KR100943036B1 - TiO2 Nanocapsule with Improved Stability and Dispersibility, TiO2 Nanocapsule Composition therefor, and Manufacturing Method thereof - Google Patents

Abstract

The present invention provides improved stability and dispersibility of TiO2 nanocapsules prepared by emulsifying and dispersing lipophilic surface-treated TiO2 with a surfactant including hydrogenated lecithin or sucrose distearate, It provides a nanocapsule composition and a method of manufacturing the same.

The TiO2 nanocapsules according to the present invention have an average particle size of 400-800 nm and are not only small and uniform in size, but also have a reflectance of 95% or more at 320 nm or less, and thus are suitable for use in sunscreen cosmetics. In addition, since the TiO2 nanocapsules according to the present invention have excellent stability and dispersibility, the TiO2 nanocapsules can be used particularly well in oil-in-water sunscreen cosmetics.

Nanocapsules, TiO2, Surfactants, Lecithin, Stability

Description

TiO₂nanocapsules with improved stability and dispersibility, nanocapsule compositions and methods for manufacturing the same {TiO2 Nanocapsule with Improved Stability and Dispersibility, TiO2 Nanocapsule Composition therefor, and Manufacturing Method

The present invention relates to TiO2 nanocapsules, nanocapsule compositions for the same, and a method for preparing the same, and more particularly, to TiO2 nanocapsules having improved stability and dispersibility suitable for preparing cosmetics, nanocapsule compositions for the same, and methods for preparing the same. will be.

Recently, the destruction of the ozone layer is rapidly accelerated due to environmental pollution, and thus human skin is threatened from harmful ultraviolet rays.

When excessive ultraviolet rays reach the skin, they are irritated to form free radicals in the skin as well as erythema, blackening, and sunburn, thereby promoting aging and causing skin cancer.

Sunscreen materials are divided into organic sunscreens and inorganic sunscreens [Gasparro et al., 1998; Klein, 1992], while organic blockers have the main function of ultraviolet absorption, inorganic blockers have increased interest because they are the main function of scattering and reflection of ultraviolet rays to protect ultraviolet rays in a wide wavelength range and have high safety.

Inorganic sunscreens include titanium dioxide, zinc oxide, zirconium oxide, and the like, and titanium oxide (TiO 2) is most commonly used. Titanium dioxide is an excellent material as a sunscreen because of its high refractive index, excellent effect of scattering light, high safety in cosmetics, and harmless to human body [光 井 武 [et al., 2002].

However, TiO2 has a disadvantage of low formulation stability, cloudiness, and poor usability and aggregation in the emulsion. Various surface treatments are performed to compensate for the disadvantages of the fine particle TiO 2 and to improve performance.

As the surface treatment agent, silicon, metal soap, fluorine compound, silica, alumina, and the like are used. As a result, the dispersibility is improved, the photocatalytic reaction is suppressed, the water resistance is improved, and the oil repellency is improved. For example, in order to increase dispersibility, a technique has been developed for treating a surface by using aluminum stearate in the oil phase and silica or a hydrophilic polymer in the water phase [Hewitt, 1999]. In addition, the surface of TiO2 is generally treated with an organic substance such as fatty acid or silicone oil to impart water repellency and act as an oily binder.

By the way, TiO2, which is used in the cosmetics industry, is mostly in the form of surface-treated powders or dispersed in silicone oil, so that oil-in-water type (O / W) cosmetics such as lotions are commonly used. There is a limit to manufacturing. That is, in order to exhibit the original characteristics of TiO2, it is necessary to disperse it sufficiently, but the lotion has a weak dispersion energy during manufacture, and the dispersant that can be used has many limitations in terms of human safety and stability.

Therefore, there is an urgent need for a method of preparing a TiO2 formulation having improved stability and dispersibility applicable to any kind of cosmetics including oil-in-water cosmetics.

In order to solve the above problems, the present invention is to improve the stability and dispersibility by nano-encapsulating TiO 2 is excellent in the effect of scattering ultraviolet rays due to high refractive index and harmless to the human body.

