KR0150271B1 - Cosmetic compositions containing chitosan microsphere comprising ultra-violet-protecting materials - Google Patents

Abstract

The present invention provides a chitosan microsphere containing a specific active ingredient and a cosmetic composition containing the same. The chitosan microsphere of the present invention is useful for one or two or more cosmetics selected from ceramides, peptide derivatives, flavonoid compounds or animal and plant extracts. ingredient; Or one or two or more sunscreens selected from inorganic powders such as titanium oxide or zinc oxide, and organic sunscreens such as citamate, salicylate, fava or fava ester derivatives, in an amount of 0.01 to 50% by weight. It is characterized in that, the composition of the present invention contains the above chitosan microspheres in an amount of 0.01 to 30% by weight based on the total weight of the composition.

Description

Chitosan microspheres containing a useful component or sunscreen material for cosmetics and a cosmetic composition containing the same.

The present invention relates to chitosan microspheres encapsulated with ceramides, peptide derivatives, flavonoid derivatives or flora and fauna derivatives, or sunscreen substances as cosmetic useful components and cosmetic compositions containing the same.

Chitosan is a naturally occurring amino polysaccharide that is homozygous of D-glucosamine obtained by deacetylating chitin contained in the cell walls of microorganisms such as crab, shrimp skin, squid bone, mold, mushrooms and bacteria. Homopolymer. Their main role in living organisms is to form the exoskeleton of living bodies, protecting them from the outside environment and maintaining homeostasis. Although not much research has been carried out compared to cellulose, which is a component of plants, in recent years, more and more studies have been conducted in terms of waste disposal and resource recycling.

Chitosan can be easily obtained from chitin, which has excellent biocompatibility, is widely present in nature, and has abundant resources, and there are active researches to use it as a medical material such as hemodialysis membrane, antithrombogenic material, surgical suture, and artificial skin. have. In addition, chitosan has an amino group, unlike cellulose, and has been studied for industrial use by synthesizing various derivatives using the same.

In addition, recent studies on tumor suppression effect and anticancer activity have been published, and US Patent No. 3,632,754 has reported that chitosan acts as a wound healing agent. Chitosan is slowly hydrolyzed by enzymes in vivo, and is particularly easily degraded by Lysozyme, an enzyme that is abundant in the wounds of the skin. Hydrolyzed products such as oligomers and dimers have been shown to continuously promote wound healing for a long time.

On the other hand, if you look briefly at some examples of chitosan microspheres, which are being studied recently for use development, first, chitosan microspheres are mostly manufactured by crosslinking reaction of chitosan and glutaraldehyde, and they have macrophage activation ability. It is reported that the microspheres thus prepared have no significant difference in chitosan itself and activity.

The present inventors have established an improved method for preparing chitosan microspheres (Korean Patent Application No. 94-8822), and most of the ceramides, peptide derivatives, etc., which are currently being spotlighted as bioactive substances in cosmetic fields, are easily used in cosmetic bases. While studying various methods to solve the problem of precipitation, decomposition or denaturation of crystals, the inclusion of these useful ingredients in chitosan microspheres solved the problems found in the past and the synergistic effect of cosmetic ingredients increased synergistically. Confirmed the facts and completed the present invention.

Furthermore, the inventors of the present invention suggest that the use of chitosan microspheres is an opaque material that blocks or disperses sunlight, and acts as a mechanical barrier. It has also been found that chemical sunscreens that exhibit selective protective action only can be entrapped simultaneously.

Accordingly, an object of the present invention is one or two or more cosmetic useful components selected from ceramides, peptide derivatives, flavonoid compounds or animal and plant extracts; Or chitosan microspheres containing inorganic powders such as titanium oxide or zinc oxide, and one or two or more sunscreen materials selected from organic sunscreens such as citamate, salicylate, fava or fava ester derivatives. To provide.

Another object of the present invention is to provide a cosmetic composition containing the chitosan microspheres described above.

Other objects and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

Substances that can be used in cosmetics had to satisfy functionalities such as appearance, usability, safety, stability and efficacy, effects, and usability. Bioactive substances such as ceramides, peptide derivatives, and natural plant and animal extracts have relatively good appearance, usability, and functional safety, but have problems such as precipitation or deterioration with time-dependent changes in cosmetics, especially liquid products. , Chitosan has excellent film forming ability on skin and maintains proper moisture even in small amount. In addition, it has excellent biocompatibility and excellent affinity with skin or hair, and has a property of forming a very natural and soft film, and thus has been used as a cosmetic raw material itself.

According to the research of the present inventors, chitosan is a polymer electrolyte having an amino group and has a property of forming a liquid crystal, and ceramide also strengthens the connective tissue of the skin through liquid crystal formation and maintains proper moisture on the skin. It is known to give. Peptide compounds are known to be effective as epidermal growth factor of the tripeptide derivatives of glycine histidine-lysine, which can promote wound healing of the skin. Therefore, microspheres of these useful components with chitosan can quickly heal wounds at the inflamed area of the skin and at the same time strengthen the connective tissues of the cells and maintain proper moisture on the skin, as well as maintain the activity of the materials used for a long time. Can increase the effect.

In particular, it is well-known that herbal medicines, pollen containing flavonoids, and some natural plant and animal extracts such as flavonoids and placenta may promote skin cell growth, antioxidant activity or whitening effect depending on their function. to be. Herbal medicines containing flavonoids have been used to treat various diseases since ancient times, and are known to have the effect of restoring vitamin C and vulnerable capillaries. Currently considered flavonoids in plants have been reported to filter against ultraviolet rays and antioxidants by scavenging free radicals and various radicals that are harmful to living organisms. Recently, it has been found that the flavonoid component inhibits the production of lipid peroxide, which causes aging, in animal cells.

