KR102370217B1 - Manufacturing method of nanocomplex comprising yuja oil - Google Patents

Abstract

The present invention relates to a method for producing a nanocomposite containing citron oil and a nanocomposite according thereto.
The nanocomposite containing citron oil according to the present invention has excellent preservability and stability, so that the fragrance component in citron oil lasts for a long time even after long-term storage, so it is very useful to be applied to food compositions, cosmetic compositions, perfume compositions, etc. Do.

Description

Manufacturing method of nanocomposite comprising yuja oil

The present invention relates to a method for producing a nanocomposite containing citron oil and a nanocomposite according thereto.

The scientific name of citrus is Citrus junos Tanaka , which belongs to the genus rutaceae and citrus, and while citron is not cultivated in China, the country of origin, as the climate changes, it is a rare variety among citrus fruits cultivated and produced only in Korea and Japan worldwide.

Citron (柚子) is a fruit that has been treated very preciously in Korea since ancient times due to its superior taste and fragrance. It has served as a source of vitamins, minerals, and various organic acids as well as prevention of colds and has been used in various prescriptions in oriental medicine. In addition, due to the recent development of mass-cultivation technology, the price has been lowered and many are supplied to the market.

The fragrance of citron is very unique and intense compared to the fragrance of other citrus fruits, and it has a different scent from lemon or grapefruit, and it is popular with no one who dislikes it, so it is a highly marketable fragrance. In the 21st century, the demand for natural essential oils is increasing enough to be said to be the 'age of fragrance', and these natural essential oils, namely, the cosmetics and food industries using natural fragrances, are continuously growing despite the economic downturn. is in trend From this point of view, Korean citron oil (citron flavor) is expected to gradually increase in production and scale, and is expected to create more than 20 times more added value than citron as a food.

On the other hand, in the case of foreign countries, each country has its own unique fragrance, but Korea has not yet been able to properly produce and commercialize its own natural fragrance.

Accordingly, there is a demand to produce and commercialize citron incense, which is a natural fragrance unique to Korea, but domestic citron has the highest quality and is a unique special product in the world. A proper industrial scale manufacturing process has not been developed, and the reality is that the fragrance component of citron cannot last for a long time due to the sensitive characteristics of air, light, and temperature of the natural citron fragrance. In addition, in general, natural fragrance is not only easily denatured by heat, but also is not easily captured when extracted by a distillation method due to a difference in vapor pressure, and is volatilized, so extraction efficiency is extremely low. When you do, a chemical reaction with the solvent is caused, and the flavor characteristics are sometimes lost.

Accordingly, the inventors of the present inventors have studied steadily on a method for producing a unique natural fragrance in Korea using domestic citron, and as a result, the nanocomposite containing citron oil according to the present invention exhibits an effect that can sustain the fragrance component of citron for a long time. By confirming, the present invention was completed.

KR 10-2001-0035501 A

An object to be solved by the present invention is to provide a method for producing a nanocomposite containing citron oil with improved preservation and stability of the citron fragrance component.

In order to achieve the above object, the present invention comprises the steps of (a) dissolving a surfactant in distilled water to prepare an aqueous solution; (b) adding citron oil dropwise to the aqueous solution and homogenizing to prepare a citron oil nanoemulsion; (c) preparing an aqueous polymer solution containing a water-soluble polymer; (d) preparing a mixture by mixing the polymer aqueous solution and the citron oil nanoemulsion; and (e) forming a complex of a polymer and a citron oil nanoemulsion while stirring the mixture; provides a method for producing a nanocomposite comprising citron oil.

In addition, the present invention provides a nanocomposite comprising citron oil, which is prepared by the above method and has an average particle size of 1 nm or more and less than 50 nm.

In addition, the present invention provides a food composition comprising the nanocomposite containing the citron oil as an active ingredient.

In addition, the present invention provides a cosmetic composition comprising the nanocomposite containing the citron oil as an active ingredient.

In addition, the present invention provides a perfume composition comprising the nanocomposite containing the citron oil as an active ingredient.

The nanocomposite containing citron oil according to the present invention has excellent preservation and stability, so that the fragrance component lasts for a long time even after long-term storage, so it is very useful for application to food compositions, cosmetic compositions, perfume compositions, and the like.

1 is a schematic diagram showing a manufacturing process of a nanocomposite containing citron oil according to an embodiment of the present invention.
2 is a transmission electron microscope (TEM) analysis result image of the nanocomposite containing citron oil according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention comprises the steps of (a) dissolving a surfactant in distilled water to prepare an aqueous solution; (b) adding citron oil dropwise to the aqueous solution and homogenizing to prepare a citron oil nanoemulsion; (c) preparing an aqueous polymer solution containing a water-soluble polymer; (d) preparing a mixture by mixing the polymer aqueous solution and the citron oil nanoemulsion; and (e) forming a complex of a polymer and a citron oil nanoemulsion while stirring the mixture; it relates to a method for producing a nanocomposite comprising citron oil.

In the method for producing a nanocomposite containing citron oil of the present invention, step (a) is to prepare an aqueous solution by dissolving a surfactant in distilled water.

The surfactant in step (a) is polysorbate 80 (Polysorbate 80, Tween 80), polysorbate 20 (Polysorbate 20, Tween 20), lecithins, sodium dodecyl sulfate, pol It may be at least one selected from oxamers, whey protein isolate, arabic gum, and soybean soluble polysaccharide, and polysorbate 80 is preferable.