In order to achieve the above object, the present invention is the stability and powder prepared by emulsifying and dispersing lipophilic surface-treated TiO 2 with a surfactant containing hydrogenated lecithin or sucrose distearate Provides TiO 2 nanocapsules with enhanced acidity.

The present invention also provides a composition comprising a lipophilic surface-treated TiO 2, a surfactant, a co-emulsifier, an emulsifier, an antioxidant, a chelating agent, and purified water, wherein the surfactant is hydrogenated lecithin or sucrose distearic acid. It provides a TiO 2 nanocapsule composition comprising (sucrose distearate).

Furthermore, the present invention after melting and melting each of the aqueous phase component for nanocapsules containing purified water, antioxidant and chelating agent and the oil phase component for nanocapsules including surfactant and co-emulsifier to a temperature of 65 ~ 75 ℃, A first pretreatment emulsifying step of adding an oil phase component for nanocapsules to a melted nanocapsule aqueous phase component and stirring with a homomixer; A second pretreatment emulsification step of adding TiO2 suspension in which TiO2 is suspended in caprylic / capric triglyceride to the first pretreatment emulsion and then stirring with a homomixer; and using the high pressure homogenizer as the second pretreatment emulsion It provides a method for producing TiO 2 nanocapsules comprising the step of encapsulation and cooling.

The TiO2 nanocapsules according to the present invention have an average particle size of 400-800 nm and are not only small and uniform in size, but also have a reflectance of 95% or more at 320 nm or less, and thus are suitable for use in sunscreen cosmetics. In addition, since the TiO2 nanocapsules according to the present invention have excellent stability and dispersibility, the TiO2 nanocapsules can be used particularly well in oil-in-water sunscreen cosmetics.

First, the present invention provides improved stability and dispersibility of TiO2 nanocapsules prepared by emulsifying and dispersing lipophilic surface-treated TiO2 with a surfactant including hydrogenated lecithin or sucrose distearate. to provide.

In general, since particles having a dispersibility of 100 nm or less have a phenomenon of aggregation of particles because of low dispersibility, TiO 2 nanocapsules were prepared in order to prevent such aggregation and stabilize secondary particles.

Surfactants that can be used in the preparation of TiO2 nanocapsules according to the present invention are preferably natural-derived surfactants that are easy to form micelles and have good biocompatibility, and in particular, hydrogenated lecithin or It is preferred to include sucrose distearate. This is because the average size of the nanocapsules is small and uniform when using them.

In the present invention, TiO 2 is used to suppress the photocatalytic activity of TiO 2 and to make the dispersion well. In this case, it is preferable that the surface is treated with a lipophilic surface treatment agent rather than hydrophilicity. This is because when the nanocapsules are prepared using hydrophilic surface-treated TiO 2, the stability is very bad, such as a large cohesion phenomenon that can be visually confirmed after 48 to 72 hours.

The lipophilic surface treatment is more preferably performed in terms of stability of the TiO 2 nanocapsules by a surface treatment agent containing isostearic acid or aluminum stearate.

The present invention also provides a composition comprising a lipophilic surface-treated TiO 2, surfactant, co-emulsifier, emulsion stabilizer, antioxidant, chelating agent and purified water, wherein the surfactant is hydrogenated lecithin or sucrose di It provides a TiO 2 nanocapsule composition comprising stearic acid (sucrose distearate).

At this time, the TiO2 nanocapsule composition is lipophilic surface-treated TiO2, hydrogenated lecithin, caprylic / capric triglycerides, cetylphosphate, glycerin, ethanol, sodium ascorbyl phosphate, disodium EDTA and purified water TiO 2 nanocapsule composition comprising a.

At this time, the TiO2 nanocapsule composition is a lipophilic surface-treated TiO2, sucrose distearate, caprylic / capric triglycerides, cetyl phosphate, propylene glycol, ethanol, sodium ascorbyl phosphate, disodium EDTA And TiO 2 nanocapsule compositions comprising purified water.