Conventionally, the amount of these formulations used has been limited. That is, the ceramide peptide derivatives cause problems such as precipitation, and the flavonoids, especially the green tea flavonoids (-)-epicarocatechin gallate, (-)-epicarocatechin, (-)-epicatechin, and the like, are hydrolyzed and photolyzed. There was a problem as it happens easily.

However, the present inventors have been able to solve this problem by using chitosan microspheres, and at the same time, the cosmetic effect, that is, excellent stability in the formulation of cosmetics, etc., and evenly used on the skin without leaving any residues seen in conventional collagen microspheres. The present invention has completed the present invention by confirming that there is an advantage of forming a thin and moisturizing film spreading and synergistically increasing the skin inflammatory effect.

Meanwhile, many types of microspheres have been developed and used in the fields of cosmetics, ie, skin cosmetics, makeup cosmetics, and hair cosmetics. When a microsphere made of a cationic resin is added to cosmetics, It is known that it has good adsorption to the surface of the hair and maintains long-lasting properties, and especially has the effect of suppressing the generation of static electricity in hair cosmetics. [Textile Resarch Journal, No 9, 616-620 (1977) )]. In addition, although it is known that the cationic group can be introduced into a conventional ultraviolet absorber to improve the persistence of hair or skin [Cosmetics Toiletries, Vol. 102, 71-80 (1987)], There is no example of microspheres using chitosan alone or in combination with a physical type sunscreen and a chemical type UV absorber. Chitosan microspheres containing the sunscreen material of the present invention is less absorbed by the skin has fewer side effects.

Sunscreens used for the purposes of the present invention can be used without limitation as long as they are commonly used in the cosmetic field, they can be microsphereized using techniques well known in the art. Inorganic powders such as titanium oxide, magnesium silicate, magnesium oxide, zinc oxide, kaolin and the like of physical type may be added by dispersion techniques commonly used in the cosmetic field, and chemical type sunscreens such as dioxybenzone, Mixtures of lowson and dihydroxyacetone, methyl anthranilate, benzophenone-4, octyl salicylate, triethanolamine salicylate, synoxate, oxybenzone, octocrylene, decaloyltrioleyl, Paradimethyl benzoic acid amyl, diethanolamine paraethoxycinnamate, paraamino benzoic acid, glyceryl pava, ethyldihydroxypropyl pava, octyldimethyl pava, 2-phenylbenzoimda group-5-sulfonic acid, homoslate, draw Methazole, butylmethoxydibenzoylmethane, octyltrizone, 3- (4-methylbenzylidene) campa and its derivatives were added using techniques known in the emulsification art Micro spheres may hwahal.

Useful ingredients contained in the microspheres of the present invention are ceramides or derivatives thereof, peptide derivatives, flavonoid compounds or animal and plant extracts widely used in the cosmetic field, and there are no particular limitations on the kind and amount thereof. Its type and effective amount can be easily determined.

However, the amount of the useful component or sunscreen contained in the chitosan microsphere of the present invention is preferably 0.01 to 50% by weight.

Chitosan microspheres of the present invention may be contained in an amount of 0.01 to 30% by weight based on the total weight of the cosmetic composition. The cosmetic composition containing the chitosan microspheres of the present invention may have various formulations of hair cosmetics, basic cosmetics, and makeup cosmetics, and may appropriately increase or decrease the amount of microspheres added according to the formulation and use purpose of these cosmetic compositions. have.

Chitosan microspheres according to the present invention can be used in combination with most skin cosmetics such as creams, essences, shampoos, rinses, hair treatments, hair gels, hair pomades and the like.

The composition containing the chitosan microsphere of the present invention has excellent skin moisturizing power and helped to maintain homeostasis of the living body by appropriately controlling moisture evaporation of the skin. Conventional moisturizers that have been used to moisturize the skin include glycerine, propylene glycol, and the like, obtained by chemical methods. In addition, glycols such as diethylene glycol monoethyl ether and the like or ether or sorbitol solution thereof have been used. In addition to these moisturizers, natural moisturizers containing hararuronic acid and amino acids as polymers are widely used. However, they are somewhat lacking in the ability to continuously provide a constant moisture and temporarily provide sufficient moisture to give skin shine and elasticity, and they have less physiological activity and have only a moisturizing effect. However, the composition of the present invention is characterized by having a physiological activity and a moisturizing effect at the same time using a bio-use component.

In addition, since chitosan is electrically cationic, there is also an excellent conditioning and antistatic effect by electrostatic interactions on the skin and hair which are anionic under normal conditions. In addition, chitosan is a kind of amiropolysaccharide and is known to have an effect of restoring damaged skin and hair. The present inventors have found that the state of skin and hair is synergistically improved as a result of the microspheres of chitosan, which contain ceramides, peptide derivatives, and flavonoids, plant extracts.

The manufacturing method of the chitosan microsphere of the present invention is as follows.

Chitosan having a deacetylation degree of 50 to 100% is dissolved in an aqueous solution of 1 to 10% by weight of an organic or inorganic acid at a concentration of 1 to 5% by weight, and water-in-oil emulsifiers, hydrophobic solvents or oils, and 0 to 10% by weight of alcohols. Add to the solution included to make a water-in-oil colloidal suspension. At this time, the organic acid may be acetic acid, lactic acid, citric acid, tartaric acid, malic acid, formic acid, and the like as a solvent capable of dissolving chitosan, and hydrochloric acid, sulfuric acid, etc. may be used as the inorganic acid. Preferred solvents are acetic acid, and these can be used alone or in admixture at an appropriate ratio.

