) were added to a three-necked flask, followed by stirring at 50 ° C. for 1 hour. Completed. Isopropyl alcohol was removed from the mixture by distillation under reduced pressure. The result was hygroscopic, so the result was stored as a 50% solution in distilled water.

Cytotoxicity Test

As shown in Table 1, each of the cationic surfactants was subjected to cytotoxicity experiments. MTT test was performed by culturing V79-4 cells (Chinese Hamster, CCL of lung tissue fibroblast), and the samples were diluted (10%, 1%, 0.1%, 10%, 1%, 0.1%) in an appropriate concentration in medium (3% FBS DMEM). ) Was incubated for 24 hours and MTT test was performed. And the absorbance was measured at 570nm to measure the viability of the cells. In the comparative example, a conventional cationic surfactant was used, and in the experimental example, a quaternary ammonium cationic surfactant represented by Formula 1, which can be obtained by the method according to the synthesis example described above, was used. Specifically, Comparative Examples 1 and 2 are quaternary ammonium salts, Comparative Examples 3 to 8 are tertiary amidoamine salts, and Experimental Examples 1 to 4 are represented by the aforementioned Formula 1, and glyceryl ammonium having different alkyl numbers. Salt.

Raw material name IC50 (%) Comparative Example 1 CETAC-50 0.0000005 Comparative Example 2 Genamin KM-P 0.00008 Comparative Example 3 Hepamine + Glutamic acid 0.00005 Comparative Example 4 Hepamine + Miami CT-130 0.00005 Comparative Example 5 Hepamine + Malic acid 0.00005 Comparative Example 6 Hepamine + Succinic acid 0.00005 Comparative Example 7 Hepamine + Aspartic acid 0.00005 Comparative Example 8 Hepamine + Glutaric acid 0.00005 Experimental Example 1 BGA- 0.0015 Experimental Example 2 SGA- 0.0015 Experimental Example 3 LGA- 0.0002 Experimental Example 4 HGA- 0.00175 1) CETAC-50 (Cetrimonium Chloride)
2) Genamin KM-P (Behentrimonium chloride)
3) Hepamine (Stearamido propyl dimethylamine)
4) BGA- (R1 = behenyl, n = 2 in Formula 1)
5) SGA- (R 1 = stearyl, n = 2 in Formula 1)
6) LGA- (R1 = lauryl, n = 2 in Formula 1)
7) HGA- (R1 = Staramido propyl dimethyl, n = 2 in Formula 1)

Referring to Table 1, the results of IC50 (%) confirming the measurement of the concentration of killing 50% of the cells, the samples of Experimental Examples 1 to 4 used in the skin cleanser composition of the present invention remarkably compared to Comparative Examples 1 to 8 Low cytotoxicity was shown.

Comparative Examples 1 to 4 and Examples 1 to 2

According to the components and contents shown in Table 2 below, the aqueous phase components of the raw materials 1 to 7 were mixed and warmed to 70 ° C. The oily ingredients of the raw materials 8 to 9 were mixed at 70 ° C., stirred for 30 minutes, emulsified, cooled, and the raw materials 10 and 11 were added at 45 ° C., stirred to be uniform, and cooled to 35 ° C. In Table 2, the unit is weight percent.

NO. Raw material name Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Example
One Example
2 One Sodium Lauret Sulfate (28%) 35 35 35 35 35 35 2 Cocamidopropyl Betaine (30%) 10 10 10 10 10 10 3 Cocamide diethanolamide 3 3 3 3 3 3 4 SGA- (40%) - - - - 5 5 5 CETAC-50 5 5 - - - - 6 Genamin KM-P - - 5 5 - - 7 glycerin 2 2 2 2 2 2 8 Soybean oil 5 - 5 - 5 - 9 PEG150-distearate One One One One One One 10 Spices Spices Quantity Quantity Quantity Quantity Quantity 11 antiseptic antiseptic Quantity Quantity Quantity Quantity Quantity 12 Purified water To 100 To 100 To 100 To 100 To 100 To 100

<Measurement of initial bubble and bubble holding force>

Each sample was prepared as a 5% solution and measured using the semi-micro TK Method, and the results are shown in Table 3 below. The unit is ml.

division 0 min 15 minutes Comparative Example 1 200 190 Comparative Example 2 190 170 Comparative Example 3 200 185 Comparative Example 4 195 170 Example 1 245 245 Example 2 240 240

Looking at the Table 3, in the case of Examples 1 to 2 it was found that not only the initial bubble power is very excellent compared to Comparative Examples 1 to 4, but also the bubble is maintained very stable.

<Measurement of adsorption amount of useful skin components>

Pig skin of 10 × 10 cm 2 was pretreated by leaving for 18 hours in a desiccator containing 30% glycerin. Samples of Comparative Examples 1, 3 and 1 containing soybean oil were prepared as 10% solutions, respectively, and the skin was added to each sample and stirred for 3 minutes. The skin was then rinsed with tap water for 20 seconds at a flow rate of about 13 cc / min. After rinsing, the skin was dried by tapping once with a paper towel and dried in air for 2 minutes.

The soybean oil adsorbed on the skin was extracted with 50 ml of ethanol and quantitatively analyzed by HPLC.

Comparative Example 1 Comparative Example 3 Example 1 Soybean oil adsorption amount
(㎍ / ㎠) 22.9 25.4 37.2

Looking at the Table 4, it can be seen that in the case of Example 1 is a much larger amount of the skin useful components than the case of Comparative Examples 1 and 3.