Among the auxiliary components, caprylic / capric triglycerides are used as stabilizing oils for nanoemulsions, and such caprylic / capric triglycerides have low solubility in water and are lipophilic. Since this oil is high, it is possible to improve the stability by reducing the size of the droplets of the nanocapsules [Kang, et al., 2003].

Furthermore, the present invention after melting and melting each of the aqueous phase component for nanocapsules containing purified water, antioxidant and chelating agent and the oil phase component for nanocapsules including surfactant and co-emulsifier to a temperature of 65 ~ 75 ℃, A first pretreatment emulsifying step of adding an oil phase component for nanocapsules to a melted nanocapsule aqueous phase component and stirring with a homomixer; A second pretreatment emulsification step of adding TiO2 suspension in which TiO2 is suspended in caprylic / capric triglyceride to the first pretreatment emulsion and then stirring with a homomixer; and using the high pressure homogenizer as the second pretreatment emulsion It provides a method for producing TiO 2 nanocapsules comprising the step of encapsulation and cooling.

In the preparation of the TiO2 nanocapsules according to the present invention, it is particularly preferable to use a microfluidizer (MF), which is a kind of a high pressure homogenizer, and when using the microfluidizer, the nano It is possible to increase the dispersion stability by making the capsule size small and uniform.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the scope of the present invention is not determined accordingly, but is presented by way of example only.

< Example >

< Example  1 to 4, Comparative example  1 to 8 TiO2  Preparation of Nanocapsules

(One) TiO2  sample

TiO 2 used in this example and the comparative example was surface-treated as hydrophilic or lipophilic, and is shown in Table 1 below. All are manufactured by Tayca, Japan, and the particle size is 10-15 nm, and the crystal structure is all rutile. TiO 2 used will be referred to as A, B, C, D according to the type as shown in Table 1 below.

product name MT-150EX (A) MT-100TV (B) MT-01 (C) MT-100AQ (D) Particle size (nm) 15 15 10 15 Surface characteristics Lipophilic Lipophilic Lipophilic Hydrophilic Surface treatment Aluminum hydroxide / isostearic acid Aluminum hydroxide / aluminum stearate Aluminum Hydroxide / Stearic Acid Aluminum Hydroxide / Hydrated Silica / Alginic Acid Titanium Dioxide (TiO2) Content (%) 78 83 73 74

(2) TiO2 Nanocapsule Sample of Surfactant

In order to make TiO 2 nanocapsules, three types of surfactants were used as surfactants, the main component of which is shown in Table 2 below. The surfactants used will be designated as I, II, III according to the type as shown in Table 2 below.

division Lecithin base (I) Sugar base (II) NSV base (III) chief ingredient hydrogenated lecithin sucrose distearate Brassica campestris (rapeseed) sterols PEG-5 rapeseed sterol ceteth-3 ceteth-5 cholesterol characteristic amphoteric nonionic nonionic product name LIPOID S75-3 Cosmelike S-50 NSV manufacturer LIPOID GmbH, Germany Croda, UK H & A Pharmachem, Korea

(3) TiO2  Supplementary Ingredients for Nanocapsules

Of TiO2 nanocapsules Auxiliary ingredients include cetylphosphate (Amphisol A, Roche, Switzerland) as an auxiliary emulsifier, glycerin (Prisorine9091, Uniqema, UK), emulsifiers and moisturizers, PG (PG-USP, SK OXICHEMICAL, Korea), ethanol (Union carbide, USA) ), Caprylic / capric triglyceride (TCG-M, Kokyu Alcohol Kogyo, Japan) was used as an emulsifier. In addition, sodium ascorbyl phosphate (BASF, Germany) was used as an antioxidant, methylparaben (Clericant Co., Germany) was used as a preservative, and disodium EDTA (Clewat N2, Nagase Chemtex Corp.) was used as a chelating agent. , Japan), and deionized purified water was used.

