ANTI-POLLUTION ECO-FRIENDLY MATERIAL AND METHOD FOR PREPARING THE SAME
20240238176 ยท 2024-07-18
Assignee
Inventors
Cpc classification
B01J20/3219
PERFORMING OPERATIONS; TRANSPORTING
A61Q17/04
HUMAN NECESSITIES
B01J20/3274
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3204
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3293
PERFORMING OPERATIONS; TRANSPORTING
B01J20/06
PERFORMING OPERATIONS; TRANSPORTING
B01J20/265
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
B01J20/06
PERFORMING OPERATIONS; TRANSPORTING
B01J20/32
PERFORMING OPERATIONS; TRANSPORTING
A61Q17/04
HUMAN NECESSITIES
Abstract
Disclosed are an anti-pollution cosmetic material and a method for preparing the same, wherein the anti-pollution cosmetic material contains a material having ultraviolet-blocking properties or heavy metal adsorption capacity or an organic-inorganic hybrid material having both ultraviolet-blocking properties and heavy metal adsorption capacity, so that the use of the inventive titanium dioxide (TiO.sub.2) composite particles and heteroatomic polymer-attached polyamino acid polymer can provide not only an ultraviolet-blocking or anti-pollution cosmetic composition but also a cosmetic composition having both an ultraviolet-blocking effect and an anti-pollution effect, and such a material can mitigate the white cast and the harmfulness of a microparticle powder, which are problems of existing inorganic sunblocks, and can be utilized as an anti-pollution material for skin protection having heavy metal adsorption capacity.
Claims
1. A method for preparing titanium dioxide composite particles, the method comprising: (a) preparing a titanium dioxide (TiO.sub.2) derivative with an amine (NH.sub.2) functional group introduced to the surface of titanium dioxide (TiO.sub.2); and (b) reacting the titanium dioxide (TiO.sub.2) derivative obtained in step (a) and a polyamino acid derivative to fuse the titanium oxide derivative and the polyamino acid derivative.
2. The method of claim 1, further comprising, before step (b), attaching a heteroatomic compound to the polyamino acid derivative.
3. The method of claim 1, wherein the titanium dioxide (TiO.sub.2) derivative with the amine functional group is formed by reaction of titanium dioxide and an aminosilane at a weight ratio of 1:1 to 1:5.
4. The method of claim 1, wherein the polyamino acid derivative is at least one selected from the group consisting of polysuccinimide, polyaspartic acid, polyaspartamide, and polyhydroxyethyl aspartamide.
5. The method of claim 1, wherein the polyamino acid derivative has a heteroatomic compound further attached thereto.
6. The method of claim 5, wherein the heteroatomic compound is at least one selected from the group consisting of histamine, aminoimidazole, aminomethylimidazole, aminopropylimidazole, aminomethylbenzimidazole, and histidine.
7. A titanium dioxide composite particle represented by Chemical Formula 1 below: ##STR00012## Z is a titanium dioxide particle; X is a C.sub.1 to C.sub.6 linker; and Y is ##STR00013## where Y, and Y, each are independently Compound A, Compound B, or a copolymer of Compound A and Compound B. wherein Compound A is ##STR00014## and Compound B is ##STR00015## where m and n each are independently an integer of 1 to 1500.
8. The particle of claim 7, wherein in the copolymer of Compound A and Compound B, Compound A and Compound B are present in a random sequence.
9. The particle of claim 7, wherein in the copolymer of Compound A and Compound B, Compound A and Compound B are present in an alternating sequence.
10. The particle of claim 7, wherein Y has the following structure: ##STR00016## where l is an integer of 0 to 1500.
11. The particle of claim 7, wherein Y has the following structure: ##STR00017## where l and k each are independently an integer of 0 to 1500.
12. The particle of claim 7, wherein Y has the following structure: ##STR00018## wherein k is an integer of 1 to 800.
13. The particle of claim 7, wherein Y has the following structure: ##STR00019## where l and k each are independently an integer of 1 to 1500.