In the manufacturing method of the present invention, the surfactant may be added in an amount of 10 to 25 parts by weight, preferably 10 to 20 parts by weight, more preferably 14 to 18 parts by weight based on 100 parts by weight of distilled water.

In the method for producing a nanocomposite containing citron oil of the present invention, step (b) is to prepare a citron oil nanoemulsion by adding citron oil dropwise to the aqueous solution and then homogenizing it. In this way, when citron oil is added dropwise after preparing an aqueous solution by sufficiently dissolving the surfactant in distilled water, a more stable nanoemulsion can be prepared, and then a nanocomposite with better preservation and stability can be prepared. do.

The citron oil is used in an amount of 2 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 13 parts by weight, even more preferably 5 to 13 parts by weight, most preferably based on 100 parts by weight of the distilled water. 5 to 10 parts by weight may be added.

In one embodiment, the surfactant and citron oil may be in a weight ratio of 3: 0.5 to 3.5, preferably 3: 0.5 to 2.5, more preferably 3: 0.5 to 1.5 by weight.

In one embodiment, after the citron oil is added dropwise to the aqueous solution, the emulsion may be prepared by mixing at 8,000 to 15,000 rpm for 5 to 15 minutes using a high-speed homogenizer. And, it is possible to prepare a nano-emulsion by ultrasonication of the emulsion.

The sonication may be performed for 5 to 20 minutes at an amplitude of 20 to 40% in the range of 20 to 60 kHz, preferably 20 to 40 kHz.

In the present invention, it is possible to control the particle size of the nanoemulsion by treating ultrasonic waves, and in particular, by controlling the ultrasonic treatment intensity and time together within the above range, it is possible to obtain a nanoemulsion having a small particle size and a stabilized nanoemulsion.

When the ultrasonic treatment intensity and the ultrasonic treatment time are out of the above ranges, nanoemulsion agglomeration or layer separation may occur, and dispersion stability may be lowered.

In addition, in the manufacturing method of the present invention, it is preferable that the weight ratio of the surfactant and the citron oil is within the above range in terms of preservation and stability enhancement.

In the method for producing a nanocomposite containing citron oil of the present invention, step (c) is to prepare an aqueous polymer solution containing a water-soluble polymer.

The water-soluble polymer is DE (Dextrose equivalent) of 16 to 20 maltodextrin (Maltodextrin), DE 11 to 14 maltodextrin (Maltodextrin), gum arabic (Gum Arabic), hydroxypropyl methyl cellulose (hydroxypropylmethyl cellulose; HPMC), corn Corn starch, polyvinyl alcohol, polyethylene oxide, chitosan, sodium alginate, sodium hyaluronate, dextran, carbo Carbomer, methyl cellulose, carboxymethyl cellulose, natural cellulose, whey protein isolate (WPI), carrageenan, aloe vera gel ) and at least one selected from starch adhesive, preferably a mixture of maltodextrin of DE 11-14, or maltodextrin of DE 16-20, and gum arabic.

In the present invention, the maltodextrin of DE 11 to 14 is preferably the maltodextrin of DE 11 to 13, and more preferably the maltodextrin of DE 12. In the present invention, it is preferable to use glucidex 12 as the maltodextrin of DE 11 to 14. The glucidex 12 is a starch hydrolyzate using corn starch as a main raw material and functional properties between starch and starch syrup, and is a maltodextrin powder of DE (dextrose equivalent) 11 to 14. Glucidex 12 is used in food processing fields that require various functional quality characteristics such as texture, viscosity, moisture composition, and film formation. In addition, it has no odor and has excellent heat resistance, so it has the advantage of less browning by heating. As described above, in the case of the maltodextrin of DE 11 to 14, the molecular weight is relatively small, and thus, like an emulsifier, it has the characteristic of good particle formation at the interface between oil and water.

The mixture of maltodextrin and gum arabic may include DE 16-20 maltodextrin and gum arabic in a weight ratio of 1: 0.5 to 1.5. As described above, in the case of a mixture of maltodextrin and gum arabic of DE 16-20, when mixed with a nanoemulsion containing citron oil, it penetrates into the nanoemulsion and condenses strongly, thereby reducing the particle size while By maximizing the stability, it is possible to form a nanocomposite that is very good for containing citron oil. On the other hand, when the DE value of the maltodextrin is out of the above range, it becomes difficult to satisfy the effect expected in the present invention.

On the other hand, among the maltodextrins, in the case of the maltodextrin of DE 11 to 14, the molecular weight is relatively small, so it has a property of forming particles well at the interface between oil and water. In the case of DE 16-20 maltodextrin, mixing with other polymers, especially gum arabic, forms more strongly condensed particles when mixed with a nanoemulsion, so the nanocomposite of the present invention It is more preferable to form

In addition, the polymer aqueous solution is preferably in a concentration of 0.5 to 5% by weight, preferably 0.5 to 2% by weight.

In the method for producing a nanocomposite containing citron oil of the present invention, step (d) is to prepare a mixture by mixing the polymer aqueous solution and the citron oil nanoemulsion.

The aqueous polymer solution and the citron oil nanoemulsion may be mixed in a weight ratio of 1: 0.5 to 1.5.

