KR20220058253A - Cosmetic composition with water resistance comprising zwitterionic chitosan derivative - Google Patents

Abstract

A cosmetic composition having water resistance including a zwitterionic chitosan derivative is provided. The present invention has excellent durability.

Description

Cosmetic composition with water resistance comprising zwitterionic chitosan derivative

It relates to a cosmetic composition having water resistance.

Chitosan is a kind of naturally-derived aminopolysaccharide, obtained by deacetylating chitin contained in the cell walls of microorganisms such as crabs, shrimp shells, squid bones, molds, mushrooms and bacteria. is a homopolymer of Their main role in living organisms is to form an exoskeleton of the living body to protect the living body from the external environment and to maintain homeostasis.

The main component of chitosan is polyglucosamine, which is a colorless amorphous powder with a polymer structure. Chitosan, which is a glucosamine bond, has a molecular structure similar to that of human tissue, and has excellent affinity for the human body and does not cause an immune response. It is a very valuable biomaterial used. However, since most of the chitosan that has been used in the cosmetic field is fat-soluble chitosan, only a very small amount is dissolved in oil or simply used as a concept ingredient in order to exhibit practical efficacy.

Chitosan is an insoluble substance that is not soluble in water because it is firmly bound by strong hydrogen bonds between neighboring molecules. Organic acids including lactic acid, acetic acid, propionic acid, formic acid, ascorbic acid, and tartaric acid in order to dissolve the conventional chitosan; and an inorganic acid composed of hydrochloric acid, nitric acid and sulfuric acid. Recently, research on grafting sugar acids to develop water-soluble chitosan that is more suitable for in vivo application has also been conducted (Patent Document 1).

However, water-soluble chitosan has been limitedly applied to anticancer treatment and food additives. In particular, since low molecular weight chitosan in the form of an oligomer has been mainly used in the food industry, studies on the effect of high molecular weight chitosan of 100,000 kDa or more have not been made. In particular, chitosan used for medical purposes is beta-chitosan in an isomeric form, and there is a realistic entry barrier that it is difficult to apply to the cosmetic industry because it is very expensive.

Therefore, there is a need for research on water-soluble high molecular weight chitosan derivatives applicable to the cosmetic industry.

KR 10-2019-0080845 A

It provides a cosmetic composition having water resistance comprising a zwitterionic chitosan derivative.

Provided is a use of a zwitterionic chitosan derivative for preparing a cosmetic composition having water resistance.

One aspect provides a cosmetic composition having water resistance comprising a zwitterionic chitosan derivative.

The term "water resistance" refers to the property of resisting and resisting moisture.

In one embodiment, it was confirmed that the cosmetic composition containing the zwitterionic chitosan derivative has very good water resistance.

In another embodiment, since it was confirmed that the zwitterionic chitosan derivative does not have cytotoxicity and skin side effects, it can be safely applied to the cosmetic composition.

The term "zwitterionic" is used interchangeably with "amphoteric," and has acidic (eg -COOH) and basic (eg -NH ₂ ) groups in the molecule, resulting in acids and bases. It means that it is capable of reacting with all of them.

The term “chitosan” refers to a substance obtained by deacetylation of chitin. The chitosan may include all forms of chitosan, such as an alpha or beta isomer.

The term “derivative” refers to a similar compound obtained by chemically modifying part of a compound.

The "zwitterionic chitosan derivative" may be a derivative obtained by modifying chitosan to have zwitterionic properties. Specifically, the derivative modified to have an anionic moiety in chitosan has an amine group (-NH ₂ ) present in chitosan has a positive charge, and the anion moiety has a negative charge, so it can have zwitterionic properties.

The zwitterionic chitosan derivative may include a repeating unit represented by the following formula (1).

[Formula 1]

(In Formula 1, X is the same or different from each other in each repeating unit and is each independently H, -COCH ₃ or an anionic moiety.)

In Formula 1, the repeating unit in which X is H may be a repeating unit of deacetylated chitosan (hereinafter, referred to as “repeating unit A”).

In Chemical Formula 1, the repeating unit in which X is -COCH ₃ may be a non-deacetylated repeating unit of chitosan (hereinafter, referred to as “repeating unit B”).