14. A polyamino acid polymer comprising Compound A and Compound B as monomers, wherein Compound A is ##STR00020## and Compound B is ##STR00021## where t and r each are independently an integer of and 1 to 1500.
15. The polymer of claim 14, wherein Compound A and Compound B are present in a random sequence.
16. The polymer of claim 14, wherein Compound A and Compound B are present in an alternating sequence.
17. An ultraviolet-blocking cosmetic composition containing the titanium dioxide composite particle of claim 7.
18. An anti-pollution cosmetic composition containing the polyamino acid polymer of claim 14.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0078] The above and other aspects, features and advantages of the present disclosure will be more apparent from the following detailed description taken in conjunction with the accompanying drawings.
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DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS
[0099] Hereinafter, the present disclosure will be described in more detail with reference to exemplary embodiments. These exemplary embodiments are provided only for the purpose of illustrating the present disclosure in more detail, and therefore, according to the purpose of the present disclosure, it would be apparent to a person skilled in the art that these exemplary embodiments are not construed to limit the scope of the present disclosure.
EXAMPLES
[0100] Throughout the present specification, the % used to express the concentration of a specific material, unless otherwise particularly stated, refers to (wt/wt) % for solid/solid, (wt/vol) % for solid/liquid, and (vol/vol) % for liquid/liquid.
Preparation Examples 1
Preparation Example 1-1. Preparation of Titanium Dioxide (TiO.SUB.2.) Composite Particles (Material 1, T-PSI) Having Ultraviolet-Blocking Properties
(1) Synthesis of Titanium Dioxide Derivative (T-NH.SUB.2.)
[0101] First, titanium dioxide (TiO.sub.2) and an aminosilane were reacted to prepare a TiO.sub.2 derivative with an amine (?NH.sub.2) functional group introduced to the surface of titanium dioxide (TiO.sub.2). A schematic diagram of the reaction is shown in (a) of
[0102] Specifically, TiO.sub.2 (1.5 g) was added into 50 ml of toluene under nitrogen conditions, followed by ultrasonic treatment for 30 min. Thereafter, 200 wt % of (3-aminopropyl) triethoxysilane (APTS) was added, followed by stirring in a reflux state at 150? C. for 3 days. The product was obtained by centrifugation, and the yield was 65.0%.
(2) Synthesis of Titanium Dioxide (TiO.SUB.2.) Composite Particles (Material 1, T-PSI)
[0103] Next, the titanium dioxide (TiO.sub.2) derivative prepared in (1) above was reacted with polysuccinimide (PSI) belonging to a hydrophilic biodegradable polyamino acid polymer to produce titanium dioxide (TiO.sub.2) composite particles (Material 1) having ultraviolet-blocking properties. A schematic diagram of the reaction is shown in (b) of
[0104] Specifically, the TiO.sub.2 derivative (2 g) modified with the amine group was added to 200 ml of DMSO, followed by ultrasonic treatment for 30 min. Thereafter, 100 wt % of polysuccinimide (PSI) was added, followed by stirring at room temperature for 2 days. The product was obtained by centrifugation, and the yield was 60.0%.
[0105] In order to conduct qualitative evaluation of the material prepared in the present disclosure, Fourier transform infrared analysis (FT-IR) and thermogravimetric analysis were performed.
[0106] Specifically, the Fourier infrared spectroscopy analysis was performed by a Vertex70 spectrometer (Bruker Optics, MA, USA) in the range of 600 cm.sup.?1 to 4000 cm.sup.?1, and the thermogravimetric analysis was performed by a TG/DTA7300 instrument (SEICO Instrument, Tokyo, Japan) from 0? C. to 800? C. with a temperature change of 10? C./min.