In the method for producing a nanocomposite containing citron oil of the present invention, step (e) is to form a complex of a polymer and a citron oil nanoemulsion while stirring the mixture.

In one embodiment, the mixture may be mixed for 5 to 15 minutes at 8,000 to 15,000 rpm using a high-speed homogenizer. And the nano-composite of the polymer and the citron oil nano-emulsion is prepared by ultrasonically treating the mixture.

In the present invention, in the process of forming the nanocomposite, the polymer penetrates into the citron oil nanoemulsion to form more condensed composite particles, thereby forming smaller and more stable particles.

The sonication may be performed at an amplitude of 20 to 40% in the range of 20 to 60 kHz, preferably 20 to 40 kHz, for 5 to 20 minutes, preferably for 10 to 20 minutes.

The average particle size of the nanocomposite thus prepared is 1 to 500 nm, preferably 1 to 300 nm, more preferably 1 to 250 nm, more preferably 1 to 100 nm, most preferably 1 nm or more, and It may be less than 50 nm.

When the average particle size of the nanocomposite containing citron oil is within the above range, less surfactant is used, so there are fewer side effects to the body, thermodynamically stable, and it is possible to prevent precipitation forehead creaming, so that the stabilization of citron oil and It is preferable in terms of efficiency enhancement. In particular, since the nanocomposite has very small particles, when applied to food, it has good digestion and absorption in vivo, and when applied to cosmetics, it is useful because it can deliver a trace amount of active ingredient to the skin uniformly.

In the method for producing a nanocomposite comprising citron oil of the present invention, after step (e), a pH adjusting agent is added to the prepared nanocapsule composition to adjust the pH to 6.5 to 8.5, preferably pH 7.0 to 8.5 ; may be further included.

The pH adjusting agent may be a buffer or sodium hydroxide or other pH adjusting agent or a combination thereof.

The nanocomposite composition of the present invention is preferably prepared under conditions adjusted to pH 6.5 to 8.5, and when the pH is less than 6.5 or exceeds pH 8.5, the dispersion degree is 0.4 or more, and the average particle size is also large as 500 nm or more. There is a risk of losing the problem.

In addition, the present invention provides a nanocomposite composition comprising citron oil, which is prepared according to the above method and has an average particle size of 1 nm or more and less than 50 nm.

The composition may be a nanocomposite composition comprising 0.5 to 10% by weight of citron oil, 1 to 30% by weight of a surfactant, 15 to 30% by weight of a water-soluble polymer, and 50 to 70% by weight of distilled water, based on the total weight. The content of the water-soluble polymer is exclusive of the content described above.

More preferably, it is a nanocomposite composition comprising 1 to 5% by weight of citron oil, 3 to 15% by weight of a surfactant, 20 to 30% by weight of a water-soluble polymer, and 60 to 70% by weight of distilled water, based on the total weight of the composition, It should contain the nanocomposite composition prepared according to the order and conditions of the method, and when used, maximize the stability of citron oil, and because of its excellent solubility in water, it can be stored for a long time and the fragrance is strong, so food, cosmetics, perfume It has the advantage that it can be used in a variety of ways for manufacturing, etc.

If any one of the above components is out of the range under preferred conditions, the above-mentioned effects cannot be achieved, further agglomeration, coagulation, or suspension problems occur, and when the pH conditions are changed, the citron oil easily collapses A problem arises in which this is leaked.

In addition, the nanocomposite formed in the nanocomposite composition is characterized in that the citron oil holding power calculated through Equation 1 below is 50-93%.

In addition, the present invention provides a food composition comprising the nanocomposite containing the citron oil as an active ingredient.

In addition, the present invention provides a cosmetic composition comprising the nanocomposite containing the citron oil as an active ingredient.

In addition, the nanocomposite containing the citron oil may be used as an active ingredient in a cosmetic composition. In this case, the cosmetic composition may be in the form of a solution, powder, emulsion, lotion, spray, ointment, aerosol, cream or foam. In addition, in the cosmetic composition of the present invention, it may contain a carrier acceptable in the cosmetic formulation. As used herein, "acceptable carrier for cosmetic preparations" refers to compounds or compositions that are already known and used that can be included in cosmetic preparations, or compounds or compositions to be developed in the future, which have toxicity, instability, or irritation beyond the level that the human body can adapt to when in contact with the skin. say nothing

The carrier may be included in the cosmetic composition of the present invention in an amount of from about 1% to about 99.99% by weight, preferably from about 90% to about 99.99% by weight of the total weight of the composition. Examples of the carrier include alcohol, oil, surfactant, fatty acid, silicone oil, humectant, humectant, viscosity modifier, emulsion, stabilizer, UV scattering agent, UV absorber, color developer, and the like. The alcohol, oil, surfactant, fatty acid, silicone oil, humectant, humectant, viscosity modifier, emulsifier, stabilizer, UV scattering agent, UV absorber, color developer, etc. are already known in the art, so those skilled in the art may use appropriate substances or compositions can be selected to use.

As an embodiment of the present invention, the cosmetic composition according to the present invention may include glycerin, butylene glycol, propylene glycol, polyoxyethylene hydrogenated castor oil, ethanol, triethanolamine, etc. in addition to the nanocomposite containing the citron oil. , preservatives, fragrances, coloring agents, purified water, etc. may be included in a trace amount as needed.

