KR100628815B1 - Method for production of microcapsule containing water insoluble cellulose derivative and the microcapsule - Google Patents

Abstract

The present invention relates to a method for preparing microcapsules using water-insoluble cellulose derivatives and to microcapsules prepared therefrom. In particular, the present invention provides a method for preparing a microcapsule using a water-insoluble cellulose derivative capable of simply collecting the active ingredient inside the microcapsule and at the same time stabilizing the active ingredient, and a microcapsule prepared therefrom.

In another aspect, the present invention provides a cosmetic containing the microcapsules that can maintain the effect of the active ingredient for a long time by applying the microcapsules prepared by the method of the present invention to the cosmetic.

Microcapsules, Water Insoluble Cellulose, Active Ingredients

Description

METHOD FOR PRODUCTION OF MICROCAPSULE CONTAINING WATER INSOLUBLE CELLULOSE DERIVATIVE AND THE MICROCAPSULE}

Figure 1 is a SEM photograph of the microcapsules prepared in Example 3.

Figure 2 is a SEM photograph of the microcapsules prepared in Example 4.

[TECHNICAL FIELD OF THE INVENTION]

The present invention relates to a method for preparing microcapsules using a water-insoluble cellulose derivative and a microcapsule prepared therefrom, and more particularly, to effectively stabilize an active ingredient or an enzyme having a characteristic of rapidly decreasing stability. It relates to a method for preparing microcapsules which are insoluble cellulose derivatives and microcapsules prepared therefrom.

[Private Technology]

With the development of the cosmetics industry, the diversification of raw materials used in cosmetics is appearing, and the development of many cosmetic raw materials having an effective function to the human body is continuously made. Recently, as the value of functional cosmetics increases in the cosmetics industry, researches on a method of stably delivering the effects of the raw materials to the human body along with the development of raw materials have been focused. However, many substances having a function effective to most humans are not easily applied to cosmetics despite their effectiveness. The main reason is the instability of the raw materials. In general, cosmetic formulations contain a number of components, such as surfactants, water and oil, so most of the effective substances have an unstable characteristic that the activity is significantly reduced.

Methods for stabilizing the active substance include liposomes, stabilization using cyclodextrins, and microencapsulation. Liposomalization is a method of capturing the active ingredient therein using the self-association properties of lecithin. However, since the membrane component lecithin is compatible with water, oxygen present in the product or air may pass through the liposome membrane. Therefore, it is difficult to expect long-term stabilization of the active ingredient trapped inside the liposome, and also the method using the cyclodextrin is difficult to stabilize due to its structural features.

Microencapsulation is a method of preparing an active material in the form of particles having a particle size of about 1-1000 μm by enclosing the active material with a coating layer or a wall material. The microcapsule has a structure according to the hardness of the coating layer, the shape of the collected material, and a manufacturing method. It can be deformed and can be manufactured in a flexible, hard or brittle form according to the type of wall material. As a wall material, gelatin, gum arabic, alginic acid derivatives, agar, polyurethane, nylon, wax or colloidal silica are used, but water-soluble materials such as gelatin and agar have a problem that the active ingredient contained therein may become unstable. .

An example of the microencapsulation method is a microencapsulation method of the photochromic pigment of the Republic of Korea Patent No. 168215. The method uses a water-soluble polymer and water-insoluble cellulose as a wall material, more specifically, a photochromic pigment is dissolved in an organic solvent in which a cellulose compound is dissolved to prepare an oil phase, and a water-soluble polymer is dissolved in water to prepare an aqueous phase. The water phase was first emulsified to prepare a water in oil (W / O) emulsion, followed by secondary emulsification by adding an aqueous solution of a water-soluble polymer, completely evaporating the organic solvent of the secondary emulsion, and then curing with water for 2-3 days. To manufacture. The method has a disadvantage in that the manufacturing period is long, which increases the manufacturing cost.

In addition, Korean Patent Publication Nos. 2005-0005438 and 2005-0005437 disclose a method of coating a coating composition comprising a water-insoluble cellulose derivative, a nitrogen-containing polymer, a plasticizer and a surfactant or a lubricant to a pharmaceutically active ingredient, but the method Silver is an artificial coating method, not an emulsification method.

In order to solve the problems of the prior art, the present invention can easily collect the active ingredient inside the microcapsules, can maintain a stable active ingredient with low stability, long-lasting effect of the active ingredient An object of the present invention is to provide a microencapsulation method using a water-insoluble cellulose derivative that can be maintained as a wall material.

In addition, an object of the present invention is to provide a microcapsules prepared by the microencapsulation method, and to provide a cosmetic containing the microcapsules.

The present invention relates to a method for preparing microcapsules using a water-insoluble cellulose derivative as a wall material.