(4) TiO2  Nanocapsules Composition

As shown in Table 1, a combination of three types of TiO2 surface-treated with hydrophilicity and three types of TiO2 surface-treated with lipophilic, and three types of surfactant bases as shown in Table 2 were used. A sample of TiO 2 nanocapsule composition was prepared.

(5) TiO2  Preparation of Nanocapsules

TiO 2 nanocapsules were prepared in the following manners for the total 12 nanocapsule compositions in Table 3, respectively. 1 is a manufacturing process diagram of the TiO2 nanocapsules according to the present invention, Figure 2 is a schematic diagram showing the manufacturing process of the TiO2 nanocapsules according to the present invention.

First, phase (W) and phase (O) are melted in a water bath by stirring to 70 ± 5 ℃. Put (O) phase on (W) and 2,000 rpm using a homo mixer (TK Auto Homomixer, Tokushukika kogyo, Japan) for 3 minutes, and add (S) phase, TiO2 suspension at 70 ℃, 2,000rpm, 3 The mixture was further stirred for a minute to preemulsion. This was passed five times under a pressure of 1,000 bar using a high pressure homogenizer (Microfluidizer M110F, Microfluidics Corp., USA) to make nanocapsules and slowly cool down to 30 ° C.

A total of 12 TiO 2 nanocapsules prepared as described above were MA-I (Example 1), MA-II (Example 2), MA-III (Comparative Example 1), and MB-I (Example 3) for convenience. ), MB-II (Example 4), MB-III (Comparative Example 2), MC-I (Comparative Example 3), MC-II (Comparative Example 4), MC-III (Comparative Example 5), MD-I (Comparative Example 6), MD-II (Comparative Example 7), MD-III (Comparative Example 8) will be described (see Table 4).

division Lecithin base (I) Sugar base (II) NSV base (III) Ti-A MA-I (Example 1) MA-II (Example 2) MS-III (Comparative Example 1) Ti-B MB-I (Example 3) MB-II (Example 4) MB-III (Comparative Example 2) Ti-C MC-I (Comparative Example 3) MC-II (Comparative Example 4) MC-III (Comparative Example 5) Ti-D MD-I (Comparative Example 6) MD-II (Comparative Example 7) MD-III (Comparative Example 8)

< Experimental Example  1> TiO2  Experiment to confirm the formation, form and distribution of nanocapsules

In order to confirm the formation, form and distribution of TiO2 nanocapsules prepared according to the embodiment of the present invention, cryo-SEM (Hitach S-4700, Hitachi, Japan), WET SEM (VEGA II LMU with WET SEM, TESCAN, Czech Republic) and TEM (JEM-2010, JEOL Ltd., Japan) were used.

(One) cryo - SEM Observation by

First, cryo-SEM was observed to confirm the formation and distribution of TiO2 nanocapsules.

Pretreatment for Cryo-SEM imaging was as follows. In order to freeze the emulsion sample and observe it with a scanning electron microscope, the sample was fixed to a copper sample carrier and -180 using a Jet Freezer (VAL-TEC JFD030, Liechtenstein). After rapid freezing with a liquid propane at 캜, freezing was performed at -120 캜 using a modular high vacuum coating system (VAL-TEC MED020, Liechtenstein) and ion-deposited with Pt for 2 minutes. The pretreated sample was observed at an acceleration voltage of 10 kV by a scanning electron microscope (Hitachi S-4700, Japan) equipped with a cooling stage.

Figure 5 shows a 5,000-fold SEM image of the TiO2 nanocapsules (MA-I) prepared by an embodiment of the present invention. Looking at the SEM photograph of Figure 5, it can be seen that the TiO2 nanocapsules are formed. Spheres of about 0.1-1 μm are TiO2 nanocapsules, and it is assumed that stabilization is achieved by TiO2 being placed in the capsule.

From the SEM photograph of FIG. 5, not only the formation of the TiO 2 nanocapsules according to the present invention can be confirmed, but also the dispersion phase thereof can be confirmed to be uniform.