As the emulsifier, nonionic HLB values of about 1 to about 8 can be used, for example fatty acid mono / diglycerides, sorbitan monostearate, sorbitan trioleate, sorbitan monooleate, sorbitan fatty acid esters, A sorbitan sesquioleate, polyoxyethylene (5) castor oil, polyoxyethylene (4) nonylphenyl ether, etc. can be used. These single holes can be mixed and used in an appropriate ratio. The amount of emulsifier used is 0.1 to 10 parts by weight based on the total weight of the emulsion.

As an oil, Hydrocarbon compounds, such as a liquid paraffin; Oils in ester form such as isopropyl myristate; Or branched higher fatty alcohols such as isocetyl alcohol.

Hydrophobic solvents include aromatic compounds such as toluene and benzene; Hydrocarbon compounds such as pentane, hexane, cyclohexane and the like; Low molecular weight ester compounds such as ethyl acetate; And petroleum ether, methylene chloride, ethylene chloride, chloroform and the like can be used.

On the other hand, the emulsification can be performed by a mechanical method using an agi-mixer, a homo-mixer, an ultrasonic device, or a colloid mill. The emulsification time to obtain the desired size, for example 200-400 mesh size microspheres, depends on several conditions, including the emulsifying apparatus used, but for example in the range of 1-80 hours when using an ultrasonic apparatus. Is in.

Examples of the crosslinking-forming reagent used to obtain the chitosan microspheres by treating the chitosan-containing emulsion obtained as described above include epichlorohydrin; Symmetric acid anhydrides such as acetic anhydride or di-t-butyl-dicarbonate; Alkali such as ammonia water, sodium hydroxide, potassium hydroxide; Or symmetric anhydride amino acid in which an amino group was protected can be illustrated.

Symmetric anhydrous amino acids in which the double amino group is protected can be prepared by reacting 2 equivalents of the amino group protected with 1 equivalent of the coupling reagent. The protecting group of the amino group is benzyloxycarbonyl group, 9-fluorenyl methoxycarbonyl group, 2,2,2, -trichloroethoxycarbonyl group, glutaraldehyde, epichlorohydrin, terephthalic group among those generally used in the field of peptide chemistry. Mostly used for the crosslinking reaction of polymers such as loyl chloride, terephthaloyl succinimide, terephthaloyl bis-ene-curprolactam, but are particularly suitable for the purposes of the present invention 읕 terephthaloyl chloride or epi Chlorohydrin.

Although it is preferable to manufacture the microsphere of the present invention by adopting the above-described method, in addition to the above-described chemical method or physicochemical method can be adopted.

Chemical methods include treatment of acid anhydride t-butyloxycarbonyl anhydride, anhydrides of t-butyloxycarbonyl-substituted amino acids, benzyloxycarbonyl chloride, acyl chloride, benzoyl chloride and the like. There is a method of changing the liquidity of the solution by a physicochemical method, a method of adding carboxymethyl chitin salt, carboxymethyl cellulose salt, hyaluronic acid salt, alginate salt and gelatin. Carboxymethylchitin salts, hyaluronic acid names, and alginates that may be used to prepare the microspheres of the present invention have a molecular weight of 100,000 to 2,000,000. Gelatin is suitable to have a molecular weight of about 20,000 to 200,000, in particular gelatin is easy to solidify below 40 ℃ to maintain the objective of the present invention to 40 to 50 ℃ and slowly added dropwise to the chitosan solution and then cooled. .

In the present invention, chitosan used to form microspheres for inclusion of various active ingredients is chitinol deacetylated, and a technique for preparing chitosan through deacetylation of chitin is generally known. It is made by the following method. Chitin in shells of crustaceans commonly used as a raw material for chitin coexists with inorganic salts containing calcium carbonate, proteins and lipids containing pigments. It is common to remove inorganic salts, proteins, pigments and lipids sequentially by treatment with hydrochloric acid, dilute sodium hydroxide and organic solvents. That is, about 220 parts by weight of dried crustacean shells were precipitated in 2 liters of 2 normal hydrochloric acid at room temperature for 5 hours, followed by washing with water, drying and grinding, and then again treated with 500 milliliters of cold hydrochloric acid for 48 hours to remove inorganic salts, and the precipitates were washed with water. Subsequently, the procedure of heating with 500 ml of 1-normal sodium hydroxide for 12 hours at 100 ° C. was repeated four times to remove proteins, and finally washed sequentially with water, ethanol and ether, and then vacuum dried. Separation of chitinol from shellfish shells, treatment with sodium carbonate for deproteinization, immersion in 10% sodium hydroxide solution at room temperature for 3 days, and shaking for 18 hours at room temperature with 90% formic acid instead of organic solvents There is this.

On the other hand, as a method for producing a biological chitin, one solution is to use chitin deacetylase or a microorganism producing the enzyme in order to avoid depolymerization of the main chain simultaneously with deacetylation when producing chitosan using high alkali. These methods cannot be compared simply depending on conditions such as treatment time and treatment temperature, but overall removal of coexisting proteins is difficult by protease treatment alone, and protein removal rate varies greatly depending on the type of raw shell and the type and combination of protease. Is common.

On the other hand, as a manufacturing method of chitosan by the chemical method, there exists a method of heating in 30-60% of concentrated alkali solution normally as a refined chitinol raw material. In addition, there is a method of obtaining chitosan having a degree of deacetylation of 95% by treatment in molten potassium hydroxide at 180 ° C. for 30 minutes, and a method of deacetylating in a mixture of 50 g of potassium hydroxide, 25 g of ethanol, and 25 g of ethylene glycol.