Specific microcapsule manufacturing method includes (a) dissolving a water-insoluble cellulose derivative in an organic solvent, adding an active ingredient to prepare an oil phase, (b) dissolving a water-soluble surfactant in water to prepare an aqueous phase, (c) ) Preparing an oil in water (O / W) emulsion by adding an oil phase to the aqueous phase, and (d) drying the emulsion to prepare microcapsules.

In the step (a), the water-insoluble cellulose derivative is added to 5 to 50 parts by weight with respect to 100 parts by weight of the organic solvent and mixed, and the active ingredient is added or dispersed to 0.1 to 30 parts by weight with respect to 100 parts by weight of the organic solvent to prepare an oil phase. do.

Examples of the water-insoluble cellulose derivative may be selected from the group consisting of ethyl cellulose, cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate. When two, three or four of the water-insoluble cellulose derivatives are selected, each component may be independently used in an amount of 1 to 10 parts by weight.

[Formula 1]

Ethyl cellulose in the formula (1) is when R is H or CH ₂ CH ₃ , cellulose acetate is when R is H or COCH ₃ . In addition, cellulose acetate propionate is when R is H, COCH ₃ or COCH ₂ CH ₃ , and cellulose acetate butyrate is when R is H, COCH ₃ or COCH ₂ CH ₂ CH ₃ .

The organic solvent may be a chlorine compound, a ketone compound or an ester compound. Preferred examples of the chlorine compound include methylene chloride, chloroform or carbon tetrachloride. Preferred examples of the ketone compound include methyl isobutyl ketone, isobutyl ketone or methyl ethyl ketone. Preferred examples of the ester compound are hexyl acetate and methyl acetate. , Ethyl acetate, dibutyl sebacate or dibutyl adipate, but are not limited thereto. The organic solvent may be used by selecting one or more kinds, and may be mixed in the range of 1 to 10 parts by weight, respectively, when using two or more kinds.

The active ingredient according to the present invention may be any conventional substance capable of inducing useful effects by exhibiting physiological activity in the human body, and preferred examples thereof are oil-soluble vitamins, oil-soluble sunscreens, oil-soluble antioxidants, oil-soluble plant extracts, enzymes. Etc., but is not limited thereto. Examples of oil-soluble vitamins include vitamin A or derivatives thereof, vitamin E or derivatives thereof, ascorbyl palmitate, ascorbyl stearate, ascorbyl palmitate, vitamin D, vitamin K, or vitamin F. Examples include menthyl anthranilate, benzophenone-3, butylmethoxydibenzoylmethane, octocrylene, octylmethoxycinnamate, and the like. Examples of oil-soluble antioxidants include lipoic acid and chlorogenic acid. Examples of plant extracts include golden extract, centella asiatica extract, and licorice extract. Examples of the enzyme are preferably papain, bromelain, protease or lipase.

Step (b) is a step of preparing an aqueous phase by adding 1 to 10 parts by weight of a water-soluble surfactant with respect to 100 parts by weight of water. The water-soluble surfactant may be a conventional water-soluble surfactant having a hydrophile lipophil balance (HLB) 12 or more, preferably a water-soluble surfactant usable in cosmetics. If the HLB of the water soluble surfactant is less than 12, it may be difficult to prepare an O / W type emulsion.

Examples of the water-soluble surfactant of the present invention include, but are not limited to, polyoxyethylene type nonionic surfactants, polyhydric alcohol ester type nonionic surfactants, polymer type surfactants, and the like. Examples of the polyoxyethylene-type nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenols, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene alkrolamides, polysorbates, and the like. Examples of the polyhydric alcohol ester nonionic surfactants include fatty acid monoglycerides, higher fatty acid sorbitan esters, sugar fatty acid esters or polyglycerol esters, and the like. Examples of polymeric surfactants include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose or hydroxypropylmethylcellulose, polyvinyl alcohol, carbomers, sodium alginate, starch derivatives and ethylene oxide / propylene oxide blocks. There is coalescence.

In the step (c), an oil phase is added to the prepared aqueous phase to prepare an O / W type emulsion, and it is preferable to add 1 to 50 parts by weight of the oil phase with respect to 100 weight of the aqueous phase. The temperature for preparing the emulsion proceeds at room temperature and the size of the capsule varies depending on the mixing speed. The emulsion is prepared using a homomixer while adding an oil phase to the aqueous phase, and the homomixer may be operated at a rotational speed of 500 to 5000. When the rotation speed exceeds 500 rpm, the size of the microcapsules may be smaller than 1 um, and when the driving speed is less than 500 rpm, the size of the microcapsules may be larger than 500 um, so that percutaneous permeability may be difficult or may not be good.

