KR20080091653A - Mesoporous composite powder containing metallic oxides and the method for preparing thereof - Google Patents

Abstract

A composite powder is provided to exhibit a wide range of ultraviolet rays(UV-A and UV-B) blocking capability and show improved feeling of use and stability by supporting a metal oxide such as Ce and Fe in pores of an inorganic complex powder and an organic complex powder, thereby being usefully used for blocking the UV. A composite powder is characterized in that a metal oxide such as CeO2, TiO2, Fe2O3 and ZnO is supported in an inorganic powder or an organic polymer. A cosmetic composition for blocking UV comprises the composite powder as an effective ingredient. To prepare the composite powder, the inorganic powder or the organic polymer is reacted with at least one metal precursor selected from the group consisting of cerium chloride, cerium nitrate, iron chloride, iron nitrate, titanium isopropoxide, titanium butoxide, titanium sulfate, TiCl4, ZnCl4 and zinc acetate through co-precipitation or impregnation. Further, the inorganic powder has 200 to 900 m^2/g of specific surface area, 0.3 to 1.5cc/g of pore volume and 2 to 20nm of pore size.

Description

Composite powder containing metal oxide in pores and manufacturing method thereof

1 is a scanning electron microscope (SEM) photograph of the medium-sized pore composite powder prepared in Example 1. FIG.

2 is a scanning electron microscope (SEM) photograph of the polymer composite powder prepared in Example 3. FIG.

FIG. 3 is an X-ray diffraction graph of the inorganic composite powder having ultraviolet blocking function prepared in Examples 1 to 3. FIG.

Figure 4 is a UV-spectrum of the inorganic composite powder having a sunscreen function prepared in Examples 1 to 3.

The present invention has a wide range of ultraviolet (UV-A and -B) blocking ability by supporting metal oxides such as cerium and iron in pores of inorganic powders such as porous silica and porous alumina silicate or organic polymers such as PMMA. The present invention relates to a composite powder having improved safety.

Sunscreens can be divided into two types, chemical and physical, depending on their mechanism of action. Chemical blocking agent refers to a substance that absorbs ultraviolet rays by trapping solar energy in a molecule and exhibits a blocking effect. This belongs here. Chemical blockers cause problems with light stability when used as cosmetics and cause irritant contact dermatitis in sensitive skin, and they are absorbed by the skin causing irritation or serious problems with safety due to photoreaction products. Most organic sunscreens are restricted in use, but most commercial sunscreens are chemical barriers, so high sunscreen index is not desirable. On the other hand, using an inorganic sunscreen can provide a sunscreen without irritation to the skin while blocking a wide range of ultraviolet spectroscopy.

Physical blockers include zinc oxide, titanium dioxide, iron oxide and magnesium oxide, which have physical properties that reflect and disperse ultraviolet rays. While they have a good blocking effect, they are disadvantageous because they are not cosmetically appropriate. Cosmetic improper means that it is not good for appearance by applying such substances to the skin, causing unpleasant and unpleasant feelings due to the wet feeling, and the skin appearing to be dull due to the clouding phenomenon. In addition, nano-dispersed excess physical blocker can penetrate into the skin, which is likely to cause safety problems, and can cause skin irritation and skin damage due to photoactivity resulting from free radicals. Particle size is increased by the second agglomeration, and there is a disadvantage in terms of functionality that the UV blocking ability is deteriorated over time.

When applied as a product, in general, W / O emulsions are prepared to stably disperse inorganic materials, and the above-described inorganic physical barriers are added to the oil of the trauma. Physical barrier agents are preferably used for even distribution in the skin and effective sun protection. It is often manufactured to have a uniform distribution of small size.

Therefore, many studies on cosmetics for reducing or delaying the above-described skin aging phenomenon have been progressed for a long time. There is a method of reducing skin penetration of ultraviolet rays by using a sunscreen. In addition, much research has been conducted on sunscreen compounds for protecting the skin from ultraviolet rays (particularly UV-A and -B).

In general, when metal oxides such as titanium (Ti), cerium (Ce), zinc (Zn), and iron (Fe) are directly used or compounded, their size increases due to the characteristic of metal and the aggregation of secondary particles. The disadvantages in terms of the aspects and the long-term irritation potential of the fine inorganic particles in the skin and the decrease in the use will occur. In addition, when used in existing sunscreen products, the affinity of the interface with the oil phase in the formulation is lower than the specific gravity of the inorganic material, the dispersion stability is lowered, and due to the aggregation of secondary particles, the size of the ultraviolet light increases over time. There is a problem such as poor blocking ability. Thus, the ideal sunscreen should be non-toxic to skin tissues and not irritating the skin, should be resistant to chemical or photodegradation when applied to the product and not absorbed by the skin. Therefore, there is a need for the development of an inorganic sunscreen having high efficiency in the broad wavelength range and excellent skin safety.