(2) WETSEM Observation by

Next, it was observed using WETSEM to confirm the formation and distribution of TiO2 nanocapsules. WETSEM is a wet scanning microscope that connects a detector for WETSEM to a SEM. It is used for analysis by taking a low vacuum reflection electron method for a wet sample having a material that cannot be dried, and a process or time for pretreating a sample such as surface cutting, freezing, coating, etc. of the sample is unnecessary. In this study, a back scattered electron (BSE) detector was used. The magnification was 20 K and the acceleration voltage was 15 mA.

Figure 6 is a 20,000-time SEM image photograph of the TiO2 nanocapsules (MA-II) prepared by WETSEM according to an embodiment of the present invention, Figure 7 is TiO2 nanocapsules (MB) prepared according to an embodiment of the present invention -2) SEM image of 20,000 times by WETSEM.

In Fig. 6, MA-II is very uniform, which is thought to be more homogeneous by the action of sucrose-based surfactants used for encapsulation and isostearic acid used for TiO2 surface treatment as an auxiliary role for emulsification or surfactant action. .

In addition, in FIG. 7, MB-II is uniform and some particle | grains are seen. This may be considered to have influenced the outside of the capsule due to the property of increasing the viscosity of aluminum stearate used for the surface treatment of MB-II. That is, the fact that the properties of the materials used for the surface treatment affects the trauma of the capsule indicates that the capsule structure is a lamellar structure that can be stabilized by the equilibrium between the inner and the trauma materials.

6 and 7, the opaque nucleus in the center of the capsule and the translucent layer on the periphery can be seen. In the middle of the opaque is TiO2, the translucent layer is assumed to be a lamellar layer.

As a result, it can be seen from FIG. 6 and FIG. 7 that the TiO 2 nanocapsules according to the present invention were well formed and they showed a uniform distribution.

(3) TEM Observation by

Finally, observation was made by TEM to confirm the distribution form of TiO2. The pretreatment for TEM imaging was first prepared by diluting the sample and 99.99% GR ethanol at 1:10 and coating the liquid on a carbon coated grid and drying at room temperature for 3 to 4 hours. TEM of the sample was taken. At this time, the magnification of the microscope is 90-300 K and the acceleration voltage is 200 kW.

3 is a 90,000-fold TEM image photograph of TiO 2 nanocapsules (MA-I) prepared according to an embodiment of the present invention, and FIG. 4 is TiO 2 nanocapsules (MA-I) prepared according to an embodiment of the present invention. 300,000 times of TEM image picture.

3 and 4, it can be seen that dozens to hundreds of 10-15 nm flaky TiO2 particles aggregate and exist as secondary particles having a size of about 200-500 nm.

< Experimental Example  2> Formulation ( 劑型 Stability experiment

(1) constellation observation experiment 1

Twelve TiO 2 nanocapsules prepared according to the above Examples and Comparative Examples were carried out after 72 hours of observation, and the results are shown in Table 5 below. At this time, when there is no change in properties compared to the room temperature (dark room) and the observation sample (standard sample) at 25 ° C, it is indicated by good or pass (○), and fine property changes (pH, viscosity change, color, fragrance, precipitation, etc.) Is one or less and a state that is not related to the instability of the sample is represented by normal (△). In addition, there was not more than one distinct property change (rapid pH change, viscosity change, precipitation, phase separation, etc.) and not related to sample instability as not bad (▲). X).

As a result of appearance observation after 72 hours of manufacture, MA-I, MA-II> MA-III, MB-I, MB-II> MB-III> MC-I '' MC-II, MC-III, MD-I, MD -II, MD-III was confirmed that the stability is good. In addition, MD-I, MD-II, and MD-III prepared with hydrophilic TiO2 were all aggregated after 24 hours and easily observed to be entangled with each other. Therefore, it can be seen that hydrophilic TiO 2 is not suitable for preparing stable nanocapsules.

In addition, MC-I, MC-II, and MC-III made of lipophilic TiO 2 having a particle size of 10 nm had a higher viscosity than MA or MB, and were able to identify a dispersed phase that was aggregated or uneven by an optical microscope.