[0107] The FT-IR data results for Material 1 are shown in
[0108] As shown in
[0109] The TGA data for Material 1 are shown in
[0110] As shown in
Preparation Example 1-2. Preparation of Biocompatible Polyamino Acid Polymer Material (Material 2, PH) Having Heavy Metal Adsorption Capacity
[0111] A biocompatible polyamino acid polymer material (Material 2) having heavy metal adsorption capacity was prepared by attaching a heteroatomic compound to polysuccinimide (PSI), a polyamino acid biocompatible polymer material. A schematic diagram of the reaction is shown in
[0112] Specifically, PSI (2 g) was added into 25 ml of DMSO and dissolved with sufficient stirring. Thereafter, histamine dihydrochloride (0.92 g) and triethylamine (1.66 ml) were added, followed by stirring at room temperature for 2 days. Then, the product was obtained by drying through vacuum. The yield was 98%.
[0113] NMR data for Material 2 (PH) are shown in
[0114] In addition, FT-IR data and TGA data for Material 2 (PH) are shown in
Preparation Example 1-3. Preparation of Titanium Dioxide (TiO.SUB.2.) Composite Particles (Material 3, T-PH) Having Ultraviolet-Blocking Properties and Heavy Metal Adsorption Capacity
[0115] The TiO.sub.2 derivative (T-NH.sub.2) of Preparation Example 1-1 and the biocompatible polyamino acid polymer material (PH) having heavy metal adsorption capacity of Preparation Example 1-2 were reacted to produce titanium dioxide (TiO.sub.2) composite particles (Material 3, T-PH) having both ultraviolet-blocking properties and heavy metal adsorption capacity.
[0116] Specifically, the TiO.sub.2 derivate (2 g) modified with the amine group was added to 40 ml of DMSO, followed by ultrasonic treatment for 30 min. Thereafter, 100 wt % of PH (Material 2) was added, followed by stirring at room temperature for 2 days. The product was obtained by centrifugation, and the yield was 64.0%.
[0117] FT-IR data and TGA data for Material 3 (T-PH) are shown in
Test Examples 1
Test Example 1-1. Verification of Ultraviolet-Blocking Effect
[0118] To verify the UV blocking effects of the titanium dioxide (TiO.sub.2) composite particles (Material 1, T-PSI) prepared in Preparation Example 1-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 3, T-PH), UV-Vis spectrum analysis was performed to evaluate the absorbance and transmittance.
[0119] In this example, powdery TiO.sub.2 confirmed to have an ultraviolet-blocking effect was used as a control group. By using (a) the composition of the water-in-oil (w/o) emulsion and (b) the preparation method thereof as shown in
[0120] The results are shown (a) and (b) of
[0121] As shown in (a) and (b) of
Test Example 1-2. Verification of Heavy Metal Adsorption Effect
[0122] To verify the heavy metal adsorption effect of the biocompatible polyamino acid polymer material (Material 2, PH) prepared in Preparation Example 1-2 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 3, T-PH), inductively coupled plasma (ICP) analysis was performed.
[0123] Specifically, Material 2 (PH) was exposed to copper (Cu.sup.2+) and nickel (Ni.sup.2+) aqueous solutions for 5 min, 30 min, and 2 h, respectively, and the adsorbed materials were re-precipitated in methanol (MeOH) two times. After that, the amounts of heavy metals adsorbed were measured to verify the heavy metal adsorption capacity. To measure the degrees of adsorption of copper (Cu.sup.2+) and nickel (Ni.sup.2+) depending on three concentrations (50,000 mg/L, 100,000 mg/L, and 300,000 mg/L), Material 2 was exposed to metal solutions with the three concentrations for 12 h, and then the adsorbed materials were re-precipitated in methanol two times to re-elute un-adsorbed heavy metals. After that, the amounts of heavy metals adsorbed were measured to verify the heavy metal adsorption capacity.
[0124] Material 3 was exposed to copper (Cu.sup.2+) and nickel (Ni.sup.2+) aqueous solutions for 12 h, and then the adsorbed materials were washed with water three times to re-elute un-adsorbed heavy metals. After that, the amounts of heavy metals adsorbed were measured to verify the heavy metal adsorption capacity.