On the other hand, the deacetylation for the production of chitosan, the penetration of the sodium hydroxide solution varies depending on the thickness and size of the shell, so the larger the particle size distribution of the raw material, the greater the molecular weight distribution of the product. Therefore, it is good to make the distribution of particle size as constant as possible when grinding raw materials. The amount of 50% sodium hydroxide used in the reaction needs to ensure that the chitin is sufficiently submerged and about 20 times that of the chitin is sufficient. The chitosan thus obtained is preferably pulverized finely in a dry state. Chitosan to be used for the purpose of the present invention is not limited to the production method, it is preferable to have a particle size of 100 mesh or more to improve the diffusion rate to the solvent.

Hereinafter, the present invention has been described in detail through various examples.

Example 1

20 grams of chitosan with 80% deacetylation was added to 980 grams of 2% acetic acid solution and dissolved. Two grams of (-)-epigallocatechin gallate (EGCG) and 1 gram of glucosyl ceramide, green tea flavonoids, were dissolved in 10 grams of purified water and added to the chitosan solution with stirring. Dissolve about 5 grams of sorbitan trioleate (trade name: Arlacel 85, manufacturer: ICI) in 600 grams of cyclohexane, add it to the chitosan solution with stirring, and emulsify at 35 ° C and 7000 rpm for 3 minutes to obtain a uniform water-in-oil emulsion. . After cooling to room temperature, the emulsion solution was slowly added to 2 liters of 2% sodium hydroxide, stirred at 800 rpm for 30 minutes, and then slowly added dropwise about 200 grams of 0.5% hyaluronate to form chitosan microspheres containing useful components. Filtration was carried out using a 200 mesh filter cloth, purified water was added thereto, washed several times, and then 95% ethanol and methanol ethyl ether were sequentially added to obtain about 18 grams of chitosan microspheres.

Example 2

25 grams of chitosan having a deacetylation degree of 65% was gradually added to 1 liter of 2% by weight of acetic acid, stirred to dissolve completely, bubbles were removed, and centrifuged to remove a small amount of insoluble matter. One gram of each of glucosyl ceramide and N-palmitoyl-glycine-histidine-lysine (trade name, Biopeptide CL, manufacturer: Cedma, France) was dispersed and dissolved in 10 milliliters of purified water, and then added to the chitosan solution. 50 grams of sorbitan monooleate (trade name: Arlacel 80, manufacturer: ICI) was dissolved in 400 grams of ethanol, and 70 grams of toluene were added thereto, followed by uniform dissolution. The organic layer was slowly added to the aqueous layer with stirring to mix to form a uniform suspended colloidal solution. 100 grams of sorbitan monooleate and 1 liter of acetic anhydride were added to 10 liters of toluene, and then the above-mentioned chitosan-containing suspension colloidal solution was slowly added dropwise to make a water-in-oil emulsion and stirred for 48 hours in a 40 ℃ thermostat. . The supernatant was removed, and about 8 liters of ethanol / ammonia (7: 3 V / V) were added, followed by stirring for about 1 hour and centrifugal filtration to obtain spherical microspheres. Again, it was dispersed in excess ethanol and acetone, filtered to remove unreacted material, and finally washed with ether and dried under reduced pressure at 30 ° C. to obtain about 20 grams of chitosan microspheres.

Example 3

10 grams of chitosan with 90% deacetylation was dispersed in 100 grams of purified water, and placed in a constant temperature water bath at 50 ° C. with 10% acetic acid while stirring to bring the pH to 5.5, followed by complete dissolution and vacuum removal. 0.5 grams of glucosyl ceramide was dissolved in 20 grams of purified water and added to the chitosan solution. A solution of 14 grams of dichloromethane, 80 grams of ethyl alcohol, and 7 grams of sorbitan sesquioleate was slowly added to form a colloidal suspension of gel, followed by 20 grams of benzyloxycarbonyl glycine symmetric anhydride, 800 grams of dichloromethane, and sorbbi. A water-in-oil emulsion was prepared by immersing the colloidal suspension slowly for about 30 minutes in an ultrasonic generator in a uniform solution containing 12 grams of tan sesquioleate and applying ultrasonic waves continuously. Ultrasonic waves were applied for 3 hours while the temperature of the emulsion solution was adjusted so as not to exceed 40 ° C. The reaction was stopped, the supernatant was removed, washed well with an excess of dichloromethane, ethanol, methanol, acetone, and ether, followed by vacuum drying to obtain about 11.5 grams of chitosan microspheres bound with glycine.

Example 4

1.6 grams of chitosan with 95% deacetylation, 0.5 grams of (-)-epigallocatechin gallate, 0.5 grams of glucosyl ceramide, 0.3 grams of panthenol in 100 grams of 5% acetic acid, and polyoxyethylene (5) castor oil ( Product name: TRYLOX CO-5, manufacturer: EMERY) 2g, sorbitan monooleate 2g, methanol 30g, and isopropyl myristate 65g were added gradually to the solution containing the dissolved solution of colloidal white turbid liquid. . Homo-mixing for 1 minute to make the chitosan uniform and agi-mixing again, 50 grams of acetic anhydride, 500 grams of isopropyl myristate, 5 grams of polyoxyethylene (5) castor oil, The above-mentioned suspension liquid was slowly added dropwise over about 20 minutes while azimixing the solution containing 3 grams of sorbitan monooleate uniformly at 1200 rpm. After stirring for 72 hours, the supernatant was removed and about 1 liter of ethanol / 1N-sodium hydroxide (6: 4, V / V) was added. After stirring for about 30 minutes, centrifugal filtration, and washed with purified water, 95% ethanol, acetone, ether. Yellow pigment 4 (0.25%) was added to about 100 milliliters, stirred for about 10 minutes, and filtered to obtain a microsphere colored in yellow. After centrifugal filtration, the product was washed with 95% ethanol, methanol, acetone, and ether, followed by vacuum drying to obtain about 1.4 grams of yellow chitosan microspheres having a particle size of 200 to 400 mesh.

