KR101404965B1 - Mesoporous composite powder containing metallic oxides and the method for preparing thereof - Google Patents

Abstract

(UV-A and -B) blocking ability by supporting a metal oxide such as cerium and iron in pores of inorganic powder such as porous silica and porous alumina silicate or organic polymer such as PMMA, And a composite powder having improved safety.

Metal oxide, ultraviolet screening, inorganic ultraviolet screening agent, composite powder, porous silica, porous alumina silicate, PMMA

Description

Technical Field [0001] The present invention relates to a composite powder containing metal oxides in pores,

1 is a scanning electron microscope (SEM) photograph of the mesoporous composite powder prepared in Example 1. Fig.

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

3 is an X-ray diffraction chart of the inorganic composite powder having ultraviolet-shielding function prepared in Examples 1 to 3. Fig.

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

(UV-A and -B) blocking ability by supporting a metal oxide such as cerium and iron in pores of inorganic powder such as porous silica and porous alumina silicate or organic polymer such as PMMA, And a composite powder having improved safety.

Sunscreens can be divided into two categories, chemical and physical, before their functional groups. A chemical blocking agent is a substance that absorbs ultraviolet rays by capturing the sunlight energy in the molecule and exhibits a blocking effect. The chemical blocking agent includes a PABA derivative, a cinamate derivative, a salicylic acid derivative, benzophenones, and anthranilates This belongs here. Chemical blockers, when used as cosmetics, are problematic in light intensity and can cause irritative contact dermatitis on sensitive skin, which can be absorbed into the skin and cause irritation or serious problems with safety due to photoreactive products Most organic UV-blocking agents are limited in their use, but high UV-blocking indexes are not desirable because chemical blocking agents are the main constituents in most commercially available UV-blocking agents. On the other hand, when an inorganic ultraviolet screening agent is used, it is possible to provide an ultraviolet screening agent having no irritation to the skin while shielding a wide range of ultraviolet ray spectroscopy.

Physical blocking agents are substances with physical properties that reflect and disperse ultraviolet radiation, such as zinc oxide, titanium oxide, iron oxide, and magnesium oxide. They have a disadvantage that they have good blocking effect but are not suitable for cosmetics. Not being cosmetically appropriate means that these substances are not clean and uncomfortable due to a feeling of use when applied to the skin, and appearance is bad due to whitening of the skin due to whitening. In addition, excessive physical blockers dispersed in the nano-size can penetrate the skin, and there is a lot of safety problems. Also, it can cause skin irritation and skin damage due to the photoactive action due to free radicals. There is a disadvantage in that the particle size is increased by secondary agglomeration and the ultraviolet shielding ability is deteriorated with time.

When applied as a product, a W / O emulsion is generally prepared to disperse the inorganic substance stably and the physical blocker of the above inorganic substance is added to the oil of the trauma. In order to distribute evenly on the skin and effectively block the ultraviolet rays, It is often manufactured to have a uniform distribution with a small size.

Accordingly, researches on cosmetics for reducing or delaying the aging of skin have been carried out in the past. In the first place, there is a method of reducing skin penetration of ultraviolet rays by using ultraviolet ray blocking agents. In addition, many studies have been made on ultraviolet blocking compounds for protecting the skin from ultraviolet rays (especially, UV-A and -B).

Generally, when metal oxides such as titanium (Ti), cerium (Ce), zinc (Zn) and iron (Fe) are directly used or compounded, the size is increased due to the characteristic of metal and the aggregation of secondary particles, There arise disadvantages such as a disadvantage in terms of the appearance and a possibility of long-term stimulation of the skin of fine inorganic particles and a feeling of use. In addition, when used in conventional ultraviolet screening products, the interface affinity with the oil phase in the formulation is lower than the specific gravity of the inorganic material, and the dispersion stability is lowered. As the secondary particles agglomerate, There is a problem that the blocking ability is decreased. Therefore, the ideal sunscreen should be non-toxic to the skin tissue, not to irritate the skin, resistant to chemical degradation or photodegradation when applied to the product, and not absorbed by the skin. Therefore, there is a need to develop inorganic ultraviolet ray blocking agents having excellent ultraviolet ray shielding ability and skin safety in a wide wavelength range.