In Formula 1, the repeating unit in which X is an anionic moiety may be a repeating unit in which the amine group (—NH ₂ ) of chitosan is modified to have an anionic moiety (hereinafter, referred to as “repeating unit C”).

In Formula 1, X may be the same or different from each other in each repeating unit. Accordingly, the zwitterionic chitosan derivative may include a repeating unit A and a repeating unit C, or include a repeating unit B and a repeating unit C, or may include a repeating unit A, a repeating unit B, and a repeating unit C. The number of repeating units A, B, and C in the total number of repeating units of the zwitterionic chitosan derivative may be different.

The term “anionic moiety” means a moiety that is negatively charged. The anionic moiety may have a negative charge of -1 or -2.

The anionic moiety is any one selected from the group consisting of -RSO ₃ H (sulfonate), -RCOOH (carboxylate) and -RPO ₂ HR' (phosphonate), and R and R' are each independently It may be a C1-C20 aliphatic or aromatic hydrocarbon group substituted or unsubstituted with R and R' are each independently a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C7 It may be a -C20 aralkylene group.

When two or more repeating units C are included in one molecule of the zwitterionic chitosan derivative, the kind of anionic moieties of the repeating unit C may be the same or different from each other in each repeating unit C. In one embodiment, when one molecule of the zwitterionic chitosan derivative includes two or more repeating units C, the type of the anionic moiety of the repeating unit C may be the same in each repeating unit C.

In one embodiment, when two or more repeating units C are included in one molecule of the zwitterionic chitosan derivative, each repeating unit C may have an anionic moiety -RSO ₃ H. Such zwitterionic chitosan derivatives may be referred to as "sulfonated chitosan". The sulfonated chitosan can be synthesized by reacting 1,3-propanesultone with the amine group of chitosan.

In another embodiment, when two or more repeating units C are included in one molecule of the zwitterionic chitosan derivative, each repeating unit C may have an anionic moiety -RCOOH. Such zwitterionic chitosan derivatives may be referred to as "carboxylated chitosan". The carboxylated chitosan may be synthesized by reacting chloroacetic acid or brominated acetic acid with an amine group of chitosan.

In another embodiment, when two or more repeating units C are included in one molecule of the zwitterionic chitosan derivative, each repeating unit C may have an anionic moiety -RPO ₂ HR′. Such zwitterionic chitosan derivatives may be referred to as “phosphorylated chitosan”. The phosphorylated chitosan may be synthesized by reacting phenyl phosphoric acid with an amine group of chitosan.

Chitosan used in the preparation of the zwitterionic chitosan derivative is not limited in its molecular weight, but may be, for example, high molecular weight chitosan. Specifically, the chitosan may be chitosan having a molecular weight of 1,000 kDa or more, 10,000 kDa or more, 100,000 kDa or more, or 1,000 kDa to 1,000,000 kDa.

The zwitterionic chitosan derivative has a total number of repeating units of 10 to 1,000, 10 to 900, 10 to 800, 10 to 700, 10 to 600, 10 to 500, 100 to 1,000, 100 to 900, 100 to 800, 100 to 700, 100 to 600, 100 to 500, or 500 to 1,000.

Chitosan used in the preparation of the zwitterionic chitosan derivative may have a deacetylation degree of 70% or more, 75% or more, 80% or more, 70 to 100%, 75 to 100%, or 80 to 100%. Accordingly, the ratio of the repeating unit (repeating unit B) in which X is -COCH ₃ in Formula 1 among the total number of repeating units of the zwitterionic chitosan derivative is 30% or less, 25% or less, 20% or less, 0 to 30 %, 0-25%, or 0-20%.

The ratio of the repeating unit (repeating unit C) in which X is an anionic moiety in Formula 1 among the total number of repeating units of the zwitterionic chitosan derivative is more than 50%, more than 60%, more than 70%, more than 80%, more than 90% % or more, 60 to 99%, 70 to 99%, 80 to 99%, or 90 to 99%. When the ratio of the repeating unit C among the total number of repeating units of the zwitterionic chitosan derivative is 50% or less, it may not be well soluble in water.

The ratio of the repeating unit C among the total number of repeating units of the zwitterionic chitosan derivative may be referred to as the "Zwitterionization degree (ZD)" or "ionization ratio" of the zwitterionic chitosan derivative.

