TWI398265B - Sunscreen cosmetics having exfoliated clay and method for preparing the same - Google Patents

Description

Desiccated clay sunscreen beauty product and preparation method thereof

The invention relates to a sunscreen beauty product and a preparation method thereof, in particular to a sunscreen beauty product with delaminated clay and a preparation method thereof.

The ingredients in the sunscreen product usually contain both a physical sunscreen and a chemical sunscreen. Among them, the application of a physical sunscreen to form a barrier layer on the skin can prevent ultraviolet rays from penetrating the skin surface and have a reflective effect to achieve skin protection. Efficacy, and chemical sunscreens are molecules that are contained in the effective chemical composition, which are absorbed by the surface of the skin and interact with ultraviolet light to transform them into harmless energy.

Recent studies have found that components in sunscreen products produce phototoxicity after photoreaction, for example, para-aminobenzoic acid (PABA), extension of p-aminobenzoic acid, and benzotrimethane. Chemical sunscreens such as dibenzoylmethane form harmful intermediates such as free radicals or reactive oxygen molecules during photoreaction. However, free radicals and reactive oxygen molecules cause human aging and various Disease, even one of the important causes of cancer. Furthermore, the commonly used physical sunscreen ingredients are titanium dioxide and zinc oxide, both of which are semiconductor materials, and have an absorption gap of about 3.2 eV, wherein the energy gap plays the role of absorbing energy, and this absorption helps in blocking ultraviolet light. Improve the shielding effect of ultraviolet light, but on the other hand, because these materials are photocatalysts, illumination It is easy to generate a free radical reaction in the solution, which causes phototoxicity and peroxidase after photocatalysis, and also inactivates biomolecules.

In view of this, there is an urgent need to develop a sunscreen beauty product which can effectively reduce free radicals generated by the skin, which not only blocks ultraviolet rays, but also enhances the stability of sunscreen beauty products, and achieves the effects of protecting the skin, reducing body damage or other complications.

The main object of the present invention is to provide a method for preparing a sunscreen beauty product having a delaminated clay, by adding delaminated clay to a sunscreen beauty product, and using the delaminated clay for chemical sunscreen of sunscreen beauty products. The special adsorption of the amine component and the adsorption of the physical sunscreen component on the acid base of the chemical sunscreen component, so that the physical sunscreen component forms a bridge by chemical sunscreen components and adsorbs to the delaminated clay, blocking free radicals that may be generated. Prevent possible damage to the skin from ingredients in sunscreen beauty products.

Another object of the present invention is to provide a sunscreen beauty product having a delaminated type clay, which can be applied to the human body to effectively reduce free radicals which may be generated during the sun protection process to prevent the skin from being peroxidized or comprehensively oxidized. Attacks, therefore, can be applied to a wide range of sunscreen products.

In order to achieve the above object, the present invention provides a method for preparing a sunscreen beauty product having a delaminated clay, which comprises the following steps: providing a a delaminated clay; providing a sunscreen composition comprising at least a physical sunscreen component, a chemical sunscreen component, and a substrate; and adding the delaminated clay to the sunscreen composition and mixing evenly Forming a mixture. Wherein, the physical sunscreen component is adsorbed to the delaminated clay by forming a bridge by the chemical sunscreen component.

In addition, the preparation method of the above delaminated clay may include the following steps: providing a layer of clay; adding a water-soluble starter and at least one monomer having polarity to perform emulsification-free emulsification with the layered clay; Polymerization; and, a solvent is provided to remove the polymer portion. Among them, the water-soluble starter may include one of the following groups: potassium persulfate (KPS), ammonium persulfate (APS), and water soluble azo-initiator. The polar monomer may have a vinyl or a vinyl, for example, may comprise one of the following groups: methyl acrylate, ethyl acrylate, methyl Methyl methacrylate (MMA), hydroxy methacrylate, amine methacrylate, acrylic acid, methacrylic acid, isopropyl acrylamide N-isopropylacrylamine; NIPAAm), hydroxylethylacrylate, vinyl acetate (VAc), or a copolymer thereof; and the solvent may include one of the following groups: toluene, benzene , tetrahydrofuran (THF), cyclohexane, tetrachloromethane, and chloroform.

