Polyvinylpyrrolidone-coated dye composition having improved stability and color retention, and uses thereof

Abstract

The present invention relates to a polyvinylpyrrolidone-coated dye composition having improved stability and color retention, and uses thereof. More specifically, the present invention relates to: a dye composition having improved stability and color retention and comprising dye nanoparticles and polyvinylpyrrolidone (PVP) coated on the surfaces of the dye nanoparticles; and uses of the dye composition in a cosmetic composition, an ink composition, a paint composition, a resin composition, a food composition, and the like.

Description

Polyvinylpyrrolidone coating dye composition having improved stability and color retention and use thereof

[0001] The present invention relates to a polyvinylpyrrolidone-coated dye composition having improved stability and color retention and its use. More specifically, the present invention relates to a dye composition having improved stability and color retention, comprising dye nanoparticles and polyvinylpyrrolidone (PVP) coated on the surface of the dye nanoparticles, and to the use of the dye composition in cosmetic compositions, ink compositions, paint compositions, resin compositions, food compositions, and the like.

[0002] A tattoo is a method of creating letters or designs by incising a wound in the skin or subcutaneous tissue and then coloring it with a dye composition. Semi-permanent makeup is also available for eyebrows, eyeliner, lips, and hairlines. Recently, tattoos have been utilized and recognized as a way to compensate for physical weaknesses or express individuality. Since tattoos inflict damage to the skin and color the skin with a dye composition, ensuring the safety of the dye is crucial. However, caution is required as heavy metals such as lead and nickel, which can cause cancer and allergies, are consistently detected in existing dyes. Furthermore, there have been numerous reports of pain, blisters, swelling, and mild inflammation after getting a tattoo on an area like the eyebrows, or of the dye getting into the eyes after getting an eyeliner tattoo, causing pain and visual impairment.

[0003]

[0004] Prior art literature

[0005] Patent Document 1. Patent Registration No. 10-2451153

[0006] The present inventors have made extensive efforts to develop a dye composition having excellent stability and biocompatibility while also having improved color retention, and as a result, have confirmed that when dye nanoparticles are coated with polyvinylpyrrolidone (PVP), not only is the composition excellent in dispersibility and storage stability, but also has excellent biocompatibility and is not affected by oxidative stress, and the color retention ability can be improved, thereby completing the present invention.

[0007]

[0008] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0009] The present invention seeks to provide a polyvinylpyrrolidone coating dye composition having improved stability and color retention and uses of the dye composition, for example, uses in cosmetic compositions, ink compositions, paint compositions, resin compositions or food compositions.

[0010]

[0011] The present invention

[0012] dye nanoparticles, and

[0013] The present invention relates to a dye composition having improved stability and color retention, comprising polyvinylpyrrolidone (PVP) coated on the surface of the dye nanoparticles.

[0014] In the present invention, the dye nanoparticles may include carbon black, titanium dioxide, iron oxide black, iron oxide yellow, iron oxide red, or a combination thereof.

[0015] According to one exemplary embodiment, the weight ratio of the carbon black nanoparticles and polyvinylpyrrolidone may be 1:1 to 100. The polyvinylpyrrolidone-coated carbon black nanoparticles may include carbon black and 10 kDa polyvinylpyrrolidone in a weight ratio of 1:50.

[0016] According to another exemplary embodiment, the weight ratio of the titanium dioxide, iron oxide black, iron oxide yellow or iron oxide red and polyvinyl pyrrolidone may be 1:1 to 20. The dye composition may include iron oxide red and polyvinyl pyrrolidone of 40 kDa in a weight ratio of 1:10.

[0017] In the present invention, the dye composition can be used on hair, skin, eyes, eyebrows or eyelashes.

[0018] In the present invention, the dye composition can be used in a cosmetic composition, an ink composition, a paint composition, a resin composition, or a food composition.

[0019] The dye composition comprising the dye nanoparticles according to the present invention and polyvinylpyrrolidone (PVP) coated on the surface of the dye nanoparticles not only has excellent dispersibility and storage stability, but also has excellent biocompatibility, is not affected by oxidative stress, and has significantly improved color retention ability.

[0020]

[0021] Meanwhile, the scope of the present invention is not limited by the effects described above.

[0022] Figure 1 shows (A) photographs, (B) UV-Vis spectra, (C) sizes, (D) particle size distributions, and (E) dispersion values ​​of CB and CB / PVP NPs.