[0125] The results are shown in
[0126] As shown in
[0127] As shown in
[0128] Resultantly, the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 3, T-PH) of the present disclosure exhibited not only an ultraviolet-blocking effect but also an excellent heavy metal adsorption effect.
Test Example 1-3: White Cast Reducing Effect
[0129] To evaluate an effect of mitigating the white cast, a typical disadvantage shown when titanium dioxide (TiO.sub.2) is used in the composition of a cosmetic product, the titanium dioxide (TiO.sub.2) composite particles (Material 1, T-PSI) prepared in Preparation Example 1-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 3, T-PH) were measured for whiteness index by using a colorimeter.
[0130] The results are shown in Table 1.
TABLE-US-00001 TABLE 1 Classification Whiteness index Cream 47.03 TiO.sub.2 46.51 T-PSI 41.04 T-PH-21 35.14
[0131] As shown in Table 1, compared with titanium dioxide (TiO.sub.2), Material 1 (T-PSI) and Material 3 (T-PH) showed reduced whiteness indexes, indicating a reduced white cast.
Test Example 1-4: Verification of Photo-Catalytic Property Reducing Effect
[0132] The use of titanium dioxide (TiO.sub.2) in the cosmetic composition may cause skin oxidation due to the photo-catalytic properties of TiO.sub.2. Hence, the titanium dioxide (TiO.sub.2) composite particles (Material 1) prepared in Preparation Example 1-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 3) were investigated for a photo-catalytic property reducing effect.
[0133] Each titanium dioxide composite particle material (0.1 g) was added to 100 ml of a 10 ppm methylene blue solution, followed by exposure to 254 nm UV light (24 W), and then the photo-catalytic property effect of the titanium dioxide (TiO.sub.2) composite particle material was compared while the degree of reduction in methylene blue absorbance was verified at a wavelength of 666 nm.
[0134] The results are shown
[0135] As shown in
Preparation Examples 2
Preparation Example 2-1. Preparation of Biocompatible Polyamino Acid Polymer Material (Material 4, PA) Having Heavy Metal Adsorption Capacity
[0136] A biocompatible polyamino acid polymer material (Material 4) having heavy metal adsorption capacity was prepared by attaching a heteroatomic compound to polysuccinimide (PSI), a polyamino acid biocompatible polymer material. A schematic diagram of the reaction is shown in
[0137] Specifically, PSI (1 g) was added into 30 ml of DMSO and dissolved with sufficient stirring. Thereafter, 1-(3-Aminopropyl) imidazole (0.36 mL) was followed by stirring at room temperature for 24 h. Then, the product was obtained by drying through vacuum. The yield was 99%.
[0138] NMR data for Material 4 (PA) are shown in
[0139] In addition, FT-IR data and TGA data for Material 4 (PA) are shown in
Preparation Example 2-2. Preparation of Titanium Dioxide (TiO.SUB.2.) Composite Particles (Material 5, T-PA) Having Ultraviolet-Blocking Properties and Heavy Metal Adsorption Capacity
[0140] The TiO.sub.2 derivative (T-NH.sub.2) of Preparation Example 1-1 and the biocompatible polyamino acid polymer material (PA) having heavy metal adsorption capacity of Preparation Example 2-1 were reacted to produce titanium dioxide (TiO.sub.2) composite particles (Material 5, T-PA) having both ultraviolet-blocking properties and heavy metal adsorption capacity.
[0141] Specifically, the TiO.sub.2 derivate (T-NH.sub.2) (2 g) modified with the amine group was added to 40 ml of DMSO, followed by ultrasonic treatment for 30 min. Thereafter, 100 wt % of PA (Material 4) was added, followed by stirring at room temperature for 24 h. The product was obtained by centrifugation, and the yield was 70.0%.
[0142] FT-IR data and TGA data for Material 5 (T-PA) are shown in
Test Examples 2
Test Example 2-1. Verification of Ultraviolet-Blocking Effect
[0143] To verify the UV blocking effects of the titanium dioxide (TiO.sub.2) composite particles (Material 1, T-PSI) prepared in Preparation Example 1-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 5, T-PA), UV-Vis spectrum analysis was performed to evaluate the absorbance and transmittance.