Step (d) is to recover the microcapsules by evaporating the organic solvent contained in the emulsion. Removal of the organic solvent can be easily carried out using a conventional dryer, such as a vacuum distillation.

The microcapsules prepared by the method of preparing microcapsules of the present invention contain a size of 1 to 1000 μm, preferably 1 to 50 μm, and when mixed with a conventional cosmetic, it is possible to stably maintain the active ingredients collected in the microcapsules. When used as a cosmetic, it can fully exert the effect of the active ingredient.

The present invention also provides a cosmetic containing the microcapsules. The cosmetics may be provided for the use of basic cosmetics, makeup cosmetics, body cosmetics, hair cosmetics, scalp cosmetics or shaving cosmetics. Examples of the basic cosmetics include creams, cleansing foams, packs, massage creams, latexes, etc. The makeup cosmetics include foundations, makeup bases, lipsticks, eyeshadows, eyeliners, eyebrow pencils, and the like. Soaps, body cleansers, baths, sunscreen creams, sunscreen lotions, sunscreen liquids, etc. For hair cosmetics, shampoo, conditioner, hair treatment, hair mousse, hair colorant, hair bleach, color conditioner The scalp cosmetics include scalp treatments, the shaving cosmetics include aftershave and shaving creams, and the oral cosmetics include toothpaste.

Hereinafter, examples of the present invention will be described. The following examples are only for illustrating the present invention and the present invention is not limited to the following examples.

Example 1 Preparation of Microcapsules Containing Bromelain

95 g of cellulose acetate was dissolved in 400 g of methylene chloride, and 5 g of bromelain was dispersed therein to prepare an oil phase. In addition, 20 g of sodium alginate was dissolved in 980 g of water to prepare an aqueous phase. The oil phase prepared in the aqueous phase was added and emulsified for about 5 minutes at a speed of 3000 using a homomixer to prepare an O / W emulsion, and the emulsion was completely removed from methylene chloride using a vacuum distillation unit. After distillation under reduced pressure, the dispersion was filtered to recover only the capsules, and the recovered capsules were dried in a dryer to obtain powdered microcapsules.

Example 2 Preparation of Microcapsules Containing Lipase

90 g of ethylcellulose was dissolved in 400 g of methylene chloride and 10 g of lipase was dispersed therein to prepare an oil phase. A water phase was prepared by dissolving 50 g of Polysorbate-60 in 950 g of water. The oil phase prepared in the water phase was added and emulsified for about 5 minutes at 2500 rpm using a homomixer to prepare an O / W emulsion, and the emulsion was completely removed by methylene chloride using a vacuum distillation unit. After the completion of vacuum distillation, the dispersion was filtered to recover only the capsules, and the recovered capsules were dried in a dryer to obtain powdery microcapsules.

Example 3: Usability Preparation of microcapsules containing licorice extract

90 g of ethylcellulose was dissolved in 400 g of methylene chloride, and 10 g of an oil-soluble licorice extract was dispersed therein to prepare an oil phase. Licorice used for extraction was commercially available as a raw material of functional cosmetics. 20 g of polyvinyl alcohol was dissolved in 980 g of water to prepare an aqueous phase. The oil phase prepared in the aqueous phase was added and emulsified for about 5 minutes at a rotational speed of 3000 rpm using a homomixer to prepare an O / W emulsion, and the emulsion was completely removed by methylene chloride using a vacuum distillation unit. After the completion of vacuum distillation, the dispersion was filtered to recover only the capsules, and the recovered capsules were dried in a dryer to obtain powdery microcapsules. SEM photographs of the microcapsules are shown in FIG. 1.

Example 4 Preparation of Microcapsules-1

90 g of cellulose acetate was dissolved in 400 g of methylene chloride, 5 g of papain was dispersed therein to prepare an oil phase, and microcapsules were obtained in the same manner as in Example 1 except that an aqueous phase was prepared from 20 g of sodium alginate and 980 g of water. . SEM pictures of the obtained microcapsules are shown in FIG. 2.

Example 5 Preparation of Microcapsules-2

Microcapsules were prepared in the same manner as in Example 1, except that 80 g of cellulose acetate butyrate was dissolved in 300 g of methyl acetate, 10 g of tocopherol was dispersed therein to prepare an oil phase, and an aqueous phase was prepared from 20 g of hydroxypropylmethylcellulose and 980 g of water. Obtained.

Example 6 Preparation of Microcapsules-3

A microcapsule was prepared in the same manner as in Example 1 except that 80 g of cellulose acetate butyrate was dissolved in 300 g of methyl acetate, 15 g of tocopherol was dispersed therein to prepare an oil phase, and an aqueous phase was prepared from 50 g of polysorbate 60 and 950 g of water. Obtained.