In the preparation method of the delaminated clay sunscreen beauty product of the present invention, the delaminated clay is in the form of a sheet, and may be at least one selected from the group consisting of smetite clay and vermiculite ( Vermiculte), halloysite, sericite, and mica. Wherein, the smetite clay may be at least one selected from the group consisting of montmorillonite, saponite, hectorite, beidelite, and iron smoothing. Nontronite, and stevensite, preferably delaminated montmorillonite. Further, the delaminated clay of the present invention is of a nanometer grade and can be applied to a sunscreen beauty product of a general nanometer grade.

Furthermore, in the preparation method of the delaminated clay sunscreen beauty article of the present invention, the sunscreen composition may be an emulsion, a cream, a gel, a paste, a powder, a lotion, or the like.

The above sunscreen composition, comprising at least one physical sunscreen component, which may be titanium dioxide (TiO ₂ ), ultrafine titanium dioxide (TTO), zinc oxide (ZnO), or a combination thereof; a chemical sunscreen component, which may have A chemical sunscreen compound having at least one carboxyl group and at least one amine group, preferably para-aminobenzoic (PABA); and a matrix, may include propylene glycol (PG).

The present invention also provides a sunscreen beauty product having a delaminated clay comprising: a delaminated clay; a sunscreen composition comprising at least a physical sunscreen component, a chemical sunscreen component, and a matrix. Wherein the delaminated clay is added to the sunscreen composition and mixed After homogenization, a mixture is formed; and the physical sunscreen component is adsorbed to the delaminated clay by forming a bridge by the chemical sunscreen component.

Further, the above-mentioned delaminated clay is in the form of a sheet, and may be at least one selected from the group consisting of smetite clay, vermiculte, halloysite, sericite ( Sericite), and mica. Wherein, the smetite clay is at least one selected from the group consisting of montmorillonite, saponite, hectorite, beidelite, and iron smoothing. Stone (nontronite), and magnesium talc (stevensite). Preferred is delaminated montmorillonite. Furthermore, the delaminated clay of the present invention is of a nanometer grade and can be applied to sunscreen beauty products of general nanometer grade.

Further, in the defrosted clay sunscreen beauty product of the present invention, the sunscreen composition may be an emulsion, a cream, a gel, a paste, a powder, a lotion, or the like.

The above sunscreen composition, comprising at least one physical sunscreen component, which may be titanium dioxide (TiO ₂ ), ultrafine titanium dioxide (TTO), zinc oxide (ZnO), or a combination thereof; a chemical sunscreen component, which may have A chemical sunscreen compound having at least one carboxyl group and at least one amine group, preferably para-aminobenzoic (PABA); and a matrix, may include propylene glycol (PG).

The above-mentioned sunscreen beauty product with delaminated clay, because the delaminated clay can adsorb the amine base of the chemical sunscreen component, and the acid base of the other end of the amine base of the chemical sunscreen component can adsorb the physical sunscreen component, so that the physical sunscreen component Adsorbed on the surface of the delaminated clay by forming a bridge of chemical sunscreen ingredients, Therefore, when illuminated, the excited state electrons generated by the physical sunscreen component are easily captured by the delaminated clay, which reduces the chance of lipid peroxidation in the skin.

The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily appreciate the other advantages and advantages of the present invention. The present invention may be embodied or applied in various other specific embodiments. The details of the present invention can be variously modified and changed without departing from the spirit and scope of the invention.