[0023] Figure 2 shows the dispersion stability of CB / PVP NPs. UV-Vis spectra of CB / PVP NPs in (A) DIW and (B) PBS after 2 weeks of storage at room temperature (25 ℃).

[0024] Figure 3 shows the (A) size and (B) dispersion values ​​of CB and CB / PVP NPs before and after freeze-drying (FD).

[0025] Figure 4 shows the size change of CB / PVP NPs after 4 weeks of storage in (A) DIW and (B) PBS at 37°C. The dispersion value change of CB / PVP NPs after 4 weeks of storage in (C) DIW and (D) PBS at 37°C.

[0026] Figure 5 shows (A) the photograph, (B) the UV-Vis spectra, (C) the size, and (D) the dispersion values ​​of CB / PVP10k NPs at different ratios.

[0027] Figure 6 shows the dispersion stability of CB / PVP10k NPs at different ratios. (A) Photographs and (B) UV-Vis spectra of CB / PVP10k NPs at different ratios are shown after 2 weeks of storage in DIW at room temperature (25°C).

[0028] Figure 7 shows the (A) size and (B) dispersion values ​​of nanoparticles after freeze-drying (FD) and redispersion in DIW and PBS at different CB / PVP10k NP ratios.

[0029] Figure 8 shows the change in size after 4 weeks of storage in (A) DIW and (B) PBS at 37°C at different CB / PVP10k NP ratios, and the change in dispersion value after 4 weeks of storage in (C) DIW and (D) PBS at 37°C at different CB / PVP10k NP ratios.

[0030] Figure 9 shows the cytotoxicity results according to the concentration of CB / PVP10k NP (1:50).

[0031] Figure 10 shows cell morphology results according to the concentration of CB / PVP10k NP (1:50); (i) negative control, (ii) positive control, (iii) 0.1 mg / mL, and (iv) 1 mg / mL CB / PVP10k NP (1:50).

[0032] Figure 11 shows the results of oxidative stress induced by reactive oxygen radicals of CB / PVP10k NP (1:50).

[0033] Figure 12 shows the results of the 8-week tattoo retention ability of CB / PVP10k NP (1:50); the results of administration of the original solution (left) and a 1 / 2 dilution (right).

[0034] Figure 13 shows the H&E staining analysis results of (A) the original solution and (B) a 1 / 2 dilution solution 4 weeks after CB / PVP10k NP (1:50) treatment.

[0035] Figure 14 shows photographs and UV-Vis spectra of (a) TiO2 and three kinds of (b) Yellow, (c) Red, (d) Black IONP coated with PF127 or PVP (10 kDa).

[0036] Figure 15 shows (a) the size and (b) dispersion values ​​of PF127 or PVP (10 kDa) coated TiO2 and three types of IONPs.

[0037] Figure 16 shows photographs of PF127 or PVP (10 kDa) coated TiO2 and three types of IONPs after storage at 25 °C for 0, 3, and 11 days.

[0038] Figure 17 shows the changes in (a) size and (b) dispersion values ​​of PF127 or PVP (10 kDa) coated TiO2 and three types of IONPs after 4 weeks of storage in DIW at 25 °C.

[0039] Figure 18 shows (a) a photograph, (b) UV-Vis spectra, (c) size, and (d) dispersion values ​​of Red IONP / PVP according to PVP molecular weight.

[0040] Figure 19 shows (a) the size and (b) dispersion values ​​of nanoparticles after freeze-drying (FD) and redispersion in DIW and PBS of Red IONP / PVP according to PVP molecular weight.

[0041] Figure 20 shows the size change of Red IONP / PVP according to PVP molecular weight after storage in DIW at (a) 25°C for 2 weeks and (b) 37°C for 4 weeks. It also shows the change in dispersion value of Red IONP / PVP according to PVP molecular weight after storage in DIW at (c) 25°C for 2 weeks and (d) 37°C for 4 weeks.

[0042] Figure 21 shows the cytotoxicity results according to the concentration of Red IONP / PVP40k.

[0043] Figure 22 shows cell morphology results according to Red IONP / PVP40k concentration; (i) negative control, (ii) positive control, (iii) 0.1 mg / mL, and (iv) 1 mg / mL Red IONP / PVP40k.

[0044] Figure 23 shows the results of oxidative stress induced by reactive oxygen radicals of Red IONP / PVP40k.

[0045] Figure 24 shows the results of the 8-week tattoo retention ability of Red IONP / PVP40k; the results of administration of the original solution (left) and 1 / 2 dilution (right).