The cosmetic composition contains 0.1 to 10% by weight of the zwitterionic chitosan derivative, 0.1 to 5% by weight, 0.1 to 3% by weight, 0.1 to 2% by weight, 0.5 to 10% by weight, 0.5 to 5% by weight based on the total weight of the composition , 0.5 to 3% by weight, or 0.5 to 2% by weight may be included.

The cosmetic composition may be an oil-in-water emulsion formulation.

The cosmetic composition comprises: an aqueous phase comprising a zwitterionic chitosan derivative; And it may be an oil-in-water emulsion formulation comprising an oil phase.

The aqueous phase may be included in an amount of 70 to 95% by weight based on the total weight of the composition, but is not limited thereto.

The aqueous phase may further include a polyol. The terms "polyol" and "polyhydric alcohol" are used interchangeably and refer to an aliphatic compound having two or more hydroxyl groups (-OH). The polyol may be glycerol, glycols, sorbitol, or a combination thereof. The glycerol may be glycerin, diglycerin, polyglycerin, glyceritol, glycyl alcohol, or a combination of two or more thereof. The glycerin may be used interchangeably with other commonly used names such as lysline, propane-1,2,3-triol, 1,2,3-propenetriol, and trihydroxypropane. The glycols may be propylene glycol, dipropylene glycol, butylene glycol, diethylene glycol, triethylene glycol, hexylene glycol, pentylene glycol, polyethylene glycol, methylpropanediol, or a combination of two or more thereof.

The oil phase may be included in an amount of 5 to 30% by weight based on the total weight of the composition, but is not limited thereto.

The oil phase may further include an ester-based oil, a hydrocarbon-based oil, a vegetable oil, or a combination thereof.

The ester oil is ethylhexyl isononanoate, ethylhexyl isopalmitate, ethylhexyl isostearate, ethylhexyl myristate, isopropyl myristate, octyldodecyl myristate, ethylhexyl neopentanoate, trie Chilhexanoin, ethylhexyl oleate, ethylhexyl palmitate, ethylhexyl stearate, isononyl isononanoate, phytosteryl isostearyl dimerinoate, polyglyceryl-2 triisostearate, pentaerythrityl from the group consisting of tetraisostearate, cetylethylhexanoate, caprylic/capric triglyceride, butylene glycol dicaprylate/dicaprate, tocopherol acetate dicaprylic carbonate, and diisostearyl malate It may be one or more selected.

The hydrocarbon-based oil may be paraffin-based, olefin-based, squalane, or hydrogenated polydecene, but is not limited thereto.

As the vegetable oil, vegetable oils such as macadamia seed oil, meadow foam seed oil, olive oil, camellia oil, hazelnut oil, and argan oil, and waxes having a low melting point such as shea butter and hydrogenated vegetable oil may be used.

The oil phase may further include silicone oil. The silicone oil may be dimethicone, cyclomethicone, alkylsiloxane, cycloalkylsiloxane, etc., but is not limited thereto.

The cosmetic composition may include a surfactant. The surfactant may be any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and the like, and the type thereof is not limited. The surfactant may be included in the aqueous phase or oil phase depending on the type thereof. The surfactant may be included in an amount of 0.05 to 1% by weight, 0.05 to 0.5% by weight, 0.05 to 0.3% by weight, 0.1 to 1% by weight, 0.1 to 0.5% by weight, or 0.1 to 0.3% by weight based on the total weight of the composition.

The cosmetic composition may further include a sunscreen. The sunscreen may be an organic sunscreen or an inorganic sunscreen. The type of the sunscreen is not particularly limited as long as it is a conventional component used in a cosmetic composition. Accordingly, the cosmetic composition may be a cosmetic composition for sunscreen.

The cosmetic composition may further add components such as antioxidants, preservatives, pH adjusters, humectants, and lubricants as necessary. In addition, the cosmetic 　 composition may further include a substance capable of providing essential nutrients to the skin auxiliary. The cosmetic composition may contain adjuvants including, but not limited to, natural fragrance, cosmetic fragrance, or plant extract.