Method for preparing delaminated clay

Take 28.512g montmorillonite (MMT) powder and 4.6224g potassium persulfate (KPS) (K ₂ S ₂ O ₈ , initiator) into serum bottle containing 1500ml deionized water, use magnet at room temperature Stirring was carried out for 72 hours to uniformly disperse montmorillonite and KPS in an aqueous solution. Next, 9.5 g of methyl methacrylate (MMA, C ₅ H ₈ O ₂ ) was weighed and added to a two-necked flask containing 20 wt% of MMT/KPS 125 ml, and heated and stirred at 70 ° C for 24 hours. The MMA is polymerized into polymethyl methacrylate (PMMA), and then degassed water is removed by suction filtration, and the white solid remaining on the filter paper is the PMMA/MMT composite.

The PMMA/MMT composite was immersed in a 1 L toluene solution for three days, and then stirred for one day with a DC stirrer to dissolve the PMMA in toluene. 3 L of deionized water was added to the above toluene solution, and the flaky montmorillonite in the half angel toluene phase was extracted and extracted into the aqueous phase, and allowed to stand for one day to separate the toluene phase from the aqueous phase. The aqueous phase is extracted to obtain a delaminated nano-flaky montmorillonite aqueous solution. The remaining toluene solution was further added with 3 L of deionized water. The residual flaky montmorillonite in the half-angel toluene phase was extracted and extracted into the aqueous phase. After standing for one day, the toluene phase was separated from the aqueous phase, and the aqueous phase was extracted to obtain delamination. The nano-flaky montmorillonite aqueous solution can be repeated three times to completely extract the delaminated nano-flaky Montmorillonite in the toluene phase, which is a delaminated Montmorillonite nanosheet (exMMT) aqueous solution (as shown in the figure). 1)).

Preparation of sunscreen beauty products

The sunscreen solutions of various comparative examples and examples were prepared as follows:

Comparative Example 1 Preparation of PABA/PG solution

The quantitative para-aminobenzoic acid (PABA) was weighed and stirred with a propanol (PG) solvent for 20 minutes to uniformly disperse it. This is a purified sunscreen lotion.

Comparative Example 2 PABA/TTO/PG sunscreen solution

Quantitative PABA and ultrafine titanium dioxide (TTO) (ie, titanium dioxide), with PG as solvent, because TTO itself is easy to aggregate, it is not easy to be uniformly dispersed in PG, so PABA should be first studied in the mortar. TTO is homogenized in PG solvent, and then vortexed by ultrasonic for 20 minutes to uniformly disperse. This is a sunscreen type solution of PABA/TTO/PG.

Example 1 Sunscreen solution of PABA/exMMT/PG

First, the solvent of the exMMT aqueous solution was replaced with PG, and the PABA powder was added to the PG solution containing exMMT, and then ultrasonically oscillated for 20 minutes to uniformly disperse. This was a sunscreen type solution of PABA/exMMT/PG.

Wherein, if the chemical sunscreen component PABA is added to a 2% by weight aqueous solution of exMMT, it is fully stirred, diluted and sampled by a copper mesh, and the TEM image after drying, as shown in FIG. 2, is due to the presence of an amine group on the PABA molecule and delamination. The negative electricity on the surface of the smectite produces an electrostatic force that is adsorbed on the surface of the smectite, and hydrogen bonds adsorbed on the montmorillonite cause montmorillonite to aggregate.

Example 2 PABA/exMMT/TTO/PG sunscreen solution

First replace the solvent of exMMT aqueous solution with PG, weigh the appropriate amount of PABA and TTO, add PABA and TTO powder to exMMT/PG solution, pre-mix PABA, exMMT and TTO in PG solvent in the mortar, then Surge with ultrasound for 20 minutes to evenly disperse. This is a sunscreen solution of PABA/exMMT/TTO/PG.

Wherein, if 2wt% PABA and 2wt% TTO are added to 2wt% exMMT aqueous solution, fully stirred, diluted and sampled by copper mesh, and dried TEM image, as shown in Fig. 3, TTO particles can be found under electron microscope observation. It is adsorbed on the surface of exMMT, mainly because the carboxyl group at one end of PABA is adsorbed by TTO particles, and the amine group at the other end is adsorbed by exMMT, causing TTO particles to bridge the surface of exMMT by PABA molecules. Show.