[0046] Figure 25 shows the H&E staining analysis results of (A) the original solution and (B) the 1 / 2 dilution after 4 weeks of Red IONP / PVP40k treatment, and (C) the original solution and (D) the 1 / 2 dilution after 8 weeks.

[0047]

[0048] Hereinafter, a polyvinylpyrrolidone coating dye composition having improved stability and color retention according to specific embodiments of the invention and its use will be described in detail. However, this is presented as one example of the invention, and the scope of the invention is not limited thereby, and it is obvious to those skilled in the art that various modifications to the embodiments are possible within the scope of the invention. Unless otherwise specified, throughout this specification, "include" or "containing" refers to including a certain component (or component) without any particular limitation, and cannot be interpreted as excluding the addition of other components (or components).

[0049]

[0050] 1. Polyvinylpyrrolidone coating dye composition

[0051] The present invention

[0052] dye nanoparticles, and

[0053] It is an object of the present invention to provide a dye composition having improved stability and color retention, comprising polyvinylpyrrolidone (PVP) coated on the surface of the dye nanoparticles.

[0054] In the dye composition according to the present invention, the dye nanoparticles may include carbon black, titanium dioxide, iron oxide black, iron oxide yellow, iron oxide red, or a combination thereof.

[0055]

[0056] In one exemplary embodiment, when the dye nanoparticles are carbon black, the molecular weight of the polyvinylpyrrolidone may be 1 to 1500 kDa, preferably 10 to 40 kDa, and most preferably 10 kDa. The weight ratio of the carbon black nanoparticles to the polyvinylpyrrolidone may be 1:1 to 100, preferably 1:2 to 50, and most preferably 1:50. The polyvinylpyrrolidone-coated carbon black nanoparticles may include carbon black and 10 kDa polyvinylpyrrolidone in a weight ratio of 1:50.

[0057]

[0058] In another exemplary embodiment, when the dye composition is titanium dioxide, black iron oxide, yellow iron oxide or red iron oxide, the molecular weight of the polyvinyl pyrrolidone may be 10 to 1500 kDa, preferably 10 to 360 kDa, and most preferably 40 kDa. The weight ratio of the dye nanoparticles to the polyvinyl pyrrolidone may be 1:1 to 20, preferably 1:5 to 15, and most preferably 1:10. The dye composition may include red iron oxide (Iron Oxide Red) and 40 kDa polyvinyl pyrrolidone in a weight ratio of 1:10.

[0059]

[0060] In the dye composition according to the present invention, the diameter of the dye composition may be 1 to 500 nm, preferably 1 to 400 nm, and most preferably 1 to 300 nm.

[0061] In the dye composition according to the present invention, the dye composition can be used on hair, skin, eyes, eyebrows or eyelashes.

[0062]

[0063] 2. Use of polyvinylpyrrolidone coating dye composition

[0064] The present invention seeks to provide the use of the polyvinylpyrrolidone coating dye composition described above in a cosmetic composition, an ink composition, a paint composition, a resin composition, a food composition, etc.

[0065]

[0066] (1) Cosmetic composition

[0067] In the use of the dye composition according to the present invention, the cosmetic composition is an eye shadow, an eyebrow, an eye liner, a mascara, an eyebrow mascara, an eyebrow quick tattoo, an aegyo-sal liner, a shade and shadow, a shading, a contouring, a concealer, a powder, a pact, a foundation, a base, a highlighter, a lipstick, a lip tint, a tint, a lip balm, a tinted lip balm, a lip gloss, a lip liner, a lotion, a toner, a serum, an eyelash serum, a mask pack, a sunscreen, a blusher, a plumper, an ampoule, an essence, a hair tint, a hair mist, a hair spray, a cream blusher, a lip serine, a sun cushion, a sun spray, a tone-up cream, a primer, a blur, a glitter, a lip and cheek, a fixer, a balm, a modeling pack, a patch, a skin pad, a cleansing balm, a spot gel, a black pigment, a black pigment spray, a shampoo, a rinse, It can be formulated as a treatment, hair mask, hair wax, hair gel, hairline cover, gray hair cover, hair dye, dye shampoo, toothpaste, bath salt, cleansing foam, cleansing oil, cleansing gel, cleansing water, cleansing mask, soap, shaving cream, shaving gel, massage cream, deodorant, body wash, scrub, cosmetic cotton swab, or cosmetic adhesive.