Skin in the present invention is a concept that includes not only the face, but also the scalp and the whole body. As a cosmetic composition that can be applied to the scalp, there are shampoos, conditioners, treatments, hair growth agents, etc., body cleansers that can be applied to the whole body, etc. It can be prepared in various forms for the use of.

In addition, the present invention provides a perfume composition comprising the nanocomposite containing the citron oil as an active ingredient.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following examples.

<Example>

Preparation Example 1: Preparation of citron oil nanoemulsion

a-1) separating citron oil from citron peel

A citron peel was obtained from 10 kg of domestic citron washed thoroughly using a peeler, distilled water was mixed with the pulverized product of the citron peel, and 5 kg of a citron peel extract containing distilled water and citron oil was obtained from the mixture. did

Sodium chloride was added to the citron peel extract to a concentration of 1% (w/v), mixed uniformly, and left to stand until layer separation occurred, and 150 g of citron oil as a supernatant was separated.

a) preparing an aqueous solution by dissolving a surfactant in distilled water

An aqueous solution was prepared by adding 18.75 parts by weight of tween80 as a surfactant to 100 parts by weight of distilled water and stirring for 3 hours.

b) preparing citron oil nanoemulsion

An emulsion was obtained by stirring at 400 rpm for 2 hours while dropping 6.25 parts by weight of the citron oil obtained in a-1) with respect to 100 parts by weight of the distilled water.

Then, the emulsion was homogenized for 10 minutes at 10,000 rpm using a high speed homogenizer. Thereafter, the homogenized emulsion was finely granulated using an ultrasonic homogenizer at 30 kHz and an amplitude of 30% for 15 minutes to prepare a nanoemulsion.

Production Examples 2-4

A citron oil nanoemulsion was prepared in the same manner as in Preparation Example 1 except as shown in Table 1 below by varying the weight ratios of distilled water, surfactant, and citron oil.

Category (weight ratio) Distilled water Surfactants citron oil Distilled water: Surfactant: Yuzu oil Preparation Example 1 100 18.75 6.25 80:15:5 Preparation 2 100 21.43 21.43 70:15:15 Preparation 3 100 28.57 14.29 70:20:10 Preparation 4 100 12.5 12.5 80:10:10

Preliminary Experimental Example: Particle Size and PDI Measurement of Nanoemulsion

The size of the particles contained in the citron oil nanoemulsion prepared in Preparation Examples 1 to 4 was measured using an Otsuka particle size analyzer (Zeta-potential & Particle size Analyzer (Marvern zetasizer, Nano-ZS)). In addition, the polydispersity index of each citron oil nanoemulsion was measured and shown in Table 2 below.

division Particle size (nm) Polydispersity Index (PDI) Preparation Example 1 293.2 0.276 Preparation 2 315.7 0.514 Preparation 3 727.1 0.287 Preparation 4 288.7 0.275

As shown in Table 2, the nanoemulsion of Preparation Example 1 had a particle size of 300 nm or less as well as a PDI of less than 0.3, so it was the most stable.

In the case of Preparation Example 2, the PDI was rather high, and in the case of Preparation Example 3, it was confirmed that the particle size was relatively large.

On the other hand, in the case of the nanoemulsion of Preparation Example 4, both the particle size and PDI were stable, but another pick appeared and the quality of the emulsion was not good.

Example 1: Preparation of nanocomposite containing citron oil (maltodextrin and gum arabic) )

1. Preparation of an aqueous polymer solution

0.5 g of a mixture of maltodextrin DE 18 and gum arabic in a weight ratio of 1:1 was added to 50 g of distilled water, and stirred overnight at room temperature to prepare a 1% (w/w) polymer aqueous solution.

2. Mixing the polymer aqueous solution and citron oil nanoemulsion

A mixture was prepared by mixing the citron oil nanoemulsion obtained in Preparation Example 1 and the polymer aqueous solution obtained in step 1. in a weight ratio of 1:1. Thereafter, the pH of the mixture was adjusted to 8.0.

3. Preparation of Nanocomposite Containing Citron Oil

The mixture obtained in step 2. was put into a high-speed homogenizer and mixed at 10,000 rpm for 10 minutes, then the mixture was placed in an ultrasonic homogenizer and sonicated at 35 kHz at 30% amplitude for 15 minutes to collect citron oil nanoemulsion. A complex was obtained.

Examples 2 to 8: Preparation of nanocomposites in which citron oil nanoemulsions with different polymer types are collected

It was carried out in the same manner as in Example 1, but as shown in Table 3 below, by changing the type of water-soluble polymer, a nanocomposite in which citron oil nanoemulsion was collected was prepared.

division Types of water-soluble polymers Mark Example 1 Mixture of maltodextrin DE 18 and gum arabic in a 1:1 ratio MD+GA Example 2 Hydroxypropyl methylcellulose (HPMC) AN15 Example 3 Maltodextrin DE 12 glucidex12 Example 4 carrageenan carrageenan Example 5 Carboxymethyl Cellulose CMC Example 6 Whey Protein Isolate WPI Example 7 pectin Pectin Example 8 gelatin Gelatin

Examples 9 to 16: Mixing two or more polymers to prepare a polymer aqueous solution

A nanocomposite was prepared by mixing the polymer as shown in Table 4 below during the preparation of the aqueous polymer solution in step 1.