From the above results, in the preparation of the TiO2 nanocapsules according to the present invention, it is preferable to use lipophilic surface-treated TiO2 rather than hydrophilic in terms of stability. Among the lipophilic surface-treated TiO2, isostearic acid or aluminum stearate is particularly preferred. It can be seen that surface treatment with a surface treatment agent containing aluminum stearate is preferable.

(2) Appearance Observation Experiment 2

To observe the change over time of TiO2 nanocapsules, take 6 samples of 30 ml each in a sample bottle for stability test, and place them in an incubator at room temperature (dark), 4 ° C, 25 ° C, and 45 ° C, respectively, and perform temperature cycling. The conditions were observed at intervals of 1 day, 3 days, 5 days, 7 days, 10 days, 21 days, 31 days, and 60 days, respectively, and 10 days at -10 ° C. The temperature cycle was repeated at 45 ° C., room temperature, 4 ° C., and room temperature in order and maintained at each temperature for 24 hours. PH and viscosity were measured every period to determine the stability of the nanocapsule, that is, the state change over time. After 4 hours and 8 hours, the discoloration of the TiO 2 nanocapsules was visually determined through an ultraviolet tester. In addition, using a particle analyzer to measure the size and distribution of the particles every 1, 3, 5 weeks and evaluated the stability through the change.

When there is no change in properties compared to the observed samples at room temperature (dark room) and 25 ° C (standard sample), it is indicated as good or pass (○), and fine property changes (pH, viscosity change, color, fragrance, precipitation, etc.) are 1 The state which is less than the branch and is not related to the instability of the sample is represented by normal (△). In addition, there was not more than one distinct property change (rapid pH change, viscosity change, precipitation, phase separation, etc.) and not related to sample instability as not bad (▲). X).

Table 6 shows the results of the stability test (time change) of the MA-I nanocapsules.

MA-I is a liquid with almost no viscosity. At -10 ℃, there was little change in smell, color, appearance and pH. Samples at 4 ° C, 25 ° C, and cycle began to sink slightly after 3 weeks due to the high specific gravity of TiO2 nanocapsules, and began to sink after 1 week at 45 ° C. However, if the dispersed phase is settled or injured due to the different gravity of the two phases (Quack et al., 1976), even if it is normal (△) or not bad (▲), even if a small shear stress or shake is applied again. It was observed to be a stable emulsion. There was little change in odor, color, appearance and pH at 4 ° C, 25 ° C, 45 ° C and cycle.

From the above results, produced by the present invention It can be seen that the TiO 2 nanocapsules show high stability over time.

(3) over time TiO2  Measurement of the size and distribution of nanocapsules

The size and distribution of TiO2 nanocapsules were observed over time. Laser diffraction was used to measure mean particle size and particle distribution of less than 1,000 nm. Mastersizer Micro (MALVERN Instruments, UK) was used as a measuring device. 0.5 ml of the sample was diluted with 500 ml of distilled water.

Figure 8 is a graph showing the change in the average particle size of TiO2 nanocapsules over time of the TiO2 nanocapsules prepared by Examples and Comparative Examples of the present invention. As shown in Figure 8, the average size of the nanocapsules were measured at 1 day, 1 week, 3 weeks, 5 weeks. Over time, TiO2 nanocapsules gradually grew in size, which can be roughly divided into three groups.

In the first group, the smallest group, MA-I increased 70% from 400 nm to 680 nm for one week. MA-II showed a 59% increase from 410 nm to 650 nm, and MA-III showed a 131% increase from 420 nm to 970 nm, the highest increase among MA. In the same period, MB-I increased 81% from 420 nm to 760 nm, MB-II increased 43% from 400 nm to 570 nm, and MB-III increased 108% from 400 nm to 830 nm. The change in particle size was the highest. MC-I increased significantly from 430 nm to 1,030 nm to 140%.