[0144] In this example, powdery TiO.sub.2 confirmed to have an ultraviolet-blocking effect was used as a control group. By using (a) the composition of the water-in-oil (w/o) emulsion and (b) the preparation method thereof as shown in
[0145] The results are shown (a) and (b) of
[0146] As shown in (a) and (b) of
Test Example 2-2. Verification of Heavy Metal Adsorption Effect
[0147] To verify the heavy metal adsorption effect of the biocompatible polyamino acid polymer material (Material 4, PA) prepared in Preparation Example 2-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 5, T-PA), inductively coupled plasma (ICP) analysis was performed.
[0148] Specifically, Material 4 (PA) was exposed to copper (Cu.sup.2+) and nickel (Ni.sup.2+) aqueous solutions for 5 min, 30 min, and 2 h, respectively, and the adsorbed materials were re-precipitated in methanol (MeOH) two times. After that, the amounts of heavy metals adsorbed were measured to verify the heavy metal adsorption capacity. To measure the degrees of adsorption of copper (Cu.sup.2+) and nickel (Ni.sup.2+) depending on three concentrations (50,000 mg/L, 100,000 mg/L, and 300,000 mg/L), Material 4 was exposed to metal solutions with the three concentrations for 12 h, and then the adsorbed materials were re-precipitated in methanol two times to re-elute un-adsorbed heavy metals. After that, the amounts of heavy metals adsorbed were measured to verify the heavy metal adsorption capacity.
[0149] Material 5 was exposed to copper (Cu.sup.2+) and nickel (Ni.sup.2+) aqueous solutions for 12 h, and then the adsorbed materials were washed with water three times to re-elute un-adsorbed heavy metals. After that, the amounts of heavy metals adsorbed were measured to verify the heavy metal adsorption capacity.
[0150] The results are shown in
[0151] As shown in
[0152] As shown in
[0153] Resultantly, the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 5, T-PA) of the present disclosure exhibited not only an ultraviolet-blocking effect but also an excellent heavy metal adsorption effect.
Test Example 2-3: White Cast Reducing Effect
[0154] To evaluate an effect of mitigating the white cast, a typical disadvantage shown when titanium dioxide (TiO.sub.2) is used in the composition of a cosmetic product, the titanium dioxide (TiO.sub.2) composite particles (Material 1, T-PSI) prepared in Preparation Example 1-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 5, T-PA) were measured for whiteness index by using a colorimeter.
[0155] The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Classification Whiteness index Basic Cream 47.03 TiO.sub.2-21 52.26 T-PSI-21 41.04 T-PA-21 36.21
[0156] As shown in Table 2, compared with titanium dioxide (TiO.sub.2), Material 1 (T-PSI) and Material 5 (T-PA) showed reduced whiteness indexes, indicating a reduced white cast.
Test Example 2-4: Verification of Photo-Catalytic Property Reducing Effect
[0157] The use of titanium dioxide (TiO.sub.2) in the cosmetic composition may cause skin oxidation due to the photo-catalytic properties of TiO.sub.2. Hence, the titanium dioxide (TiO.sub.2) composite particles (Material 1, T-PSI) prepared in Preparation Example 1-1 and the titanium dioxide (TiO.sub.2) composite particles with the heteroatomic compound further attached thereto (Material 5, T-PA) were investigated for a photo-catalytic property reducing effect.
[0158] Each titanium dioxide composite particle material (0.1 g) was added to 100 ml of a 10 ppm methylene blue solution, followed by exposure to 254 nm UV light (24 W), and then the photo-catalytic property effect of the titanium dioxide (TiO.sub.2) composite particle material was compared while the degree of reduction in methylene blue absorbance was verified at a wavelength of 664 nm.
[0159] The results are shown
[0160] As shown in