division polymer Mixing ratio (weight) Example 9 Gum Arabic + Maltodextrin 2:1 Example 10 Gum Arabic + HPMC (AN15) 2:1 Example 11 Maltodextrin DE 18 + HPMC (AN15) 2:1 Example 12 Gum Arabic + HPMC (AN15) 1:1 Example 13 Maltodextrin DE 18 + HPMC (AN15) 1:1 Example 14 Gum Arabic + Maltodextrin 1: 2 Example 15 Gum Arabic + HPMC (AN15) 1: 2 Example 16 Maltodextrin DE 18 + HPMC (AN15) 1: 2

Comparative Example 1: MD+GA; Preparation of polymer aqueous solution -> Addition of surfactant -> Addition of oil

a) 0.5 g each of maltodextrin DE 18 and gum arabic was added to 100 g of distilled water and stirred at room temperature for 5 hours to prepare a 1% (w/w) polymer aqueous solution. Then, it was kept refrigerated for one day so that it could be completely hydrated.

b) The aqueous polymer solution was placed in an ultrasonic homogenizer and sonicated at 35 kHz at 30% amplitude for 10 minutes.

c) 18.75 parts by weight of a surfactant, tween80, was added to 100 parts by weight of the ultrasonicated aqueous polymer solution and stirred for 3 hours.

d) An emulsion was obtained by stirring at 400 rpm for 2 hours while dropping 6.25 parts by weight of citron oil with respect to 100 parts by weight of the mixture using a syringe.

Then, the emulsion was homogenized for 10 minutes at 10,000 rpm using a high speed homogenizer. Thereafter, the homogenized emulsion was finely divided using an ultrasonic homogenizer at 30 kHz and an amplitude of 30% for 15 minutes to prepare a nanoemulsion.

Comparative Example 2: AN15; Preparation of polymer aqueous solution -> Addition of surfactant -> Addition of oil

It was carried out in the same manner as in Comparative Example 1, except that in step a), HPMC AN15 (Lotte Chemical) was added instead of a mixture of maltodextrin DE 18 and gum arabic, heated to 80 ° C. and stirred for 1 hour, and then again at room temperature for 5 A 1% polymer aqueous solution was prepared by stirring for a period of time.

Comparative Example 3: MD+GA; Double yuzu oil added

It was carried out in the same manner as in Comparative Example 1, except that in step d), 12.5 parts by weight of citron oil was added instead of 6.25 parts by weight.

Comparative Example 4: AN15; Double yuzu oil added

It was carried out in the same manner as in Comparative Example 2, except that in step d), 12.5 parts by weight of citron oil was added instead of 6.25 parts by weight.

Test Example 1: Particle Analysis of Nanocomposites Containing Citron Oil (Particle Size and PDI)

1-1: Nanocomposite prepared by different types of polymers

The size of the particles of the nanocomposite prepared in Examples 1 to 6 was measured using an Otsuka particle size analyzer (Zeta-potential & Particle size Analyzer, ELSZ-2000Z). In addition, the polydispersity index of each nanocomposite was measured and shown in Table 5 below.

division Particle size (nm) Polydispersity Index (PDI) Example 1 41.91 0.217 Example 2 47.42 0.335 Example 3 417.3 0.484 Example 4 123.8 0.528 Example 5 61.75 0.555 Example 6 57.74 0.455

As shown in Table 5, the nanocomposite of Example 1 was the most stable as the particle size was less than 50 nm and the PDI was less than 0.3.

In the case of Example 2, it was confirmed that the particle size of the nanocomposite was less than 50 nm, but the PDI was 0.3 or more, and in the case of Example 3, the particle size and PDI were relatively large.

1-2: Nanocomposite prepared by varying the concentration of aqueous polymer solution

After preparing the nanocomposites prepared in Examples 1 to 8 by varying the concentration of the polymer aqueous solution to 1% (w/w), 2.5% (w/w) and 5% (w/w), each nanocomposite The particle size and polydispersity index were measured and shown in Table 6 below.

division 1% polymer aqueous solution 2.5% polymer aqueous solution 5% polymer aqueous solution Particle size (nm) PDI Particle size (nm) PDI Particle size (nm) PDI Example 1 41.91 0.217 77.9 1.520 102.89 0.764 Example 2 47.42 0.335 175.73 1.799 - - Example 3 417.3 0.484 436.06 1.175 586.63 0.516 Example 4 123.8 0.528 - - - - Example 5 61.75 0.555 193.93 1.418 - - Example 6 57.74 0.455 273.63 1.74 214.4 0.833 Example 7 87.04 0.533 - - - - Example 8 132.97 0.375 - - - -

(In Table 6, the '-' mark confirms that the capsule is not formed properly and the precipitation phenomenon occurs.)

As shown in Table 6, the nanocomposite prepared using a 1% (w/w) polymer aqueous solution was the most stable.

1-3: Nanocomposite prepared by mixing two or more polymers

The size and polydispersity index of each nanocomposite prepared in Examples 9 to 16 were measured and shown in Table 7 below.

division Particle size (nm) Polydispersity Index (PDI) Example 9 132.93 0.504 Example 10 168.53 0.447 Example 11 166.77 0.441 Example 12 183.27 0.393 Example 13 175.87 0.396 Example 14 130.93 0.490 Example 15 212.73 0.362 Example 16 193.00 0.396

1-4: Nanocomposite prepared by different methods

The size and polydispersity index of each nanocomposite prepared in Comparative Examples 1 to 4 were measured and shown in Table 8 below.

division Particle size (nm) Polydispersity Index (PDI) Comparative Example 1 262.1 0.275 Comparative Example 2 323.3 0.568 Comparative Example 3 321.0 0.283 Comparative Example 4 346.1 0.400

As shown in Table 8, even using the same polymer, the nanocomposites of Examples 1 and 2 had smaller particle sizes and lower PDI than the nanocomposites of Comparative Examples 1 and 2 and were stable.