Therefore, the present inventors have developed an inorganic powder such as porous silica, porous alumina silicate, or organic powder such as PMMA to develop inorganic particles having a submicron size so as to have effective dispersion stability and even distribution in the skin in the formulation of physical barrier agent. It was found that by supporting metal oxides such as cerium and iron in pores such as polymers, composite powders having a wide range of ultraviolet (UV-A and UV-B) blocking ability and improved usability and safety can be produced. The invention was completed.

Accordingly, an object of the present invention is to block ultraviolet rays (UV-A and -B) in a wide area by supporting metal oxides such as cerium and iron in pores of inorganic powders such as porous silica and porous alumina silicates or organic polymers such as PMMA. It is to provide a composite powder having the ability to improve the usability and safety.

In order to achieve the above object, in the present invention, by supporting metal oxides such as cerium and iron in pores such as porous inorganic powder or organic polymer, it has a wide range of ultraviolet (UV-A and -B) blocking ability and feeling It provides a composite powder with improved safety.

The porous inorganic powder used in the present invention has a specific surface area of 200 to 900 m 2 / g, and a porous silica or porous alumina silicate having a pore volume (Vp) of 0.3 to 1.5 cc / g and a pore size of 2 to 20 nm. desirable.

The porous alumina silicate used in the present invention is a zeolite having a BEA type, MFI type, MOR (mordenite) type and FER (ferrierite) type structure in which the molar ratio of silica (Si) / alumina (Al) is in the range of 10 to 100. It is good to use.

In addition, in the present invention, a composite powder having an organic polymer as a support in addition to the porous inorganic powder may be prepared. Due to the high density and polarity of nano-sized inorganic particles, agglomeration with each other in the formulation to form large secondary particles has been a major factor in reducing the instability and UV blocking performance of the formulation. In the present invention, highly surface-treated inorganic nanoparticles are used to disperse the particles into MMA monomers to form particles. Thus, the surface has characteristics of an organic polymer, and the inorganic particles present in the polymer phase are unique due to the optical transmittance of the organic polymer after polymerization. A composite powder prepared to maintain ultraviolet scattering ability is prepared. At this time, the organic polymer used in the present invention is preferably PMMA (polymethylmethacrylate), but is not limited thereto.

Preferred examples of the metal oxide supported in the pores of the porous inorganic powder or organic polymer in the present invention include ultraviolet-B blocking components such as cerium oxide (CeO ₂ ) and titanium oxide (TiO ₂ ); and iron oxide (Fe ₂ O _3). UV-A blocking components such as) and zinc oxide (ZnO) are preferred.

The average particle size of the metal oxide supported in the present invention is 5 ~ 15nm, the size of the atomized particles in the mixture prepared through the embodiment of the present invention is preferably about 0.3 ~ 5㎛. The content of the metal oxide may be 5 to 50% by weight based on the total weight of the porous inorganic powder or the organic polymer composite powder, more preferably 30 to 40% by weight.

In the present invention, the metal precursor used to prepare the metal oxide-supported composite powder is cerium chloride (cerium chloride), cerium nitrate (cerium nitrate), iron chloride (iron chloride), iron nitrate (iron nitrate), Titanium isopropoxide, titanium butoxide, titanium sulfate, titanium tetrachloride (TiCl ₄ ), zinc tetrachloride (ZnCl ₄ ) and zinc acetate. and by a well-known coprecipitation (coprecipitation) or combining method (impregnation) in the art and they are converted to the metal oxide impregnated in the porous inorganic powder or the organic polymer, through which _{CeO 2 -Fe 2 O 3, CeO} 2 -ZnO, TiO _Two- component compounds such as ₂ -Fe ₂ O ₃ and TiO ₂ -ZnO can be prepared. In addition to the above method, the composite powder according to the present invention can be produced by a conventionally well-known method in a range that does not impair the object of the present invention.

The present invention also relates to a cosmetic composition for sunscreen containing the composite powder on which the metal oxide is supported as an active ingredient. The cosmetic composition according to the present invention may contain the composite powder in an amount of 5 to 50% by weight based on the total weight of the composition. When the content of the composite powder is less than 5% by weight, the effect is insignificant, and when the content of the composite powder is more than 50% by weight, it may cause difficulty in formulation stability.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are intended to illustrate the invention, it is apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Reference Example 1 Medium Porosity Silica Manufacturing Process

Polyethylene oxide block (polypropylene oxide) 20 g of polyethylene oxide was dissolved in 602.57 g of 2N sulfuric acid, and 43.11 g of tetraethylorthosilicate was added thereto while stirring vigorously at room temperature using a magnetic stirring device. The reaction mixture was stirred at room temperature for 1 hour and then the solution was stirred at 40 ° C. for 24 hours. The reaction mixture was hydrothermally reacted in an oven at 100 ° C. for 24 hours. The precipitate was filtered off and dried at 100 ° C. In order to remove the surfactant contained in the dried sample was washed clean with ethanol and calcined for 10 hours at 550 ℃ in air.