[0068] (2) Ink composition

[0069] In the use of the dye composition according to the present invention, the ink composition can be used for corneal tattoo, nipple tattoo, areola tattoo, scar tattoo, radiotherapy marker, eyebrow tattoo, eyeliner tattoo, lip tattoo, aegyo-sal tattoo, nail tattoo, tooth tattoo, scalp tattoo, scalp black tattoo, sideburn tattoo, beard tattoo, pubic tattoo, or henna tattoo.

[0070] In the use of the dye composition according to the present invention, the ink composition can be used as pen ink, fountain pen ink, printer ink, toner cartridge or art paint.

[0071] In the use of the dye composition according to the present invention, the ink composition can be used to print packaging packages, wrapping paper, wallpaper, fibers, cosmetic boards, textiles, various films or labels.

[0072] In the use of the dye composition according to the present invention, the ink composition can be used to print packaging packages, wrapping paper, wallpaper, fibers, cosmetic boards, textiles, various films or labels.

[0073]

[0074] (3) Paint composition

[0075] In the use of the dye composition according to the present invention, the paint composition can be used for ceramic paint, ship paint, sunglasses, insecticides and high-efficiency spray fertilizers, sterilizers, exteriors of automobiles, motorcycles and bicycles, building materials, roof tiles, furniture, household goods, containers, office supplies or sporting goods.

[0076]

[0077] (4) Resin composition

[0078] In the use of the dye composition according to the present invention, the resin composition can be used in containers for cosmetics, food containers, wall coverings, flooring, crafts, housings for home appliances, accessories, stationery, toys, bathtubs, bath products, shoes, sporting goods or toiletries.

[0079]

[0080] (5) Food composition

[0081] In the use of the dye composition according to the present invention, the food composition can be used as a colorant for processed foods such as beverages, desserts, seasonings, spices, natural food coloring agents, animal feed, preservatives, capsules of health functional foods, confectionery, candy, breads, rice cakes, chocolates, beverages, alcoholic beverages, jellies, cereals, sugars, ice creams, seasonings, dressings, sauces, seasoned foods, pickles, agricultural and marine products, starch products, vegetable creams, ready-to-eat foods, grain products, edible oil products, sugar products, processed paper products, and processed dairy products.

[0082]

[0083] (6) Other purposes

[0084] In the use of the dye composition according to the present invention, the dye composition can be used in addition to the above-mentioned uses in rubber, antistatic agents, semiconductive or conductive materials, papermaking, adsorption and deodorization, horticulture and agriculture, energy storage materials, directional carbon materials, abrasives or absorbent implants, medical devices, etc.

[0085] In the use of the dye composition according to the present invention, the rubber can be used in automobiles, aircraft, industrial tires, rubber seals, or packing.

[0086] In the use of the dye composition according to the present invention, the antistatic agent can be used in housings, cassettes, mechanical parts of electrical appliances, vehicle fuel tanks, hoses for chemical solvents, conveyor belts, V-belts, safety shoes, rollers for copiers, explosion-proof containers, integrated circuit packages (IC packages), storage warehouses, trays, containers, film canisters, magnetic tapes for video or audio, or backings (backings) of carpets in computer rooms.

[0087] In the use of the dye composition according to the present invention, the semiconductive and conductive materials can be used in a semiconductive compound, a cross-linked polyethylene cable, an ignition cable, a communication cable, a next-generation storage battery (Zn-Br type and Zn-Cl type), a ferrite magnet, a magnetic storage device (Hard Disk Drives-HDDs), magnetic particles of a magnetic cassette tape, a discharge resistor, a conductive element, an electric filter, or an electrostatic dissipation (ESD) material.

[0088] In the use of the dye composition according to the present invention, the adsorption and deodorization can be used as an activated carbon filter and mask, an air purifier and filter, an automobile air purifier, a deodorizer for shoes, an air freshener and a room freshener, a refrigerator deodorizer, a clothing and shoe storage box, a toilet, a deodorizer for baby diapers, and a moisture remover.

[0089] In the use of the dye composition according to the present invention, it can be used in the horticultural and agricultural fields as a biodeodorizer, biofertilizer, seed coating, and soil conditioner.

[0090] In the use of the dye composition according to the present invention, the energy storage material can be used in ultra-high capacity batteries, energy storage systems, automobiles and transportation vehicles, power grid stabilization, and mobile power supply devices.

[0091] In the use of the dye composition according to the present invention, the directional carbon material can be used in carbon fibers, carbon composites, electrically conductive and thermally conductive polymers (electronic devices, biosensors, LED lighting, automobile parts), deep-sea underwater exploration equipment, and military and aviation radar penetrators.