In addition, even when prepared in the same manner, the nanocomposites of Comparative Examples 1 and 2 had smaller particle sizes and lower PDI than the nanocomposites of Comparative Examples 3 and 4 prepared by adding two times more citron oil, and were stable.

Test Example 2: Measurement of holding capacity of nanocomposite containing citron oil

In order to measure the citron oil holding power of the nanocomposite containing citron oil, the nanocomposite prepared in Example 1 was centrifuged twice at 4,000 rpm for 10 minutes under various pH conditions (pH 6.5-9.0). The citron oil from the untreated supernatant was removed, filtered through a 0.45 μm filtration membrane to obtain a precipitate, and then dissolved in hexane and the collected citron oil content was analyzed by GC. At this time, the citron oil holding power (%) of the nanocomposite containing citron oil was calculated as follows.

[Equation 1]

Citron oil retention capacity (%) = ((Total content of citron oil added (g) ?? Content of citron oil removed because it was not captured in the nanocomposite (g)) / Total content of citron oil added (g)) ㅧ 100

Table 9 below shows the retention of the nanocomposite prepared in Example 1 under various pH conditions (pH 4.0-9.0).

division Citron Oil Retention (%) pH 4.0 60.5 pH 4.5 57.8 pH 5.0 58.5 pH 5.5 62.3 pH 6.0 69.7 pH 6.5 70.5 pH 7.0 71.7 pH 7.5 74.1 pH 8.0 90.5 pH 8.5 90.2 pH 9.0 69.2

As shown in Table 9, the citron oil retention of the nanocomposite containing citron oil prepared in the pH range of 6.5-8.5 was in the range of 65-91%, and when the pH was adjusted in the range of 8.0-8.5, the retention power was 90%, the maximum value was shown.

Test Example 3: Quantitative analysis of fragrance component of nanocomposite containing citron oil

The content of fragrance components (DL-limonene and γ-terpinene) contained in the sample was analyzed using GC-FID (7890A GC, Agilent Technologies), and it is shown in Table 10 below.

The column was DB-WAX (60 cm × 0.25 mm, 0.25 μm, Agilent Technologies), and the column temperature program was maintained at 70 °C for 2 minutes, then increased to 230 °C at a rate of 2 °C/min and maintained for 20 minutes. did. The temperature of the inlet and the detector were set at 250 °C, respectively, and the flow rate of carrier gas (nitrogen) was set to 1.0 mL/min.

After mixing 1.9 mL of methanol with 0.1 mL of sample, 1 μL was injected into the GC, and analysis was performed using split (10:1) inlet mode. Identification of each material was performed by comparison with the retention time of the peak obtained by analyzing the standard, and an external standard method was used for quantification.

division indicator substance immediately after manufacturing 4 weeks after storage at room temperature Residual content ratio (%) content (wt%) content (wt%) control
(citron oil) DL-limonene 3.23 1.07 33.13 γ-Terpinene 0.31 0.21 67.74 Preparation Example 1 DL-limonene 3.31 2.42 73.11 γ-Terpinene 0.32 0.26 81.25 Example 1 DL-limonene 3.33 3.32 99.67 γ-Terpinene 0.32 0.32 100.0 Example 3 DL-limonene 3.29 2.91 88.45 γ-Terpinene 0.30 0.28 93.33 Comparative Example 1 DL-limonene 3.25 2.59 79.69 γ-Terpinene 0.31 0.25 80.65

Test Example 4: Transmission electron microscope (TEM) measurement of nanocomposites containing citron oil

An attempt was made to confirm the particle shape and the degree of distribution of the citron oil nanoemulsion of the present invention and the nanocomposite containing citron oil.

2 is a citron oil nanoemulsion prepared in Preparation Example 1 of the present invention, a nanocomposite (1% glucidex) prepared in Example 3, a nanocomposite prepared in Example 2 (1% AN15), prepared in Example 1 Transmission electron microscope (TEM) analysis result image of one nanocomposite (1% MD+GA).

For the transmission electron microscope analysis, 7 μl of citron oil nanoemulsion or nanocomposite containing citron oil was fixed on a carbon-coated copper grid for negative staining, washed once with ultrapure water, and immediately after washing with ultrapure water, 7 μl of 2% uranyl acetate was added to dye, washed with ultrapure water, and dried in the air. The prepared specimen was photographed with an accelerated electron beam of 200 kV to obtain a transmission electron microscope picture.

Referring to FIG. 2, the citron oil nanoemulsion prepared in Preparation Example 1 was observed to have a somewhat shrunken shape as moisture evaporated during the sample drying process before TEM observation, but when observed at a higher magnification, the particle shape was circular. was confirmed to be maintained. And, in the nanocomposites prepared in Examples 2 and 3, most of the particle shapes maintained the original shape, but in the case of a small number of particles, it was observed that they became shrunken during the sample drying process. On the other hand, in the case of the nanocomposite prepared in Example 1, it was observed that it was a circular particle with a very round and smooth surface.