The present inventors have found that an inorganic powder such as porous silica and porous alumina silicate or an inorganic powder such as PMMA can be used in order to develop inorganic particles having a submicron size so as to have effective dispersion stability and uniform distribution in skin in the form of a physical barrier agent. (UV-A and UV-B) shielding ability by supporting metal oxides such as cerium and iron in the pores of polymer, etc., it is possible to manufacture a composite powder having improved feeling and safety. Thereby completing the invention.

Accordingly, it is an object of the present invention to provide a method and apparatus for protecting ultraviolet light (UV-A and -B) from a wide range by supporting a metal oxide such as cerium and iron in pores of inorganic powder such as porous silica and porous alumina silicate or organic polymer such as PMMA. And the composite powder is improved in feeling and safety.

In order to achieve the above-mentioned object, the present invention provides a porous inorganic powder or organic polymer having metal oxide such as cerium and iron in a pore, thereby having a capability of blocking ultraviolet rays (UV-A and -B) And a composite powder having improved safety.

The porous inorganic powder used in the present invention is a porous inorganic porous powder having a specific surface area of 200 to 900 m2 / g, 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 structure of BEA type, MFI type, MOR (mordenite) type and FER (ferrierite) type having a molar ratio of silica (Si) / alumina It is good to use.

Further, in the present invention, in addition to the porous inorganic powder, a composite powder having an organic polymer as a support may be produced. Due to the high density and polarity of the nano-sized inorganic particles, they aggregated within the formulation to form a large secondary particle, which served as a main factor in the instability of the formulation and in the deterioration of UV blocking performance. Therefore, in the present invention, highly dispersed inorganic nanoparticles are dispersed in an MMA monomer to be granulated so that the surface of the inorganic nanoparticle has the characteristics of an organic polymer, and the inorganic particles existing in the polymer phase due to the optical transparency of the organic polymer after polymerization A composite powder prepared so as to maintain ultraviolet scattering ability is prepared. At this time, the organic polymer used in the present invention is preferably PMMA (polymethylmethacrylate), but it is not limited thereto.

In the present invention, preferred examples of the metal oxide supported in the pores of the porous inorganic powder or the organic polymer include ultraviolet-B blocking components such as cerium oxide (CeO ₂ ) and titanium oxide (TiO ₂ ) and iron oxide (Fe ₂ O ₃ ) And zinc oxide (ZnO).

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

In the present invention, the metal precursor used for preparing the metal oxide-supported composite powder includes cerium chloride, cerium nitrate, iron chloride, iron nitrate, Titanium isopropoxide, titanium butoxide, titanium sulfate, titanium tetrachloride (TiCl ₄ ), zinc tetrachloride (ZnCl ₄ ), and zinc acetate. They are converted into metal oxides by the coprecipitation or impregnation which is well known in the art and are carried in porous inorganic powder or organic polymer, through which CeO ₂ -Fe ₂ O ₃ , CeO ₂ -ZnO, TiO _2- Fe ₂ O ₃ and TiO ₂ -ZnO can be produced. In addition to the above methods, the composite powder according to the present invention can be produced by a conventionally known method within the range not detracting from the object of the present invention.

The present invention also relates to a cosmetic composition for protecting ultraviolet rays, which contains 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. When the content of the composite powder is more than 50% by weight, the formulation stability may be difficult.

Hereinafter, the present invention will be described in more detail with reference to examples. It will be apparent, however, to those skilled in the art that these embodiments are for describing the present invention and that the scope of the present invention is not limited to these embodiments.