Example 7 Cosmetics Containing Microcapsules

To prepare phase A and phase B in the ratio of the following Table 1, the phase A and phase B were first warmed to 75 ° C. to completely dissolve. The emulsification was performed for 5 minutes using a homomixer, putting phase B into the number A phase. In addition, 3.0 wt% of the cyclomethicone based on the total weight by weight of each of the microcapsules of Examples 1 to 6 are uniformly prepared, and then emulsified for 3 minutes while introducing a liquid phase mixed with the A phase and B phase It was. In the next step, 0.15% by weight of triethanolamine was added to emulsify for 1 minute and cooled to 30 ° C to prepare a cosmetic containing microcapsules.

Ingredient Name Content (% by weight) A Purified water TO 100 Carbomer 0.15 Methylparaben 0.2 glycerin 5.0 B Propylparaben 0.1 Cetyloctanoate 5.0 Macadamia Nut Oil 3.0 Glyceryl Stearate 1.0 Sorbitan stearate / sucrosecoate 3.0 Glyceryl Stearate / Pig-100stearate 1.5 Cetostearyl alcohol 1.0 Caprylic / Capric Triglycerides 3.0

Experimental Example 1 Analysis of Stability of Bromelain in Microcapsules

The stability of bromelain contained in the microcapsules of Example 1 was analyzed.

2 g of microcapsules were added to 100 mL of acetone, and ultrasonically injected for 10 seconds, followed by centrifugation at 12000 rpm for 5 minutes. The process was repeated three times to obtain only pure bromelain. The obtained bromelain was reacted with casein as a substrate and then measured the reactivity using a UV absorber at 280 nm (Table 2).

Storage temperature Immediately after manufacture after 2 weeks 1 month later 2 months later Room temperature 100 98 97 95 40 ℃ 100 96 93 91

In Table 2, it can be seen that the microcapsules of Example 1 can be stored in a stable state of bromelain.

Experimental Example 2 Analysis of Stability of Lipase in Microcapsules

The lipase stability in the microcapsules of Example 2 was measured in the same manner as in Experimental Example 1, and as a result, it was found that the lipase can be stored in the microcapsules for a long time in a stable state.

Storage temperature After manufacturing after 2 weeks 1 month later 2 months later Room temperature 100 97 95 93 40 ℃ 100 96 92 90

Experimental Example 3 Analysis of Stability of Licorice Extract in Microcapsules

The stability of the licorice extract contained in the microcapsules of Example 3 was measured.

2 g of microcapsules were added to 100 mL of acetone, and ultrasonically injected for 10 seconds, followed by centrifugation at 12000 rpm for 5 minutes. The procedure was repeated three times to obtain only licorice extract. The obtained licorice extract was analyzed by HPLC to analyze the change in the content of glabridine contained.

After manufacturing after 2 weeks 1 month later 2 months later Room temperature 100 98 98 97 40 ℃ 100 97 96 95

As shown in Table 4, the licorice extract in the microcapsules of Example 3 almost no change in the content of the active ingredient even after a long period of time, it can be confirmed that the licorice extract is present in a stabilized state.

As described above, the method for preparing microcapsules using the water-insoluble cellulose derivative of the present invention has the advantage of being able to simply collect the active ingredient inside the microcapsules and at the same time stabilize the active ingredient. Therefore, the microcapsules prepared by the method of the present invention can be applied to cosmetics to maintain the effects of the active ingredients for a long time.

Claims (7)

(a) dissolving a water-insoluble cellulose derivative in an organic solvent and adding an oil-soluble active ingredient to prepare an oil phase; (b) dissolving at least 12 hydrophile lipophil balance (HLB) water-soluble surfactants in water to prepare an aqueous phase; (c) emulsifying while adding an oil phase to the water phase to prepare an oil in water (O / W) emulsion; And (d) drying the emulsion to prepare microcapsules; Method for producing a microcapsule comprising a. The method of claim 1, wherein the water-insoluble cellulose derivative is at least one selected from the group consisting of ethyl cellulose, cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate.         The method of claim 1, wherein the oil-soluble active ingredient is one or more selected from the group consisting of oil-soluble vitamins, oil-soluble sunscreens, oil-soluble antioxidants, oil-soluble plant extracts, enzymes, and oil-soluble whitening agents. The method of claim 3, wherein the enzyme is at least one selected from the group consisting of papain, bromelain, protease and lipase. The method of claim 1, wherein the water-soluble surfactant is at least one selected from the group consisting of polyoxyethylene type nonionic surfactants, polyhydric alcohol ester type nonionic surfactants, and polymer type surfactants. delete delete

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