Test Example 5: Measurement of storage stability of nanocomposite containing citron oil

The storage stability of the nanocomposite containing citron oil of Example 1 was measured by methods such as particle size and polydispersity index while stored at room temperature (21° C.) and 37° C. thermostat for 3 months. Table 11 shows the results. In Table 10, 'PS' means 'particle size (nm)'.

pH immediately after manufacturing 1 month after manufacturing 3 months after manufacturing Room temperature (21°C) Room temperature (21°C) 37 ℃ Room temperature (21°C) 37 ℃ PS PDI PS PDI PS PDI PS PDI PS PDI 6.5 47.11 0.285 49.15 0.280 65.12 0.285 52.69 0.290 75.65 0.295 7.0 45.56 0.231 45.45 0.228 44.05 0.220 44.64 0.263 47.68 0.211 7.5 42.12 0.225 43.35 0.229 44.59 0.224 45.15 0.230 46.55 0.245 8.0 41.91 0.217 43.12 0.220 44.57 0.232 44.35 0.228 45.14 0.251 8.5 45.35 0.220 44.13 0.212 45.77 0.220 45.75 0.226 45.10 0.240

Looking at Table 11, the particle size of the nanocomposite containing citron oil during storage at room temperature (21 ° C) was slightly increased in the range of 47-53 nm during storage for 3 months from immediately after preparation when the pH was adjusted to 6.5 immediately after preparation. and maintained a very stable state while maintaining the 41-46 nm range throughout the pH control 7.0-8.5 range. On the other hand, even when stored at 37 °C, stable nanocomposites were formed at 44-48 nm over the pH control range of 7.0-8.5.

In addition, the polydispersity index (PDI) during storage of the nanocomposite containing citron oil was in the range of 0.20-0.295 over the pH-adjusted 6.5-8.5 range during storage for 3 months from immediately after production at room temperature and 37 ° C. By maintaining the degree of dispersion in a stable state, a stable nanocomposite was formed.

Test Example 6: Sensory evaluation for 6 months after preparation of nanocomposite containing citron oil

In order to find out the fragrance and durability of the nanocomposite according to the present invention, the nanocomposite according to Examples and Comparative Examples was stored at 37° C. and then sensory evaluation was performed in the following manner, and is shown in Table 12 below.

To this end, 2 mL of the nanocomposite according to the Examples and Comparative Examples of the present invention was dropped on the plate and spread, and then the odor intensity was measured after natural drying for 10 minutes.

For the sensory evaluation, 10 fragrance evaluation experts were composed of a panel, and evaluation was performed according to a five-point scale method (strength: 1. very weak; 2. weak; 3. normal; 4. strong; 5. very strong). . At this time, statistical processing was performed using the SPSS 12.0 statistical program, and significance was verified at the significance level p<0.05 by the DMR-test (Duncan multiple range test).

division immediately after manufacturing 2 months after manufacturing 4 months after manufacturing 6 months after manufacturing Control (citron oil) 4.38 0.75 - - Preparation Example 1 4.25 2.13 1.05 - Example 1 4.21 4.02 3.88 3.53 Example 2 4.13 3.85 3.40 2.78 Example 3 4.15 3.90 3.38 2.53 Comparative Example 1 4.13 3.75 2.80 2.00 Comparative Example 2 4.07 3.13 2.55 1.25

(In Table 12, the '-' mark means that the scent is too weak to be recognized by the sense of smell.)

Referring to Table 12, in the case of the non-encapsulated control group, although the degree of diffusion is strong at the beginning, it can be seen that the scent persistence significantly decreases over time after preparation. In addition, even in the case of the nanoemulsion of Preparation Example 1, although the fragrance persistence is higher than that of the control, the fragrance persistence sharply falls after 2 months after preparation, and it was confirmed that the fragrance strength weakens after 4 months after preparation.

On the other hand, in the case of Examples 1 to 3 according to the present invention, although the intensity of the fragrance is weakened over time, it can be confirmed that the fragrance is emitted above a certain level. In particular, in the case of Example 1, compared to Examples 2 and 3, it can be seen that the fragrance persistence over time is very strong.

Preparation examples for the nanocomposite containing citron oil of the present invention are exemplified below.

<Production Example> Manufacturing of cosmetics

<Production Example 1> Softening lotion (skin)

In order to prepare a softening lotion containing the nanocomposite containing the citron oil of the present invention, it can be prepared according to a conventional manufacturing method in the cosmetic field by mixing as shown in Table 13 below.

ingredient content (wt%) Nanocomposite comprising citron oil of the present invention 0.1-30% 1,3-butylene glycol 3.0 glycerin 5.0 Polyoxyethylene (60) hydrogenated castor oil 0.2 ethanol 8.0 citric acid 0.02 sodium citrate 0.06 antiseptic a very small amount Spices a very small amount Purified water To 100

<Preparation Example 2> Nutrient lotion (lotion)

In order to prepare a nutrient lotion containing the nanocomposite containing citron oil of the present invention, it can be prepared according to a conventional manufacturing method in the cosmetic field by mixing as shown in Table 14 below.