Analysis of experimental results of various sunscreen solutions

Using the above various sunscreen solution samples, the composition ratios are as shown in the following Table 1, and the amount is applied to fresh pigskin under a fixed area, and then placed in a UV light box (Unilux AC, 144W, 420~470nm) for different illumination. After the time was taken out, the change in the IR spectrum of the pig skin surface layer was analyzed by ATR-FTIR.

First, the IR analysis of the pig skin without any sunscreen solution, measured at different times under UV light, is shown in Figure 5, where -CH ₃ and CH ₂ are stable due to the stable structure of the saturated fatty acids in the lipid. The characteristic peaks (v=2920 cm ^-1 and v=2851 cm ^-1 ) did not change significantly, so long-term processing was performed on the basis of 2920 cm ^-1 . The untreated pigskin showed a significant increase in the amine-based characteristic peak (v=3280 cm ^-1 ) under different ultraviolet light exposures (as shown in Figure 5(a)), probably because of the pig skin. The guanamine group of the protein undergoes a broken bond after illumination, resulting in an increase in the number of amine groups. Further, in Fig. 5(b), the characteristic peak from the lipid is observed by the conventional peak treatment of the characteristic peak C=O (v = 1640 cm ^-1 ) of the protein amide I (amide I), such as Triglyceride comprising C=O characteristic peak of CO-O (v=1745 cm ^-1 ), CO characteristic peak (v=1164 cm ^-1 ), and -CH ₃ characteristic peak (v=1366 cm ^-1 ), and the UV irradiation at different times, to change the lipid structure of the skin cells, so that the intensity of 1366cm ^-1 to 1745cm decreased ^-1, 1260 cm ^-1 but the intensity increased significantly, 1260 cm ^-1 peak is mainly characterized in membrane peroxidation The damage caused by CO stretching and in-plane bending vibrations. In addition, the amideII characteristic peak of the amino acid in the protein structure (v = 1539 cm ^-1 ) (i.e., the in-plane NH bending of the amide group) was observed by IR pattern, 1574 cm. ^-1 is also an asymmetric stretching vibration of -COO from the amino acid structure of the protein, and the intensity of 1539 cm ^-1 and 1574 cm ^-1 is decreased by ultraviolet light irradiation. Therefore, ultraviolet light may cause damage to the protein, protein structure There are many possibilities for the mechanism of destruction, and one of the mechanisms may be the formation of an amine group.

However, ultraviolet radiation on the skin in addition to the protein, but on the human DNA that we also have an impact, the IR spectrum of 1231cm ^-1 and 1095cm ^-1 PO from the DNA phosphate (phosphate) of _2, 1231cm ^-1 PO ₂ from ^- asymmetric vibration, 1095cm ^-1 is PO ₂ ^- symmetric vibration caused by ultraviolet irradiation intensity of 1231cm ^-1 is weakened, and the vibration frequency is widened displaced to 1240 cm ^-1, the intensity of 1095cm ^-1 of enhanced so that Ultraviolet light irradiation will affect the change in phosphate structure in the DNA. It can be seen that ultraviolet light illuminates the skin and affects the lipid, protein and DNA of the skin cells. Since lipid peroxidation is a generation cause of cancer, and therefore the characteristic peaks oxidized lipid (v = 1260m ^-1) of PO ₂ ^- The relative intensity (I ₁₂₆₁ / I ₁₂₃₁ asymmetric vibration characteristic peaks (v = 1231cm ^-1) _-1240 ) As a reference index, compare the effect of solutions containing different components on the degree of lipid peroxidation. Figure 5(c) shows the IR spectrum of wavenumber range 1400~1100cm ^-1 , and untreated pig skin is irradiated by ultraviolet light for 60 minutes. _Thereafter , I ₁₂₆₁ /I _1231-1240 was increased from 0.28 to 1.46, and it was found that ultraviolet rays illuminate the skin and cause severe peroxidation of lipids to skin cells.