The cosmetic composition may be used for skin, mucous membranes, scalp or hair. The cosmetic composition may include a basic cosmetic such as a softening lotion, a nutrient lotion, a cream, a pack, a gel, and a patch; color cosmetics such as lipstick, makeup base, and foundation; cleaning agents such as shampoo, conditioner, body cleanser, toothpaste, and mouthwash; It may be used as a hair conditioner such as hair tonic, gel, mousse, etc., and as a cosmetic for hair such as a hair conditioner and a hair dye, but is not limited thereto.

Another aspect provides the use of a zwitterionic chitosan derivative for preparing a cosmetic composition having water resistance.

Details of the water resistance, zwitterionic chitosan derivative, and the cosmetic composition are as described above.

Since the cosmetic composition according to an aspect has excellent water resistance by including the zwitterionic chitosan derivative, it is not easily erased even in water after the cosmetic composition is applied, so that it can have excellent durability.

1 is a result of NMR analysis of sulfonated chitosan.
2 is a graph confirming the effect of improving the glossiness when Example 1 and Comparative Example 1 were applied to the inner skin of the forearm.
3 is a graph confirming the gloss improvement effect when Example 1 and Comparative Example 1 are applied to the facial skin.
4 is a graph showing the cytotoxicity test results of zwitterionic chitosan derivatives.
5 is a water resistance evaluation result of Example 2 and Comparative Example 4.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Preparation Example 1. Synthesis of zwitterionic chitosan derivative 1

Among the zwitterionic chitosan derivatives, sulfonated chitosan was synthesized as shown in Scheme 1 below. Sulfonated chitosan was synthesized by reacting 1,3-propanesultone with the amine group (-NH ₂ ) of chitosan.

[Scheme 1]

Specifically, 0.5 g of chitosan (viscosity: 200-800 cP (1 wt% acetic acid solution, 25°C), degree of acetylation: 75-85%, Sigma-Aldrich, Inc., USA) was dissolved in 40 mL 2% acetic acid solution After stirring, it was heated to 50 °C while stirring with a magnetic stirrer. 1,3-propanesultone (TCI, Japan) having the same number of moles (3.1 mmol, 1 equivalent) of the amine group of chitosan was added to the prepared chitosan solution, and stirring was continued for 16 hours. The reaction solution was precipitated with acetone to obtain a reactant, and a white solid was obtained through centrifugation. Then, the obtained reactant was dispersed in ethanol and washed for several minutes in a sonicator. The solid obtained by centrifugation again was dissolved in distilled water and then freeze-dried.

The obtained chitosan derivative into which sulfonic acid was introduced was dissolved in deuterium oxide (D ₂ O) at a concentration of 3 g/L and subjected to nuclear magnetic resonance ( ¹ H NMR, Varian NMR System) analysis at 500 MHz, and the results were 1 is shown.

1 is a result of NMR analysis of sulfonated chitosan.

As shown in FIG. 1 , after adding 1,3-propanesultone, a sulfonation reaction was performed, and peaks corresponding to a, b, and c of Scheme 1 were confirmed. Therefore, it was confirmed that sulfonated chitosan was prepared.

Preparation Example 2. Synthesis of zwitterionic chitosan derivatives 2

Among the zwitterionic chitosan derivatives, carboxylated chitosan was synthesized as shown in Scheme 2 below. Carboxylated chitosan was synthesized by reacting chloroacetic acid with an amine group (-NH ₂ ) of chitosan.

[Scheme 2]

Specifically, 8.5 equivalents of chlorinated acetic acid (26.35 mmol) was dissolved in distilled water, and the pH was adjusted to 7 using sodium hydroxide solution. 0.5 g of chitosan (viscosity: 200-800 cP (1 wt% acetic acid solution, 25°C), degree of acetylation: 75-85%, Sigma-Aldrich, Inc., USA) was added to the solution, and stirred with a magnetic stirrer while heating to 90 °C. The reaction time was 4 hours, and pH 7 was maintained by dropwise addition of 20% sodium carbonate solution every 30 minutes. The reaction solution was precipitated with ethanol to obtain a reactant, and a white solid was obtained through centrifugation. Then, the obtained product was dispersed in ethanol and washed for several minutes in a sonicator. The solid obtained by centrifugation again was vacuum-dried.

Preparation Example 3. Zwitterionic chitosan derivative synthesis 3

Among the zwitterionic chitosan derivatives, phosphorylated chitosan was synthesized as shown in Scheme 3 below. Phosphorylated chitosan was synthesized by reacting phenyl phosphoric acid with an amine group (-NH ₂ ) of chitosan.