[Reference Example 1] Preparation of mesoporous silica

After 20 g of polyethylene oxide block (polypropylene oxide) polyethylene oxide was dissolved in 602.57 g of 2N sulfuric acid, 43.11 g of tetraethyl orthosilicate was added with vigorous stirring at room temperature using a magnetic stirring apparatus. The reaction mixture was stirred at ambient temperature for 1 hour and then the solution was stirred at 40 < 0 > C for 24 hours. The reaction mixture was subjected to hydrothermal reaction in an oven at 100 ° C for 24 hours. The precipitate was filtered and dried at 100 < 0 > C. To remove the surfactant contained in the dried sample, it was cleaned with ethanol and calcined in the air at 550 ° C for 10 hours.

[Example 1] Production of a 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 mesoporous silica prepared in Reference Example 1 was taken out, mixed with the cerium precursor solution at room temperature, thoroughly stirred for 1 to 3 hours, Vacuum-dried at room temperature, and fired to obtain 16 g of a mesoporous composite powder carrying cerium oxide.

After 5.8 g of iron chloride was completely dissolved in 12 g of distilled water, the cerium oxide-supported mesoporous composite powder obtained above was mixed with the iron precursor solution at room temperature, stirred for 1 to 3 hours, and filtered Vacuum-dried at room temperature and fired to obtain 17.5 g of a final porous silica composite powder carrying cerium oxide and iron oxide.

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

[Example 2] Production of porous alumina silicate composite powder carrying metal oxide

After completely dissolving 17 g of cerium chloride in 12 g of distilled water, 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, Vacuum-dried at room temperature and fired to obtain 16 g of cerium oxide-supported alumina silicate composite powder.

After 5.8 g of iron chloride was completely dissolved in 5 g of distilled water, the cerium oxide-supported porous alumina silicate thus obtained was mixed with the iron precursor solution at room temperature, stirred for 1 to 3 hours, filtered, Vacuum drying and firing were carried out to obtain 17.5 g of porous alumina silicate composite powder carrying final cerium oxide and iron oxide.

[Example 3] Production of a composite oxide of a metal oxide-supported composite organic polymer

(Sigma, Aldrich, CeO ₂ ) and 1.5 g of iron oxide (Sigma Aldrich, Fe ₂ O ₃ ) were mixed to prepare a composite powder of metal oxide-supported polymethylmethacrylate (PMMA) 15 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) And dispersed by sonication for 5 minutes. After confirming the dispersion, the mixture was poured into a solution containing 2% PVA aqueous solution and surfactant, and homomixed at 5000 rpm for 5 minutes. The prepared emulsion solution was put into a double wall reactor and reacted for 6 hours with stirring at 300 rpm under nitrogen filling. The reaction temperature was maintained at 60 ° C. 0.01 wt% of sodium nitrate was added to the aqueous solution to be polymerized. After polymerization, the mixture was washed several times with a mixture of water and ethanol, and then dried to obtain 48.2 g of a final product.

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

[Test Example 1]

The X-ray diffraction (X-ray diffraction, Rigaku) of the composite powders prepared in Examples 1 to 3 is shown in Fig. As can be seen from FIG. 3, it was confirmed from the X-ray graph of the porous composite powder carrying cerium and iron prepared in Examples 1 to 3 that cerium oxide and iron oxide were carried.

[Test Example 2] Safety of composite powder for ultraviolet shielding

Since the ingredients of cosmetics are used in the human body, the safety of the human body is of utmost importance. Thus, the present inventors examined the toxicity and irritancy of the porous composite powder obtained in Examples 1 to 3, which are ultraviolet blocking compounds, to the human body through the following experiments. At this time, in the safety test, a solution prepared by dispersing the composite powder at a concentration of 20% in PEG-400 oil was used.

1-1. First skin irritation test ( Primary skin irritation test )

For the first skin irritation experiment, twelve back hairs of 12 rabbits (NZ White Rabbit, Hallym) were removed 24 hours before application of the test material, and 2.5 cm x 2.5 cm wide pores of Examples 1 to 3 The composite powder was applied by 0.1 ml each for 24 hours and observed.

As a result, it was judged that there was no stimulation.