Referring to Fig. 6, the pig skin containing the PABA/PG sunscreen solution of Comparative Example 1 was applied, and the FTIR spectrum was irradiated with ultraviolet light at different times, and normalized on the basis of the 1640 cm ^-1 peak. Apply the PABA/PG sunscreen solution to the pig skin for UV irradiation, then wash the solution on the pig skin, and use the reference value of the pig skin which is not illuminated at zero time but wash away the solution, wherein the characteristic peak of cell membrane peroxidation (v=1260cm ^-1 ) showed some improvement after UV irradiation, but the degree of increase was not as good as that of untreated pig skin. Therefore, the application of PABA/PG solution to pig skin can reduce the degree of lipid peroxidation in cells. Furthermore, pigskin after 60 minutes to ultraviolet irradiation, oxidized lipid peaks characteristic of PO ₂ ^- the relative intensity (I ₁₂₆₁ / I _1231-1240) asymmetric vibration characteristic peaks increased from 0.5 to 0.89.

Further, referring to Fig. 7, the pig skin containing the PABA/TTO/PG sunscreen solution of Comparative Example 2 was irradiated with ultraviolet light for FTIR patterns at different times, and normalized on the basis of the 1640 cm ^-1 peak. deal with. Apply PABA/TTO/PG sunscreen solution to pig skin for UV irradiation, then wash the solution on pig skin, and use the reference value of pig skin which is not illuminated at zero time but wash away the solution. after 60 minutes of light irradiation, lipid peroxidation of characteristic peaks of PO ₂ ^- the relative intensity (I ₁₂₆₁ / I _1231-1240) asymmetric vibration characteristic peaks increased from 0.4 to 1.29. Since the TTO particles are excited by ultraviolet light, they generate excited state electrons, react with organic substances to generate free radicals, and then peroxidize the lipids of pig skin, so that the ratio of I ₁₂₆₁ /I _1231-1240 is greatly improved.

Next, referring to FIG. 8 , the pig skin containing the PABA/exMMT/PG sunscreen solution of Example 1 was applied, and the FTIR spectrum of different time was irradiated by ultraviolet light, and the conventional treatment was carried out based on the peak of 1640 cm ^-1 . . Apply PABA/exMMT/PG sunscreen solution to pig skin for UV irradiation, then wash the solution on pig skin, and use the reference value of pig skin which is not illuminated at zero time but wash away the solution. after 60 minutes of light irradiation, lipid peroxidation of characteristic peaks of PO ₂ ^- the relative intensity of asymmetric vibration characteristic peaks (I ₁₂₆₁ / I _1231-1240) increased from 0.73 to .75. It can be seen that the addition of exMMT to the PABA/PG sunscreen solution can obviously further reduce the degree of lipid peroxidation in pig skin.

Finally, please refer to FIG. 9 , which is to apply the PABA/exMMT/TTO/PG sunscreen solution of Example 2, and irradiate the FTIR spectrum at different times with ultraviolet light, and make the routine based on the 1640 cm ^-1 peak. Processing. The PABA/exMMT/TTO/PG sunscreen solution was applied to the pig skin for ultraviolet irradiation, and the solution on the pig skin was washed away, and the pig skin which was not illuminated at zero time but washed away was used as a reference value. Among them, after 60 minutes of ultraviolet light irradiation, the characteristic peak of cell membrane peroxidation (v=1260cm ^-1 ) only slightly increased after ultraviolet light irradiation, and the characteristic peak of lipid peroxidation on PO ₂ ^- asymmetric vibration characteristic peak The relative intensity (I ₁₂₆₁ /I _1231-1240 ) increased from 0.55 (0 minutes) to only 0.83, which is lower than the ratio of Comparative Example 1 and Comparative Example 2. Therefore, exMMT can enhance lipids in sunscreen formulations. Its antioxidant capacity.

In summary, the present invention proves that the present invention provides a sunscreen beauty product having a delaminated type of clay, which can effectively reduce the skin's free radicals and reduce the degree of peroxidation to achieve skin protection.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

Figure 1 is a TEM image of a 2 wt% exMMT aqueous solution at magnifications (a) 30K and (b) 100K.