Example 1 Preparation of Porous Silica Composite Powder Carrying Metal Oxide

After completely dissolving 17 g of cerium chloride in 12 g of distilled water, 10 g of the medium-porous silica prepared in Reference Example 1 was mixed, mixed with the cerium precursor solution at room temperature, stirred for 1 to 3 hours, and then filtered. Vacuum drying at room temperature and firing were carried out to obtain 16 g of a medium-porous composite powder loaded with cerium oxide.

After 5.8 g of iron chloride was completely dissolved in 12 g of distilled water, the cerium oxide-supported medium-sized porous powder was mixed with the iron precursor solution at room temperature, stirred for 1 to 3 hours, and then filtered. Vacuum drying at room temperature and calcining yielded 17.5 g of porous silica composite powder on which the final cerium oxide and iron oxide were supported.

The porous silica composite powder prepared above has a uniform shape and size, and a scanning electron microscope (SEM) photograph of the porous silica composite powder is shown in FIG. 1.

Example 2 Preparation of Porous Alumina Silicate Composite Powder Supported with Metal Oxide

17 g of cerium chloride was completely dissolved in 12 g of distilled water, and then 10 g of porous alumina silicate (zeolite Y) (Zeolyst international) was mixed with the cerium precursor solution at room temperature, stirred for 1 to 3 hours, and then filtered. 16 g of alumina silicate composite powder loaded with cerium oxide was obtained by vacuum drying at room temperature and firing.

After completely dissolving 5.8 g of iron chloride in 5 g of distilled water, the porous alumina silicate loaded with cerium oxide obtained above was mixed with the iron precursor solution at room temperature, stirred for 1 to 3 hours, and then filtered and stored at room temperature. Vacuum drying and firing gave 17.5 g of a porous alumina silicate composite powder in which the final cerium oxide and iron oxide were supported.

Example 3 Preparation of Composite Organic Polymer Composite Powder Supported with Metal Oxide

To prepare a composite organic polymer (PMMA, polymethylmethacrylate) composite powder loaded with metal oxides, 12 g of cerium oxide (Sigma, Aldrich, CeO ₂ ) in the form of inorganic particles and 1.5 g of iron oxide (Sigma Aldrich, Fe ₂ O ₃ ) were added. 16 g of MMA (Sigma, Aldrich, methylmethacrylate), 15 g of EGDMA (Sigma, Aldrich, ethyleneglycol dimethacrylate) and 1 g of ADVN (Sigma, Aldrich, 2,2'-Azobis-2,4--(dimethyllvalero nitrile)) Sonication and dispersion were carried out for 5 minutes. After confirming the dispersion, the mixture was poured into a solution containing a 2% PVA aqueous solution and a surfactant and homo-mixed at 5000 rpm for 5 minutes. The prepared emulsion solution was placed in a double wall reactor and reacted for 6 hours while stirring at 300 rpm under nitrogen filling. At this time, the reaction temperature was maintained at 60 ℃. 0.01 weight% of sodium nitrate was added to the aqueous solution to superpose | polymerize. After the polymerization, the mixture was washed several times with water and ethanol mixed solution and dried to obtain 48.2 g of the final product.

The organic polymer composite powder prepared above has a spherical uniform shape and size, and a scanning electron microscope (SEM) photograph of the organic polymer composite powder is shown in FIG. 2.

[Test Example 1]

X-ray diffraction graph (Rigaku Co., Ltd.) of the composite powder prepared in Examples 1 to 3 is shown in FIG. As can be seen in Figure 3, it was confirmed that the cerium oxide and iron oxide are supported through the X-ray graph of the porous composite powder loaded with cerium and iron prepared in Examples 1 to 3.

Test Example 2 Safety of UV-protective Composite Powder

Since raw materials for cosmetics are used in the human body, safety for the human body is important above all. Therefore, the presence or absence of toxicity and irritation to the human body of the porous composite powder obtained in Examples 1 to 3, which is a sunscreen compound, was examined through the following experiment. At this time, the safety experiment used a solution made by dispersing the composite powder in 20% concentration in PEG-400 oil.