<Skin Moisturizing Evaluation>

In order to compare and determine the moisturizing power of Comparative Examples 1 to 4 and Examples 1 to 2, the test was performed twice a day for 4 test subjects each day for 4 days.

The instrument used was measured using a skin moisture content measuring device (Skin Surface Hygrometer, model name: SKICON-200, manufactured by IBM Corporation, Japan). 1 ml of each formulation was rubbed in the hand for 10 seconds to form a foam, and the forearm was rubbed 10 times for 10 seconds with the resulting foam. After leaving the foam for 30 seconds, rinsed in running water for 30 seconds, squeezed with a tissue for 30 seconds, dried, and measured for 5 minutes.

The measurement values obtained through this instrument were made into Comparative Example 9 as 100%, and based on this value, the measured values of each Comparative Example were converted into relative comparison values with reference values, and are shown as a rising or falling rate in Table 5 below. In Table 5 below, N = 20 and Ave%.

Measurement result Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Measured value conversion value 100 84 105 89 138 119

Table 6 below is a consumer evaluation result for three weeks for 30 males and females in their 20s to 30s, and shows the evaluation results (distribution rate,%) of skin softness after showering.                     

Evaluation results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 very good 0 (0%) 0 (0%) 0 (0%) 0 (0%) 11 (36.7%) 4 (13.3%) Slightly satisfied 6 (20%) 2 (6.7%) 7 (23.1%) 3 (9%) 12 (40%) 14 (46.7%) usually 22 (73.3%) 21 (70%) 21 (70%) 22 (73.3%) 7 (23.1%) 12 (40%) dissatisfaction 2 (6.7%) 7 (23.3%) 2 (6.6%) 5 (16.7%) 0 (0%) 0 (0%) sum 30 (100%) 30 (100%) 30 (100%) 30 (100%) 30 (100%) 30 (100%)

Looking at the Tables 5 to 6, Examples 1 to 2 were measured to be superior to the moisturizing power than Comparative Examples 1 to 4, in particular, even in Example 2 that does not contain soybean oil showed excellent moisturizing power. In addition, it can be seen that the consumer evaluation shows similar results with the measurement results of the device.

As described above, the quaternary ammonium cationic surfactant included in the skin cleanser composition of the present invention contains a glyceryl group which is a hydrophilic group and is combined with an anionic surfactant which is a cleaning component to form a neutral complex having excellent solubility in water. can do. Therefore, the skin cleanser composition including the same has little irritation to the skin, and has excellent initial bubble, bubble retention, and moisturizing properties.

In addition, in addition to the above-described effects when the skin solvent is added to the skin cleanser composition, it is possible to effectively improve the adsorption of the skin oil to the skin, thereby effectively exhibiting the efficacy of the skin solvent.

Claims (8)

A skin cleanser composition comprising an anionic surfactant and a quaternary ammonium cationic surfactant represented by Formula 1 below; <Formula 1>

In Formula 1, R ₁ is any one selected from the group consisting of a straight alkyl group having 12 to 18 carbon atoms, a branched alkyl group, and an alkenyl group, R ₂ and R ₃ are independently an alkyl group having 1 to 3 carbon atoms, n is 1 to 10 and X is any one selected from the group consisting of a halogen group element, a sulfate group and an acetate group. According to claim 1, wherein the content of the anionic surfactant and the quaternary ammonium cationic surfactant is 0.1 to 40% by weight and 0.1 to 30% by weight, respectively, based on the total weight of the composition. The method of claim 1 or 2, wherein the anionic surfactant is sodium lauryl sulfate, sodium lauryl ether sulfate (SLES), linear alkylbenzenesulfonate (LAS), monoalkyl phosphate (MAP), acyl isothio Nate (SCI), alkyl glyceryl ether sulfonate (AGES), acyl glutamate (acyl glutamate), acyl taurate (acyl taurate) and fatty acid metal salt (fatty acid metal salt), characterized in that any one or more selected from the group consisting of Skin Cleanser Composition. A skin cleanser composition comprising an anionic surfactant, a quaternary ammonium cationic surfactant represented by Formula 1 below, and a skin oil solvent; <Formula 1>

In Formula 1, R ₁ is any one selected from the group consisting of a straight alkyl group having 12 to 18 carbon atoms, a branched alkyl group, and an alkenyl group, R ₂ and R ₃ are independently an alkyl group having 1 to 3 carbon atoms, n is 1 to 10 and X is any one selected from the group consisting of a halogen group element, a sulfate group and an acetate group. According to claim 4, wherein the content of the anionic surfactant, quaternary ammonium cationic surfactant and dermal solvent is 0.1 to 40% by weight, 0.1 to 30% by weight and 0.0001 to 30% by weight, respectively, based on the total weight of the composition A skin cleanser composition. The skin cleanser composition of claim 5, further comprising 0.1 to 40% by weight of a nonionic surfactant. The nonionic surfactant according to claim 6, wherein the nonionic surfactant is selected from fatty acid alkanol amides, alkyl polyglucosides, fatty alcohol ethoxylates, alkylphenol-polyethylene glycols, alkylated-polyethylene glycols, fatty amine ethoxylates, fatty acid ethoxylates, A skin cleanser composition comprising any one or more selected from the group consisting of polypropylene glycol ethoxylates, sorbitol esters, and polyglycol ethers.     5. The skin of claim 1, wherein the skin cleanser composition is prepared in a formulation selected from the group consisting of liquid, gel, powder, emulsion, cream, mousse, paste and sheet. Detergent composition.