MD-I, MD-II, and MD-III belonging to the second group had a large particle size of 1.24 ~ 4.23㎛ in one week, and showed aggregation phenomenon from the beginning. The third group, MC-II and MC-III, had the largest particle size of 218 ~ 247㎛. It is assumed that TiO2 secondary particles were aggregated from the surface treatment with lipophilic, and the MC series is thought to have large nanocapsule particles.

9 is a graph showing the particle size distribution one week after the preparation of TiO 2 nanocapsules prepared according to Examples and Comparative Examples of the present invention.

The most widespread distribution of MD, hydrophilic TiO2 surface-treated with aluminum hydroxide, hydrated silica, and alginic acid (10-12), showed agglomeration from the beginning. It can be seen that the average particle size of MD is the largest and uneven. In addition, the surface treatment with aluminum hydroxide and stearic acid, and even in the case of MC having a primary particle of 10nm, the particle size is widely distributed, the final peak of Figures 8) and 9) is 200 It appeared more than ㎛ and the viscosity increased with time. Therefore, MC series was not suitable as TiO2 nanocapsules. Referring to 1) and 4) of FIG. 9, the MBs surface-treated with aluminum hydroxide and isostearic acid and aluminum hydroxide and aluminum stearate are spreadable. It can be seen that this small, narrowly distributed and relatively uniform particle is composed.

In addition, when looking at the graph in the horizontal direction, the effect of the type of natural-derived surfactant used for encapsulation for the same type of TiO2 can be seen. Based on surfactants, lecithin bases show the best behavior. Among them, MA and MB are the most uniform particles. Sugar base can be seen that some of the particles are relatively uniform and large in the MA-II and MB-II. In the case of NSV base (NSV base), the particle distribution is wider than that of lecithin base or sugar base. Therefore, for the encapsulation of TiO2, the lecithin base and sugar base were almost equally good.

FIG. 10 shows particle size distribution curves of 1, 3, and 5 weeks with respect to MA-I, MA-II, MB-II, and MC-I which are relatively stable among 12 nanocapsule samples. In the graph, MA-I, MA-II and MB-II shifted the peak slightly to the right as the average particle grew larger. At 5 weeks, MA-II and MB-II had larger particle counts. In the case of MC-I, there was little change in the size of the nanocapsules.

From the above results, the nanocapsules prepared according to Examples 1 to 4 of the present invention are more stable than the nanocapsules prepared according to Comparative Examples 1 to 8, and the particle size does not change significantly over time. Can be confirmed.

< Experimental Example  3> TiO2  Content measurement

TiO2 content was measured to determine whether TiO2 was lost during the use of a microfluidizer used to prepare TiO2 nanocapsules. ICP (ICP Ultima-II, Jovin-Yivon, France) was used as a measuring instrument.

Looking at the measurement results in Table 7, it can be seen that 90-96% of the amount (Timonal TiO 2 content) TiO 2 is put in the manufacturing process in the TiO 2 nanocapsules. This result complies with the provision of 90% or more of TiO2 quantitative test method of the Korea Food and Drug Administration Notice 2007-44.

From the above results, it can be confirmed that despite the production of the nanocapsules according to the present invention, almost no loss of TiO2 occurs.

< Experimental Example  4> TiO2  Measurement of UV protection ability of nanocapsules

In order to confirm the UV blocking ability of the TiO2 nanocapsules in the ultraviolet region, the ultraviolet ray was irradiated with an ultraviolet / visible / near infrared spectrophotometer to measure the reflectance. In this case, an ultraviolet / visible / near infrared spectrophotometer (UV / VIS / NIR spectrometer, Cary 5000, Varian, USA) was used.

Figure 11 shows the results of measuring the MA-II weekly ultraviolet / visible / near infrared spectrophotometer for 1 to 5 weeks. MA-II reflected 85% or more at 370 nm or less and had a high reflectance of 95% or more at 320 nm or less.

The change of blocking characteristics with time (1-5 weeks) was also observed, but the blocking effect was almost unchanged in the ultraviolet region.