[Scheme 3]

Specifically, 0.5 g of chitosan (viscosity: 200-800 cP (1 wt% acetic acid solution, 25° C.), degree of acetylation: 75-85%, Sigma-Aldrich, Inc., USA) was dissolved in 1% acetic acid solution. . After dissolving the same mass of phenyl phosphoric acid as chitosan in distilled water, it was added to the chitosan solution for 2 hours. The reaction was carried out while stirring with a magnetic stirrer. After raising the temperature of the reaction solution to 80 °C, formic acid in an amount corresponding to 37% by mass of the used chitosan was added for 1 hour, followed by stirring under reflux at the same temperature for 6 hours. It was dialyzed with distilled water for 2 days using a dialysis membrane having a cutoff molecular weight of 6-8 kDa, followed by freeze-drying.

The anion group introduction ratio of the zwitterionic chitosan derivative synthesized in Preparation Examples 1 to 3 was set to 90% or more. When the anionic group introduction ratio is 90% or more, the chitosan derivative may be well soluble in water.

On the other hand, as a result of introducing each anionic group of Preparation Examples 1 to 3 into chitosan, chloroacetic acid or phenylphosphoric acid ending in -COOH caused a condensation reaction with the hydroxyl group of chitosan to produce an ester byproduct. Therefore, the sulfonated chitosan of Preparation Example 1, which has the best reaction efficiency because there is no ester by-product, was used below.

Example 1 and Comparative Examples 1-3. Preparation of oil-in-water emulsion cosmetic composition

An oil-in-water emulsion cosmetic composition was prepared with the ingredients and contents (wt%) shown in Table 1 below.

Specifically, the raw materials corresponding to the aqueous phase except for the zwitterionic chitosan were measured in a beaker and uniformly mixed at a temperature of 75° C. using an emulsion mixer at 5000 rpm. Zwitterionic chitosan was slowly added in the phase of emulsifying and mixing the aqueous phase and mixed uniformly. Then, the raw materials corresponding to the oil phase were measured in a beaker and uniformly dissolved at a temperature of 75°C. The dissolved oil phase was slowly added to the aqueous phase and emulsified at 7000 rpm for 5 minutes using an emulsification mixer.

Comparative Example 1 contains 1 wt% of chitosan (viscosity: 200-800 cP (1 wt% acetic acid solution, 25°C), acetylation degree: 75-85%, Sigma-Aldrich, Inc., USA) without introducing an anionic group was used as

In Comparative Example 2, 0.5 wt% of sulfonated chitosan having an anionic group introduced ratio (ZD) of 50% was used.

In Comparative Example 3, 1 wt% of sulfonated chitosan having an anionic group introduced ratio (ZD) of 50% was used.

In Example 1, 1 wt% of sulfonated chitosan having an anionic group introduced ratio (ZD) of 90% was used.

division ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Awards Purified water remaining amount remaining amount remaining amount remaining amount 1,2-Hexanediol One One One One 1,3-butylene glycol 2 2 2 2 glycerin 7 7 7 7 Neat-chitosan One - - - Sulfonic acid-chitosan
(ZD=50%) - 0.5 One 0 Sulfonic acid-chitosan
(ZD=90%) - - - One paid cetearyl alcohol 0.8 0.8 0.8 0.8 Glyceryl Stearate SE 0.6 0.6 0.6 0.6 beeswax 0.3 0.3 0.3 0.3 Sorbitan Stearate 0.3 0.3 0.3 0.3 Cetylethylhexanoate 4 4 4 4 Octyldodecyl Myristate 1.5 1.5 1.5 1.5 squalane 3.5 3.5 3.5 3.5 Polysorbate 60 1.2 1.2 1.2 1.2 Sorbitan Sesquioleate 0.4 0.4 0.4 0.4 etc embalming dose dose dose dose Sum 100 100 100 100

In Comparative Examples 2 and 3, zwitterionic chitosan (ZD=50%) did not dissolve well in water, so it was not possible to prepare a stable emulsion.