Example 5

6 g of deacetylation degree 75% of chitosan was added to 200 ml of a 2% acetic acid solution and dissolved at 40 ° C. to obtain a viscous colorless transparent solution. 1 gram of N-Pamitoyl-glycine-histidine-lysine (trade name: Biopeptide CL, manufacturer: Cedma, France) was added uniformly, dispersed in a viscous chitosan solution, 40 grams of isopropyl alcohol, and 5 grams of sorbitan thiolilate. , While stirring a solution of 8 grams of methylene chloride uniformly, the preceding chitosan solution was gradually added to prepare a colloidal suspension solution. This was stirred into a solution in which 10 grams of symmetric anhydrous phenylalanine, 500 milliliters of methylene chloride, and 8 grams of sorbitan trioleate prepared from 2 equivalents of benzyloxycarbonylphenyl aladin and 1 equivalent of dicyclohexylcarbodiimide were dissolved. Gradually added dropwise. The ultrasonic generator was squeezed and successively applied to make a water-in-oil emulsion, and the reaction was continued for 2 days at 30 ° C. After the reaction, the supernatant was removed using a filter cloth, washed with methanol, acetone, and ether, and dried in vacuo to obtain about 6.5 grams of microspheres colored in white.

Example 6

Six grams of chitosan having a deacetylation degree of 100% was added to 0.5% acetic acid in a 37 DEG C thermostat to uniformly dissolve and then a 1% chitosan solution. To this was added 1 gram each of (-)-epigallocatechingallate, N-famitoyl-glycine-histidine-lysine, and then 40 grams of anhydrous isopropyl alcohol and polyoxyethylene (4) nonylphenyl ether at room temperature. : TERGITOL NP-4, manufacturer: US Union Carbide) 4 grams, fatty acid mono / diglycerides (trade name: ATMER 121, manufacturer: ICI) 1 gram, 8 grams of ethylene chloride, while stirring the solution of chitosan slowly The colloidal suspension solution was prepared. A solution in which 12 grams of symmetric anhydrous phenylalanine, 500 milliliters of methylene chloride, and 8 grams of polyoxyethylene (6) nonylphenyl ether prepared uniformly from 2 equivalents of benzyloxycarbonylphenyl aladin and 1 equivalent of dicyclohexylcarbodiimide It was slowly added dropwise while stirring into it. The reaction was carried out in a water-in-oil emulsion state by applying ultrasonic waves at 30 ° C. for 8 hours, the supernatant was removed by centrifugation, and the filtrate was washed with ethanol / distilled water (1: 1) until the liquid became neutral. Again washed well with mid-water to give a pale yellow chitosan microsphere.

Example 7

About 90 grams of the chitosan-containing suspension colloidal solution prepared in Example 1 was 600 grams of cyclohexane, 3 grams of polyoxyethylene (6) nonylphenylether, 8 grams of sorbitan monooleate, and sorbitan fatty acid ester (trade name: ATPET 200 , Mate: ICI) 1 gram was slowly added dropwise under stirring to prepare a solution in water-in-oil emulsion. 40 grams of acetic acid was added thereto and stirred at 35 ° C. for 36 hours. In the same manner as in Example 1 below, about 2.0 grams of microspheres were obtained.

Example 8

100 grams of the chitosan solution prepared in Example 2 was added to the solution containing 6 grams of liquid paraffin, 30 grams of benzene, and 3 grams of sorbetane sesquioleate (trade name: ARLACEL 83, manufacturer: ICI), which was added to the colloid of a cloudy solution. A phase liquid was made. 20 grams of acetic anhydride, 800 milliliters of benzene, and 8 grams of sorbitan sesquioleate were slowly added dropwise, stirred for 17 hours, and washed to obtain about 4.2 grams of spherical microspheres.

Example 9

50 grams of chitosan solution prepared in Example 3, 1.5 grams of sorbitan sesquioleate, 1 gram of glycerol capric / caprylic acid ester (trade name: ARLACEL 83, manufacturer: Goldschmidt Chemical Co.) 25 grams, n-pentane 25 grams, methanol 30 grams was added to the dissolved solution and ultrasonic wave was added for 5 minutes to prepare a uniform colloidal suspension solution. A solution of 2 grams of sorbitan sesquioleate and 1 gram of glycerol capric / caprylic acid ester in 400 milliliters of pentane was uniformly stirred, and the above-mentioned suspended colloidal solution was slowly added dropwise over about 30 minutes. . After completion of the addition, the mixture was agitated at 3000 rpm for 1 hour, and 40 grams of ammonia water was slowly added dropwise. After stirring was continued for 3 hours, the filtrate was washed with purified water until the liquid liquid became neutral and washed in the order of 50% ethanol, ethanol, methanol. Vacuum drying yielded approximately 0.45 grams of chitosan microspheres.

Example 10

Except that in Example 2, instead of 20 grams of benzyloxycarbonyl glycine symmetric acid anhydride, 25 grams of symmetric acid anhydride was prepared using 1 equivalent of diisopropyl carbodiimide and 2 equivalents of 9-fluorooleylmethoxycarbonyl glycine. The experiment was carried out in the same manner to obtain about 12 grams of chitosan microspheres.