The remaining TiO2 nanocapsule samples were also measured, and the reflectance and graph behavior were similar. The high ultraviolet reflectance indicates that the blocking effect of ultraviolet rays is so high. That is, the TiO 2 nanocapsules prepared according to the present invention had a blocking effect of 95% or more at ultraviolet rays of 290-320 nm having the strongest biological activity, and the blocking characteristics were maintained even when the TiO 2 was nanoencapsulated.

In addition, as can be seen in Figure 11 in the case of the TiO2 nanocapsules according to the present invention, it can be seen that the reflectance is low in the visible light region (wavelength 400nm or more). In other words, the TiO 2 nanocapsules have high transparency so that less turbidity and aesthetics are better.

1 is a manufacturing process diagram of the TiO 2 nanocapsules according to the present invention.

Figure 2 is a schematic diagram showing the manufacturing process of TiO2 nanocapsules according to the present invention.

3 is a 90,000-fold TEM image photograph of TiO 2 nanocapsules (MA-I) prepared according to one embodiment of the present invention.

4 is a 300,000-fold TEM image photograph of TiO 2 nanocapsules (MA-I) prepared according to an embodiment of the present invention.

Figure 5 is a 5,000-fold SEM image of the TiO2 nanocapsules (MA-I) prepared by an embodiment of the present invention.

6 is a 20,000-time SEM image photograph of the TiO 2 nanocapsules (MA-II) prepared by WETSEM according to an embodiment of the present invention.

Figure 7 is a 20,000 times SEM image of the WETSEM of TiO2 nanocapsules (MB-II) prepared according to an embodiment of the present invention.

Figure 8 is a graph showing the change in the average particle size of TiO2 nanocapsules over time of the TiO2 nanocapsules prepared by Examples and Comparative Examples of the present invention.

9 is a graph showing the particle size distribution one week after the preparation of TiO 2 nanocapsules prepared according to Examples and Comparative Examples of the present invention.

10 is a graph showing the change in particle size distribution over time of the TiO 2 nanocapsules prepared by Examples and Comparative Examples of the present invention.

FIG. 11 is a graph showing changes in UV-reflection spectrum over time of TiO 2 nanocapsules (MA-II) prepared according to an embodiment of the present invention.

Claims (6)

delete delete A composition comprising a lipophilic surface treated TiO 2, a surfactant, an emulsifier, an emulsifier, an antioxidant, a chelating agent, and purified water, wherein the surfactant is hydrogenated lecithin or sucrose distearate. TiO2 nanocapsule composition comprising a. The method of claim 3, wherein Lipophilic surface-treated TiO2, hydrogenated lecithin as the surfactant, cetylphosphate as the co-emulsifier, caprylic / capric triglyceride as the emulsifier, sodium ascorbyl phosphate as the antioxidant, TiSO2 nanocapsule composition comprising disodium EDTA and purified water as chelating agent, and further comprising glycerin and ethanol as emulsion stabilizing and moisturizing ingredients. The method of claim 3, wherein Lipophilic surface-treated TiO2, sucrose distearate as the surfactant, cetylphosphate as the co-emulsifier, caprylic / capric triglyceride as the emulsifier, sodium ascorbyl phosphate as the antioxidant, TiSO2 nanocapsule composition comprising disodium EDTA and purified water as the chelating agent, and further comprising propylene glycol and ethanol as the emulsion stability and moisturizing component. After melting each of the aqueous phase component for nanocapsules containing purified water, antioxidant and chelating agent and the oil phase component for nanocapsules including surfactant and co-emulsifier to a temperature of 65 ~ 75 ℃, the melted nanocapsules for A first pretreatment emulsifying step of adding an oil phase component for nanocapsules to a water phase component and stirring with a homomixer; A second pretreatment emulsifying step of adding TiO2 suspension in which TiO2 is suspended in caprylic / capric triglyceride to the first pretreatment emulsion, and then stirring with a homomixer; and  Method for producing a TiO 2 nanocapsule comprising the step of encapsulating and cooling the secondary pretreatment emulsion using a high pressure homogenizer.

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