ingredient content (wt%) Nanocomposite comprising citron oil of the present invention 0.1-30% 1,3-butylene glycol 3.0 glycerin 5.0 squalane 10.0 Monooleate polyoxyethylene sorbitan 2.0 Yuchangwood Oil 0.1-30% Polyoxyethylene (60) hydrogenated castor oil 0.2 ethanol 8.0 citric acid 0.02 sodium citrate 0.06 antiseptic a very small amount Spices a very small amount Purified water To 100

<Preparation Example 3> Face wash (cleansing foam)

In order to prepare a face wash (cleansing foam) containing the nanocomposite containing citron oil of the present invention, it can be prepared according to a conventional manufacturing method in the cosmetic field by mixing as shown in Table 15 below.

ingredient content (wt%) Nanocomposite comprising citron oil of the present invention 0.1-30% Sodium N-acylglutamate 20.0 glycerin 10.0 PEG-400 15.0 propylene glycol 10.0 POE (15) Oleyl Alcohol Ether 3.0 Laurine derivatives 2.0 methylparaben 0.2 EDTA-4Na 0.03 Spices 0.2 Purified water To 100

<Preparation Example 4> Nourishing cream

In order to prepare a nourishing cream containing the nanocomposite containing citron oil of the present invention, it is prepared according to the manufacturing method in the conventional cosmetic field as shown in Table 16 below.

ingredient content (wt%) Nanocomposite comprising citron oil of the present invention 0.1-30% vaseline 7.0 liquid paraffin 10.0 beeswax 2.0 Polysorbate 60 2.5 Sorbitan sesquioleate 1.5 squalane 3.0 propylene glycol 6.0 glycerin 4.0 triethanolamine 0.5 Xanthan Gum 0.5 tocophenyl acetate 0.1 fragrance, preservative a very small amount Purified water To 100

Although the present invention has been described as the above-mentioned preferred embodiment, it is possible to make various modifications and variations without departing from the spirit and scope of the invention. It is also intended that the appended claims cover such modifications and variations as fall within the scope of the present invention.

Claims (16)

(a) dissolving a surfactant in distilled water to prepare an aqueous solution;
(b) adding citron oil dropwise to the aqueous solution and homogenizing to prepare a citron oil nanoemulsion;
(c) preparing an aqueous polymer solution containing a water-soluble polymer;
(d) preparing a mixture by mixing the polymer aqueous solution and the citron oil nanoemulsion; and
(e) forming a complex of polymer and citron oil nanoemulsion while stirring the mixture;
The water-soluble polymer is a method for producing a nanocomposite composition comprising citron oil, characterized in that the mixture of maltodextrin and gum arabic of DE 16-20. According to claim 1,
The surfactant in step (a) is
Polysorbate 80, Tween 80, Polysorbate 20, Tween 20, Lecithins, Sodium dodecyl sulfate, Poloxamers, Whey Protein Isolate ( Whey protein isolate), arabic gum (Arabic gum), and a method for producing a nanocomposite composition comprising citron oil, characterized in that at least one selected from soybean soluble polysaccharide. According to claim 1,
The method for producing a nanocomposite composition comprising citron oil, characterized in that the surfactant is added and dissolved in an amount of 10 to 25 parts by weight based on 100 parts by weight of distilled water. According to claim 1,
The method for producing a nanocomposite composition comprising citron oil, characterized in that the citron oil is added in an amount of 2 to 30 parts by weight based on 100 parts by weight of the distilled water. delete delete delete According to claim 1,
The method for producing a nanocomposite composition comprising citron oil, characterized in that the DE 16-20 maltodextrin and gum arabic are 1: 0.5 to 1.5 by weight. According to claim 1,
The polymer aqueous solution is a method for producing a nanocomposite composition comprising citron oil, characterized in that the concentration of 0.5 to 5% by weight. According to claim 1,
In step (d), a method for producing a nanocomposite composition containing citron oil, characterized in that the polymer aqueous solution and the citron oil nanoemulsion are mixed in a weight ratio of 1: 0.5 to 1.5. According to claim 1,
The method for producing a nanocomposite composition comprising citron oil, characterized in that the average particle size of the nanocomposite is 1 nm or more and less than 50 nm. According to claim 1,
The surfactant is polysorbate 80 (Polysorbate 80, Tween 80),
The surfactant is added in an amount of 14 to 18 parts by weight based on 100 parts by weight of distilled water,
The citron oil is added in an amount of 5 to 10 parts by weight based on 100 parts by weight of distilled water,
The water-soluble polymer is a mixture of DE 16-20 maltodextrin and gum arabic in a weight ratio of 1: 0.5 to 1.5,
The polymer aqueous solution has a concentration of 0.5 to 2% by weight,
The average particle size of the nanocomposite is 1 nm or more and less than 50 nm,
The polymer aqueous solution and the citron oil nanoemulsion are 1: A method for producing a nanocomposite composition comprising citron oil, characterized in that it is mixed in a weight ratio of 0.5 to 1.5. 13. A nanocomposite composition comprising citron oil, which is prepared according to the method of any one of claims 1 to 4 and 8 to 12, and has an average particle size of 1 nm or more and less than 50 nm. . A food composition comprising the nanocomposite composition comprising the citron oil of claim 13 as an active ingredient. A cosmetic composition comprising the nanocomposite composition comprising the citron oil of claim 13 as an active ingredient. A perfume composition comprising the nanocomposite composition comprising the citron oil of claim 13 as an active ingredient.

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