Example 11

About 90 grams of the chitosan-containing suspension colloidal solution prepared in Example 1 was slowly added dropwise to the solution containing 600 grams of n-hexane, 3 grams of polyoxyethylene (6) nonylphenylether, and 1 gram of sorbitan fatty acid ester. After the mixture was dispersed evenly, 3 grams of 25% glutaraldehyde was slowly added dropwise and stirred for about 30 minutes, 600 grams of n-hexane was added thereto, stirred at about 3000 rpm, filtered and washed well with ethanol, methanol, and purified water. The chitosan microsphere of the invention was obtained.

Example 12

100 grams of the chitosan solution prepared in Example 2 was added to the solution in which 6 grams of liquid paraffin, 30 benzenes, and 3 grams of sorbitassesquioleate were added with stirring, followed by 20 grams of terephthaloyl chloride, 800 milliliters of benzene, and sorbbi. 6 grams of tan sesquioleate was slowly added dropwise, stirred for about 20 hours, and washed and dried to obtain about 4.3 grams of chitosan microspheres.

Example 13

In Example 3, about 11.8 grams of chitosan microspheres containing (-)-epigallocatechin were carried out in the same manner except that 1.2 grams of (-)-epigallocatechin were used instead of 0.5 grams of glucosyl ceramide. Got it.

Example 14

(-)-Epigal was carried out in the same manner as in Example 4, except that 1.2 grams of (-)-epigallocatechin and 1 gram of titanium dioxide were used instead of 0.5 grams of (-)-epigallocatechin gallate. About 11.7 grams of chitosan microspheres containing locatechin were obtained.

Example 15

20 grams of chitosan with 80% deacetylation was added to 980 grams of 2% acetic acid solution and dissolved. Two grams of titanium dioxide and one gram of 2-hydroxy-4-methoxybenzophenone were added to the chitosan solution while stirring. Dissolve about 5 grams of sorbitan trioleate (trade name: Arlacel 85, manufacturer: ICI) in 600 grams of cyclohexane, add it to the chitosan solution with stirring, and emulsify at 35 ° C and 7000 rpm for 3 minutes to obtain a uniform water-in-oil emulsion. . After cooling to room temperature, the emulsion solution was slowly added to 2 liters of 2% sodium hydroxide, stirred at 800 rpm for 30 minutes, and then slowly added dropwise about 200 grams of 0.5% hyaluronate to form chitosan microspheres containing useful components. Filtration was carried out using a 200 mesh filter cloth, and purified water was added and washed several times to obtain about 18.5 grams of chitosan microspheres of the present invention.

Example 16

25 g of deacetylation was added slowly to 1 liter of acetic acid 2% by weight of chitosan, which was completely dissolved by stirring, to remove bubbles, and centrifuged to remove a small amount of insoluble matter. One gram of titanium dioxide is slowly added to the chitosan solution for dispersion. 50 grams of sorbitan monooleate (trade name: Arlacel 80, manufacturer: ICI) was dissolved in 400 grams of ethanol, and 70 grams of toluene were added thereto, followed by uniform dissolution. The organic layer was slowly added to the aqueous layer with stirring to mix to form a uniform suspended colloidal solution. 100 grams of sorbitan monooleate and 1 liter of acetic anhydride were added to 10 liters of toluene, and then the above-mentioned chitosan-containing suspension colloidal solution was slowly added dropwise to make a water-in-oil emulsion and stirred for 8 hours in a 40 ℃ thermostat. . The supernatant was removed, and about 8 liters of ethanol / ammonia (7: 3 V / V) were added, followed by stirring for about 1 hour and centrifugal filtration to obtain spherical microspheres. Lyophilization yielded approximately 20 grams of chitosan microspheres.

Example 17

10 grams of chitosan with 90% deacetylation was dispersed in 100 grams of purified water, and placed in a constant temperature water bath at 50 ° C. with 10% acetic acid while stirring to make the pH to 5.5, and then completely dissolved and bubbles were removed by vacuum. One gram of titanium dioxide and 0.5 grams of 2-hydroxy-4-methoxybenzophenone-5sulphonic acid were added to the chitosan solution. A solution of 14 grams of dichloromethane, 80 grams of ethyl alcohol, and 7 grams of sorbitan sesquioleate was slowly added to form a colloidal suspension of gel, followed by 2 grams of glutaraldehyde, 800 grams of dichloromethane, and sorbitan sesquioleate 12 The gram-containing homogeneous solution was immersed in an ultrasonic generator, and the gel colloid suspension was slowly added dropwise for about 30 minutes while applying ultrasonic waves continuously to form a water-in-oil emulsion. Ultrasonic waves were applied for 3 hours while the temperature of the emulsion solution was adjusted so as not to exceed 40 ° C. The reaction was stopped, the supernatant was removed, washed well with distilled water and lyophilized to obtain about 11.5 grams of chitosan microspheres of the present invention.