In addition, the viscosity of the cosmetic compositions of Example 1 and Comparative Examples 1 to 3 was measured. Viscosity was measured with a Brookfield DV2TLV equipped with an LV 64 spindle at 30 rpm for 1 minute. As a result, in the case of Example 1, the viscosity value was greatly increased to 3,000 cPs using zwitterionic chitosan (ZD=90%). On the other hand, Comparative Examples 1 to 3 had a viscosity value of 200 to 300 cPS. Therefore, it was experimentally demonstrated that zwitterionic chitosan can also serve as a viscosity-forming agent.

Experimental Example 1. Evaluation of skin luster improvement

In this experiment, in order to measure the effect of improving the skin's immediate luster, the compositions of Example 1 and Comparative Example 1 were applied to the inner skin of the forearm and the facial skin, and then a skin Gloss meter (Delfin, Finland) and VISIA-CR (Canfield Scientific, Inc., USA) using the equipment was observed for skin gloss (Skin Gloss Unit).

2 is a graph confirming the effect of improving the glossiness when Example 1 and Comparative Example 1 were applied to the inner skin of the forearm.

3 is a graph confirming the gloss improvement effect when Example 1 and Comparative Example 1 were applied to the facial skin.

2 and 3, the gloss increase rate of Example 1 containing the zwitterionic chitosan derivative was 17.7%, and the gloss increase rate of Comparative Example 1 containing chitosan was 6.3%. That is, Example 1 containing the zwitterionic chitosan derivative showed 2.8 times superior skin gloss improvement effect compared to the gloss increase rate of Comparative Example 1.

Experimental Example 2. Cytotoxicity test

Human keratinocytes HaCaT cells were cultured under defined conditions. The evaluation method is as follows. HaCaT cells were suspended in DMEM medium containing 10% FBS, inoculated into a 96-well plate at 1x10 ⁴ cells/well, and cultured until adhered to the bottom of the well. The medium was removed and a DMEM medium containing a zwitterionic chitosan derivative at a concentration of 0.3 μg/ml, 3 μg/ml, 30 μg/ml or 300 μg/ml was added, and 5% CO ₂ , 37° C. for 24 hours. cultured. Then, in order to confirm the cytotoxic effect, MTT (3-(4,5-dimetylthiazol-2-yl)2,5-diphenyltetrazolium bromide) dissolved in DPBS (Dulbecco's phosphate-buffered saline) was added and reacted by adding 20 μl per well. MTT is a pale yellow substrate and turns dark blue by the respiratory chain enzyme in the mitochondria of living cells. After 4 hours, the reaction solution was discarded and DMSO was added to measure the absorbance at 570 nm using a microplate reader for the changed color.

4 is a graph showing the cytotoxicity test results of zwitterionic chitosan derivatives.

As shown in FIG. 4 , the reduction of cells by the zwitterionic chitosan derivative was not observed. Therefore, it was confirmed that the zwitterionic chitosan derivative has no cytotoxicity.

Example 2 and Comparative Example 4. Preparation of oil-in-water emulsion cosmetic composition for UV protection

An oil-in-water emulsion cosmetic composition for UV protection was prepared with the ingredients and contents (wt%) shown in Table 2 below. In general, an oil-in-water emulsion cosmetic composition composed of an organic sunscreen is easily washed off with water.

Specifically, the raw materials corresponding to the aqueous phase except for the zwitterionic chitosan were measured in a beaker and uniformly mixed at a temperature of 75° C. using an emulsion mixer at 5000 rpm. Zwitterionic chitosan was slowly added in the phase of emulsifying and mixing the aqueous phase and mixed uniformly. Then, the raw materials corresponding to the oil phase were measured in a beaker and uniformly dissolved at a temperature of 75°C. The dissolved oil phase was slowly added to the aqueous phase and emulsified for 5 minutes at 7000 rpm using an emulsification mixer. C14-22 alcohol/C12-20 alkyl glucoside was used as a surfactant.

division ingredient Comparative Example 4 Example 2 Awards Purified water remaining amount remaining amount pentylene glycol One One 1,2-Hexanediol 2 2 glycerin 3 3 dipropylene glycol 3 3 silica One One tromethamine 0.45 0.45 acrylate copolymer 0.6 0.6 Zwitterion-chitosan
(SD=90%) 0 0.7 paid Bis-ethylhexyloxyphenol methoxyphenyltriazine 3 3 Ethylhexyltriazone 2 2 Diethylaminohydroxybenzoylhexylbenzoate 3.5 3.5 Isoamyl p-methoxycinnamate One One Polysilicon-15 One One dibutyl adipate 6 6 Dicaprylyl Carbonate 8 8 C14-22 alcohol/C12-20 alkyl glucoside 0.2 0.2 etc embalming dose dose Sum 100 100

Experimental Example 3. Water resistance evaluation

Water resistance was evaluated for the oil-in-water emulsion cosmetic composition for UV protection of Example 2 and Comparative Example 4.