1-1. Skin primary irritation test Primary skin irritation test )

For the first skin irritation test, 12 rabbit hairs (NZ White Rabbit, Hallim experimental animal) were removed 24 hours before application of the test substance, and the porosity of Examples 1 to 3 was 2.5 cm × 2.5 cm wide. The composite powder was observed by applying 0.1 ml each for 24 hours.

As a result, it was determined that there was no stimulus.

1-2. skin Writing  Experiment( Skin sensitization test )

Each of three male and female guinea pigs (Gunea pig, Hallim experimental animal) using the porous composite powder of Examples 1 to 3, respectively, according to the test method of Magnusson and Kligman Sensitization experiments were conducted.

As a result, skin abnormalities such as erythema, edema, and skin formation could not be observed.

1-3. anatomy Patch  Experiment( Human patch test )

A human patch on the porous composite powder of Examples 1 to 3 according to the CTFA Guidelines (The Cosmetic Toiletry and Fragrance Association, INC, Washington, DC20036, 1991) in 30 healthy people aged 20 to 28 years. The experiment was conducted.

As a result, there was no skin primary irritation response. In the above toxicity and safety experiments on the skin, the composite powder according to the present invention was confirmed to be a safe material as a raw material without toxicity and irritation as a cosmetic, that is, a skin external preparation.

[Test Example 3] UV protection ability investigation

In order to determine the UV blocking ability of the porous composite powder prepared in Examples 1 to 3, titanium oxide having a UV blocking ability as a positive control group (TiO ₂ ) and the porous according to Examples 1 to 3 according to the present invention. Ultraviolet ray blocking ability was compared with respect to the composite powder, and the results are shown in FIG. 4. In FIG. 4, when the UV absorption spectrum (280 to 400 nm) of the porous composite powders according to Examples 1 to 3 is compared with titanium oxide (TiO ₂ ), the porous composite powders according to Examples 1 to 3 are obtained. In the UV-B (280-320nm) region showed a similar effect as titanium oxide, the UV-A region (320-400nm) was confirmed that the absorption (absorbance) significantly increased.

Therefore, it can be expected that the porous composite powder carrying metal oxides such as cerium and iron according to the present invention can be used for UV protection.

As described above, the composite powder according to the present invention has a wide range of ultraviolet (UV-A and -B) blocking ability by supporting metal oxides such as cerium and iron in pores such as inorganic composite powder and organic composite powder. In addition, the user's feel and safety can be improved, which can be useful for UV protection.

Claims (11)

A composite powder in which a metal oxide is supported in an inorganic powder or an organic polymer. The method of claim 1, wherein the metal oxide is at least one selected from the group consisting of cerium oxide (CeO ₂ ), titanium oxide (TiO ₂ ), iron oxide (Fe ₂ O ₃ ) and zinc oxide (ZnO). Composite powder. According to claim 1, wherein the inorganic powder has a specific surface area of 200 to 900 m 2 / g, the pore volume (Vp) 0.3 to 1.5 cc / g and the pore size (pore size) of the porous silica and porous alumina silicate range Composite powder, characterized in that selected from the group consisting of. According to claim 3, wherein the porous alumina silicate is selected from the group consisting of BEA type, MFI type, MOR (mordenite) type and FER (ferrierite) type having a molar ratio of silica (Si) / alumina (Al) in the range of 10 to 100. Composite powder characterized in that the zeolite having at least one structure. The composite powder of claim 1, wherein the organic polymer is polymethylmethacrylate (PMMA). The composite powder according to claim 1, wherein the metal oxide is supported by 5 to 50% by weight based on the total weight of the composite powder. A sunscreen cosmetic composition containing the composite powder according to any one of claims 1 to 6 as an active ingredient. Inorganic or organic polymers include cerium chloride, cerium nitrate, iron chloride, iron nitrate, titanium isopropoxide, titanium butoxide ( Coprecipitation or incorporation with at least one metal precursor selected from the group consisting of titanium butoxide, titanium sulfate, titanium tetrachloride (TiCl ₄ ), zinc tetrachloride (ZnCl ₄ ) and zinc acetate Method for producing a composite powder produced by the reaction (impregnation). 9. The inorganic powder of claim 8, wherein the inorganic powder has a specific surface area of 200 to 900 m 2 / g, a pore volume (Vp) of 0.3 to 1.5 cc / g, and a pore size of 2 to 20 nm. Method for producing a composite powder, characterized in that selected from the group consisting of. 10. The method of claim 9, wherein the porous alumina silicate is selected from the group consisting of BEA type, MFI type, MOR (mordenite) type and FER (ferrierite) type with a molar ratio of silica (Si) / alumina (Al) in the range of 10 to 100. Method for producing a composite powder, characterized in that the zeolite having at least one structure. The method of claim 8, wherein the organic polymer is polymethylmethacrylate (PMMA).

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