Example 18

0.5 grams of titanium dioxide was dispersed in 100 grams of 5% acetic acid containing 1.6 grams of chitosan with 95% deacetylation, and 2 grams of polyoxyethylene (5) castor oil (trade name: TRYLOX CO-5, manufacturer: EMERY) , 2 grams of sorbitan monooleate, 30 grams of methanol, and 65 grams of isopropyl myristate were gradually added to a solution containing homogeneous dissolution to form a colloidal cloudy liquid. After homomixing for 1 minute to make the chitosan uniform and azimixing, 50 grams of acetic anhydride, 500 grams of isopropyl myristate, 5 grams of polyoxyethylene (5) hardened castor oil, and 3 grams of sorbitan monooleate The suspension liquid described above was slowly added dropwise over about 20 minutes while the dissolved solution was uniformly agitated at 1200 rpm. After stirring for 8 hours, the supernatant was removed and about 1 liter of ethanol / 1N-sodium hydroxide (6: 4, V / V) was added. After stirring for about 10 minutes, centrifugal filtration and washing with purified water, 95% ethanol, acetone, ether. Yellow pigment 4 (0.25% aqueous solution) was added to about 100 milliliters, stirred for about 10 minutes, and filtered to obtain a yellow colored microsphere. After centrifugal filtration, the product was washed with 95% ethanol, methanol, acetone, and ether, followed by vacuum drying to obtain about 1.4 grams of yellow chitosan microspheres having a particle size of 200 to 400 mesh.

Example 19

6 g of deacetylation degree 75% of chitosan was added to 200 ml of a 2% acetic acid solution and dissolved at 40 ° C. to obtain a viscous colorless transparent solution. Using colloid mill, one gram of titanium dioxide was uniformly dispersed in a viscous chitosan solution, and then the solution of the chitosan was dissolved while stirring a solution of 40 grams of isopropyl alcohol, 5 grams of sorbitan trioleate, and 8 grams of methylene chloride. The solution was slowly added to prepare a colloidal suspension solution. The same procedure was followed except that terephthaloyl chloride was used instead of glutaraldehyde of Example 1 to obtain about 6.5 grams of chitosan microspheres of the present invention.

Example 20

Six grams of chitosan having a deacetylation degree of 100% was added to 0.5% acetic acid in a 37 DEG C thermostat to uniformly dissolve and then a 1% chitosan solution. One gram of titanium dioxide and glyceryl fava were added thereto, followed by 40 grams of anhydrous isopropyl alcohol and 4 grams of polyoxyethylene (4) nonylphenyl ether (trade name: TERGITOL NP-4, manufacturer: Union Carbide corp). A colloidal suspension solution was prepared by gradually adding a chitosan solution while stirring a solution in which 1 gram of fatty acid mono / diglyceride (trade name: ATMER 121, manufacturer: ICI) and 8 grams of ethylene chloride were uniformly stirred. 1 gram of terephthaloyl chloride, 500 milliliters of methylene chloride, and 8 grams of polyoxyethylene (6) nonylphenyl ether were gradually added dropwise while stirring into a uniformly dissolved solution. The reaction was carried out in a water-in-oil emulsion state by applying ultrasonic waves at 30 ° C. for 78 hours, and the supernatant was removed by distillation by centrifugation, and the filtrate was washed with ethanol / distilled water (1: 1) until the liquid became neutral. Again washed well with mid-water to obtain about 5.8 pale yellow chitosan microspheres.

Example 21

About 90 grams of the chitosan-containing suspension colloidal solution prepared in Example 15 was added 600 grams of cyclohexane, 3 grams of polyoxyethylene (6) nonylphenylether, 8 grams of sorbitan monooleate, and sorbitan fatty acid ester (trade name: ATPET 200 , Maker: ICI) 1 gram was slowly added dropwise to the solution dissolved in water to prepare a solution in water-in-oil emulsion. 40 grams of acetic acid was added thereto and stirred at 35 ° C. for 36 hours. In the same manner as in Example 15 below, about 2.0 grams of microspheres were obtained.

Example 22

100 grams of the chitosan solution prepared in Example 16 was added to the solution in which 6 grams of liquid paraffin, 30 grams of benzene, and 3 grams of sorbetane sesquioleate (trade name: ARLACEL 83, manufacturer: ICI) were added with stirring to form a colloid of a white cloud. Phase liquid was made. 20 grams of acetic anhydride, 800 milliliters of benzene, and 8 grams of sorbitan sesquioleate were slowly added dropwise, stirred for 17 hours, and washed to obtain about 4.2 grams of spherical microspheres.

Example 23

50 grams of chitosan solution prepared in Example 17, 1.5 grams of sorbitan sesquioleate, 1 gram of glycerol capric / caprylic acid ester (trade name: ARLACEL 83, manufacturer: Goldschmidt Chemical Co.) 25 grams, n-pentane 25 grams, methanol 30 grams was added to the dissolved solution and ultrasonic wave was added for 5 minutes to prepare a uniform colloidal suspension solution. A solution of 2 grams of sorbitan sesquioleate and 1 gram of glycerol capric / caprylic acid ester in 400 milliliters of pentane was uniformly stirred, and the above-mentioned suspended colloidal solution was slowly added dropwise over about 30 minutes. . After completion of the addition, the mixture was agitated at 3000 rpm for 1 hour, and 40 grams of ammonia water was slowly added dropwise. After stirring was continued for 3 hours, the filtrate was washed with purified water until the liquid liquid became neutral and washed in the order of 50% ethanol, ethanol, methanol. Vacuum drying yielded approximately 0.45 grams of chitosan microspheres.

Example 24

About 90 grams of the chitosan-containing suspension colloidal solution prepared in Example 15 was slowly added dropwise with stirring to a solution in which 600 grams of n-hexane, 3 grams of polyoxyethylene (6) nonylphenylether, and 1 gram of sorbitan fatty acid ester were dissolved. After the mixture was dispersed evenly, 3 grams of 25% glutaraldehyde was slowly added dropwise and stirred for about 30 minutes, 600 grams of n-hexane was added thereto, stirred at about 3000 rpm, filtered and washed well with ethanol, methanol, and purified water. About 9.3 grams of chitosan microspheres of the invention were obtained.