In order to visualize the effect of water resistance, visual evaluation was performed by photographing in UV-NF mode using a UV camera VISIACR (Canfiled Scientific, USA). The detailed evaluation method and results are as follows.

First, the test site was set in a size of 2 cm * 2 cm on the flexion side of the forearm 5 cm from the wrist of the subject. After uniformly applying 2 mg/cm ² of each UV-blocking cosmetic composition to a clean test site of the subject, drying it naturally for 20 minutes, rolling it 50 times at the same pressure with 50 mL of lukewarm water, and washing it with a UV camera VISIA-CR (Canfiled Scientific, USA). At this time, after washing with lukewarm water, the water resistance effect was determined to the extent of the residual amount of each cosmetic composition for UV protection. It can be judged that the darker the contrast in the UV camera measurement, the less the UV-blocking material is washed off by water and thus has better water resistance.

5 is a water resistance evaluation result of Example 2 and Comparative Example 4.

As shown in FIG. 5 , it was confirmed that both Example 2 and Comparative Example 4 exhibited the same brightness and darkness after application and before washing with water. After washing with lukewarm water, in Comparative Example 4 without the zwitterionic chitosan derivative, a lot of sunscreen was removed, and the contrast was pale. On the other hand, Example 2 containing the zwitterionic chitosan derivative showed a strong contrast. In particular, in the case of Example 2, compared to after application, it was slightly brighter and showed similar contrast. Through this, it was confirmed qualitatively that Example 2 containing the zwitterionic chitosan derivative had a water resistance effect.

Table 3 shows the results of confirming water resistance through brightness. Brightness analysis was measured using ImageJ software. As shown in Table 3, Comparative Example 4 without zwitterionic chitosan derivative increased brightness by about 33.29% when rolling after washing with lukewarm water, and Example 2 containing zwitterionic chitosan derivative increased brightness by 11.17% became That is, when zwitterionic chitosan was contained, it was confirmed that the water resistance effect was excellent about 3 times.

group after application Washing with lukewarm water for 30 seconds + rolling 50 times Comparative Example 4 100.00 133.29 Example 2 100.00 111.17

The description of the present invention described above is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (10)

A cosmetic composition having water resistance, comprising a zwitterionic chitosan derivative. The cosmetic composition according to claim 1, wherein the zwitterionic chitosan derivative comprises a repeating unit represented by the following formula (1).
[Formula 1]

(In Formula 1, X is the same or different from each other in each repeating unit and is each independently H, -COCH ₃ or an anionic moiety.) The method according to claim 2, wherein the anionic moiety is any one selected from the group consisting of -RSO ₃ H, -RCOOH and -RPO ₂ HR', wherein R and R' are each independently substituted or unsubstituted C1-C20 of an aliphatic or aromatic hydrocarbon group. The cosmetic composition of claim 2, wherein the zwitterionic chitosan derivative has a total number of repeating units of 10 to 1,000. The cosmetic composition according to claim 2, wherein the proportion of the repeating units in which X is an anionic moiety in Formula 1 among the total number of repeating units of the zwitterionic chitosan derivative is 60 to 99%. The cosmetic composition according to claim 1, wherein the zwitterionic chitosan derivative is included in an amount of 0.1 to 10% by weight based on the total weight of the composition. The method according to claim 1, wherein the aqueous phase comprising a zwitterionic chitosan derivative; And a cosmetic composition that is an oil-in-water emulsion formulation comprising an oil phase. The cosmetic composition of claim 7, wherein the aqueous phase further comprises a polyol. The cosmetic composition of claim 7, wherein the oily part further comprises an ester-based oil, a hydrocarbon-based oil, a vegetable oil, or a combination thereof. The cosmetic composition of claim 7, further comprising a sunscreen.

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