1-2. skin Make sense  Experiment( Skin sensitization test )

Gunaa pig (hanlim experimental animal) Three male and three female hams were treated with the porous composite powders of Examples 1 to 3, respectively, according to the test method of Magnusson and Gligman (Kligman) Sensory writing experiments were carried out.

As a result, it was not possible to observe skin abnormalities such as erythema, edema, and scar formation.

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

The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. According to the CTFA guidelines (The Cosmetic Toiletry and Fragrance Association, INC, Washington, DC20036, 1991), 30 healthy twenty- Experiments were conducted.

As a result, no skin primary irritation reaction occurred. In the above toxicity and skin safety test, it was confirmed that the composite powder according to the present invention is safe as a cosmetic raw material without toxicity and irritation, that is, as a skin external preparation.

[Test Example 3] Investigation of ultraviolet shielding ability

In order to examine the ultraviolet shielding ability of the porous composite powders prepared in Examples 1 to 3, titanium oxide (TiO ₂ ) having ultraviolet shielding ability as a positive control group and porous titanium oxide (TiO ₂ ) according to Examples 1 to 3 according to the present invention The composite powders were compared with ultraviolet shielding ability, and the results are shown in FIG. 4, the UV absorption spectrum (280 to 400 nm) of the porous composite powder according to Examples 1 to 3 was compared with titanium oxide (TiO ₂ ). As a result, it was found that the porous composite powder according to Examples 1 to 3 In the UV-B region (280-320 nm), the effect was similar to that of titanium oxide. However, the absorbance of the UV-A region (320-400 nm) was significantly increased.

Therefore, it is expected that the porous composite powder carrying the metal oxide such as cerium and iron according to the present invention can be used for ultraviolet ray shielding.

As described above, the composite powder according to the present invention has a capability of blocking ultraviolet rays (UV-A and -B) in a wide range by supporting metal oxides such as cerium and iron in pores such as inorganic composite powder and organic composite powder , Feeling and safety are improved, and thus it can be usefully used for ultraviolet ray shielding.

Claims (11)

In the inorganic powder or organic polymer, Iron oxide (Fe ₂ O ₃ ) and cerium oxide (CeO ₂ ) are supported on a composite powder. delete The method of claim 1, wherein the inorganic powder is selected from the group consisting of porous silica having a specific surface area of 200 to 900 m2 / g, a pore volume (Vp) of 0.3 to 1.5 cc / g and a pore size of 2 to 20 nm and a porous alumina silicate Wherein the composite powder is selected from the group consisting of: The method according to claim 3, wherein the porous alumina silicate is selected from the group consisting of BEA, MFI, mordenite and FER having a molar ratio of silica (Si) / alumina (Al) Wherein the zeolite is a zeolite having at least one structure. The composite powder according to claim 1, wherein the organic polymer is PMMA (polymethylmethacrylate). The composite powder according to claim 1, wherein the iron oxide (Fe ₂ O ₃ ) and cerium oxide (CeO ₂ ) are supported in an amount of 5 to 50 wt% based on the total weight of the composite powder. 6. A cosmetic composition for ultraviolet shielding comprising a composite powder according to any one of claims 1 to 6 as an active ingredient. Inorganic powder or organic polymer, At least one cerium precursor selected from the group consisting of cerium chloride and cerium nitrate; And at least one iron precursor selected from the group consisting of iron chloride and iron nitrate by coprecipitation or impregnation of the iron precursor. 9. The method of claim 8, wherein the inorganic powder comprises porous silica and porous alumina silicate having a specific surface area of 200 to 900 m2 / g, a pore volume (Vp) of 0.3 to 1.5 cc / g and a pore size of 2 to 20 nm Wherein the composite powder is selected from the group consisting of: The method of claim 9, wherein the porous alumina silicate is selected from the group consisting of BEA, MFI, mordenite, and ferrierite types having a molar ratio of silica (Si) / alumina (Al) Wherein the zeolite is a zeolite having at least one structure. The method for producing a composite powder according to claim 8, wherein the organic polymer is PMMA (polymethylmethacrylate).

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