Example 25

100 grams of the chitosan solution prepared in Example 16 was added to the solution in which 6 grams of liquid paraffin, 30 benzenes, and 3 grams of sorbetane sesquioleate were added with stirring, followed by 20 grams of terephthaloyl chloride, 800 milliliters of benzene, and sorbbi. 6 grams of tan sesquioleate was slowly added dropwise, stirred for about 20 hours, and washed and dried to obtain about 4.3 grams of chitosan microspheres.

Specific cosmetic prescription examples of the present invention are as follows.

[Cosmetic Example 1]

Preparation Method: The raw materials 1, 4, 5, 7 were mixed and stirred by heating to 70 ~ 75 ℃. After adding the raw materials 2 to 3 to the raw material 10 and heating it to 70-75 ° C. to melt it, preliminary emulsification is carried out by adding the above oil phase part, and then emulsified uniformly with a homomixer, and then adding the raw materials 8 to 10 and cooling, and then the paddle. The raw material 6 was added stirring gradually with a mixer.

[Cosmetic Example 2]

Preparation Method: Raw materials 1 to 2 were added to the raw material 10, and dissolved at room temperature. Raw materials 3-5 and 7-9 were added to the raw material 6, and it melt | dissolved and added this to the water phase part mentioned above.

[Cosmetic charge example 3]

Preparation Method: Raw materials 1 to 3 were mixed and melted by heating. It cooled to 45 degreeC, and added the raw materials 4-11.

The effect of the present invention was described through the following test examples.

[Test Example 1]

Substantivity test by Rubin Dye Test [Richard J. Crawfork and Clarence R. Ronnins, J. soc. Cosmet. Chem, 31, 273-278, p273-278 (September / October 1980)]

Shampoo A (the present invention) and control shampoo B containing chitosan microspheres of Cosmetic Example 3 and the control shampoo B evenly discolored for 30 minutes with 3% hydrogen peroxide evenly for 4 minutes in 20 times the weight ratio of the hair. After washing, it was washed five times with distilled water corresponding to 50 times the weight of the hair. The red rubin die solution used in the experiment was prepared by dissolving 1.25 milliliters of acetic acid and 3.4 millimoles of Rubin Dye (molecular weight: 1472) per liter of water. The dye solution was treated for 1 minute, but the ratio of hair to rubin die urea was 1:20. The dyed hair was washed with distilled water corresponding to 50 times by weight ratio, dried at room temperature, and the intensity of the dyed color was measured through a colorimeter. The color intensity was calculated by Hunt's L * a * b * system (recording a * values).

As a result, the a * value of the shampoo containing the chitosan microspheres of the present invention was 0.35 and the control shampoo was 0.59, indicating substantivity for more than twice the hair.

[Test Example 2]

Time-lapse stability test of flavonoids by DPPH method

18 grams of chitosan microspheres of the present invention and 2 grams of the control green tea flavonoids were added to 100 milliliters of ethanol, and the stability of the green tea flavonoids over time was evaluated indirectly using the DPPH method. Y. Uehara, I., Morimoto. Y., Nakashima, M., Hatano. T., and Okuda, T: Yakugaku Zassi, 108 (2), 129 (1988)]: J. Agr. Chem. Soc (Jpn). Vol 45, no. 6, p292 (1971)]

That is, after one month of lapse, one gram of the present invention and the control solution were added to 0.5 milliliter of 0.2 mmol mol of DPPH (2,2-diphenyl-1-picrylhydrazyl) methanol solution, followed by 10 minutes at 25 ° C. After standing, the absorbance at 517 nanometers was measured. The DPPH solution was purple, and the reducibility of flavonoids was evaluated by the change in absorbance of DPPH. Experimental results showed about 50% depigmentation on DPPH wrapped in chitosan microspheres. Therefore, microspheres of flavonoids showed oxidative stability about 2 times after 1 month.

[Test Example 3]

The following results were obtained from 60 men in their 25s to 50s using the cosmetics containing no microspheres as a control for the cosmetics containing chitosan microspheres prepared in Example 1.

As described above, when the chitosan microsphere of the present invention was added to the after shave lotion, skin moisture, skin gloss, and skin elasticity were increased, and it was found that the effect of promoting wound healing was particularly excellent.

In addition, chitosan microspheres containing the sunscreen according to the present invention is a cosmetic, that is, hair cosmetics such as shampoo, hair rinse, hair mousse, hair gel and hair spray and basic cosmetics such as UV protection cream, lotion, foundation, compact, etc. It can be used in the same makeup cosmetics, especially when added to hair cosmetics, to prevent hair from being damaged, discolored or discolored by sun rays, especially ultraviolet rays, and added to basic cosmetics or makeup cosmetics. When used, it can effectively retard skin aging and burn easily. The chitosan microspheres containing the sunscreen of the present invention can be used alone, but are generally used in combination with a carrier for easy use as a cosmetic. The formulation compound of the present invention does not require special conditions.

They are known in the art and can be formulated in the form of emulsified products, aerosol products, solubilized products and used in various ways.

Claims (3)

One or two or more cosmetic useful ingredients selected from ceramides, N-palmitoyl-glycine-histidine-lysine or (-)-epigallocatechin gallate; A chitosan microsphere characterized in that one or two or more sunscreens selected from titanium oxide, zinc oxide, cinnamate, salicylate, fava, or fava ester derivatives are contained in an amount of 0.01 to 50% by weight. A cosmetic composition comprising the chitosan microspheres of claim 1 in an amount of 0.01 to 30% by weight based on the total weight of the composition. The cosmetic composition according to claim 2, wherein the cosmetic composition is a skin cosmetic or a hair cosmetic.