Figure 2 is a TEM image of an aqueous solution containing 2 wt% PABA and 2 wt% exMMT at magnifications (a) 30K and (b) 100K.

Figure 3 is a TEM image of an aqueous solution containing 2 wt% PABA, 2 wt% TTO, and 2 wt% exMMT at magnifications (a) 30K and (b) 100K.

Figure 4 is a schematic diagram showing the adsorption of PABA by titanium dioxide and montmorillonite.

Fig. 5A is an FTIR spectrum of untreated pig skin irradiated with ultraviolet light at different times on the basis of 2920 cm ^-1 .

Fig. 5B is an FTIR spectrum of untreated pig skin irradiated with ultraviolet light at different times on the basis of 1640 cm ^-1 .

Figure 5C is an FTIR map of the enlarged 1220-1340 cm ^-1 segment of Figure 5B.

Fig. 6 is a FTIR spectrum of pig skin after application of the PABA/PG sunscreen solution of Comparative Example 1, irradiated with ultraviolet light for different times.

Fig. 7 is a FTIR spectrum of pig skin after application of the PABA/TTO/PG sunscreen solution of Comparative Example 2, irradiated with ultraviolet light for different times.

Fig. 8 is a FTIR spectrum of pig skin after application of the PABA/exMMT/PG sunscreen solution of Example 1 at various times with ultraviolet light.

Figure 9 is a FTIR spectrum of pig skin after application of the PABA/exMMT/TTO/PG sunscreen solution of Example 2, irradiated with ultraviolet light for different times.

Claims (10)

A sunscreen beauty product having a delaminated clay, comprising: a delaminated clay; a sunscreen composition comprising at least a physical sunscreen component, a chemical sunscreen component, and a substrate; wherein the A layered clay is added to the sunscreen composition and uniformly mixed to form a mixture; and the physical sunscreen component is adsorbed to the delaminated clay by forming a bridge by the chemical sunscreen component. The sunscreen beauty product according to claim 1, wherein the delaminated clay is at least one group detached from the group consisting of: smetite clay, vermiculte, Halloyite, sericite, and mica. The sunscreen beauty product according to claim 2, wherein the smetite clay is at least one selected from the group consisting of montmorillonite, saponite, and lithium. Hectorite, beidelite, nontronite, and stevensite. The sunscreen beauty product according to claim 1, wherein the delaminated clay is in the form of a sheet and has a nano-grade delaminated smectite. The sunscreen beauty product according to claim 1, wherein the sunscreen composition is an emulsion, a cream, a gel, a paste, a powder, a lotion, or the like. The sunscreen beauty product according to claim 1, wherein the physical sunscreen component is titanium dioxide (TiO ₂ ), ultrafine titanium dioxide (TTO), zinc oxide (ZnO), or a combination thereof. The sunscreen beauty product according to claim 1, wherein the chemical sunscreen component is a chemical sunscreen compound having at least one carboxyl group and at least one amine group. The sunscreen beauty product according to claim 1, wherein the chemical sunscreen component is p-aminobenzoic acid (PABA). The sunscreen beauty product of claim 1, wherein the matrix comprises propylene glycol (PG). A method for preparing a sunscreen beauty product according to any one of claims 1 to 9, which is characterized in that it has a delaminated clay sunscreen beauty product, comprising the steps of: providing a delaminated clay; providing a The sunscreen composition comprises at least a physical sunscreen component, a chemical sunscreen component, and a substrate; and the delaminated clay is added to the sunscreen composition and uniformly mixed to form a mixture; wherein The physical sunscreen component is adsorbed to the delaminated clay by forming a bridge of the chemical sunscreen component; the method for preparing the delaminated clay comprises the steps of: providing a layer of clay; adding a water-soluble starter and At least one monomer having polarity is subjected to an emulsifier-free emulsion polymerization with the layered clay; and a solvent is provided to remove the polymer portion.