[0092] In the use of the dye composition according to the present invention, the medical device field can be used as a lens for vision correction and a cosmetic color lens.

[0093] Below, various examples are presented to aid understanding of the invention. These examples are provided solely to facilitate understanding of the invention and are not intended to limit the scope of protection of the invention.

[0094]

[0095] <Example>

[0096] Example 1.

[0097] 1-1. Manufacturing and characterization of polyvinylpyrrolidone (PVP)-coated carbon black nanoparticles (CB / PVP NP) by molecular weight

[0098] (1) Experimental method

[0099] To develop a semi-permanent cosmetic carbon black with excellent biocompatibility and stability, PVP-coated carbon black nanoparticles (CB / PVP NPs) were prepared. First, to compare the properties of CB / PVP NPs according to the molecular weight of PVP, four types of PVP (molecular weight = 10, 40, 360, and 1300 kDa) were prepared in 1 mL of deionized water (DIW) at a concentration of 25 mg / mL. The PVP solution was added to carbon black (CB; 5 mg), transferred to a 20 mL vial, and reacted with magnetic stirring at 300 rpm for 30 minutes. Then, 4 mL of DIW was added, and the reaction was continued at 400 rpm for an additional 30 minutes. The mixture was homogenized using an ultrasonic homogenizer (amplitude = 20%, 5 s on / 15 s off) for 1 h, centrifuged (2000 rpm, 10 min) to remove uncoated CB, and then freeze-dried for 3 days. The CB / PVP NPs thus manufactured were named CB / PVP10k NP, CB / PVP40k NP, CB / PVP360k NP, and CB / PVP1300k NP according to the molecular weight of the coated PVP. CB nanoparticles were also prepared without polymer coating using the same method. The morphologies of CB and CB / PVP NP were photographed, and their absorbance was analyzed using UV-Vis spectroscopy. The size and dispersion values ​​of the nanoparticles were measured using a Zetasizer (ELSZ-2000, Otsuka). To evaluate the dispersion stability of CB / PVP NPs, for which characterization was completed, the UV-Vis spectra of the dispersed nanoparticles were analyzed while storing them in DIW or phosphate-buffered saline (PBS) at room temperature (25°C) for 2 weeks. In addition, to evaluate the freeze-drying stability, the size and dispersion values ​​of the nanoparticles of CB and CB / PVP NPs were measured before freeze-drying and after redispersion in DIW or PBS.The in vivo stability of nanoparticles was measured using a zetasizer device to measure changes in size and dispersion values ​​in DIW or PBS at 37°C for 4 weeks.

[0100] (2) Results

[0101] Characterization: As can be seen in Fig. 1, both CB and CB / PVP NPs were prepared as dark black solutions after ultrasonic homogenization (Fig. 1A). In the case of CB, the yield of CB contained in the nanoparticles was confirmed by the intensity of the CB's unique UV-Vis absorption peak (λ = 250 nm), which showed very low absorbance due to poor dispersion stability. On the other hand, when coated with PVP, the CB dispersibility was improved, and the absorbance was also confirmed to be high. Among them, the yield was highest when coated with low-molecular-weight PVP (10, 40 kDa) (Fig. 1B). In addition, the size of CB before coating was approximately 260 nm, but it was found to decrease to approximately 140 nm after PVP coating (Fig. 1C). As can be seen in the particle size distribution, the nanoparticles were prepared in a monodisperse size, and the size of CB / PVP NPs coated with high-molecular-weight PVP was found to be larger (Fig. 1D). It was confirmed that the dispersion values ​​of CB / PVP NPs were all less than 0.3, indicating that they were manufactured with uniform sizes (Fig. 1E).

[0102] Dispersion stability: As can be seen from Fig. 2, in order to evaluate the dispersion stability of CB / PVP NPs for 2 weeks, the yield of CB was analyzed using UV-Vis spectroscopy after 2 weeks of storage in DIW and PBS. In the case of CB before coating, the stability was low and the yield was not measured, whereas the absorbance of CB / PVP10k NPs was the highest, indicating the best dispersion stability.

[0103] Freeze-drying stability: As can be seen from Fig. 3, in the case of CB before coating, it was completely precipitated after freeze-drying and redispersion was impossible, whereas in the case of CB / PVP NP, the size and dispersion values ​​were stably maintained.

[0104] Storage stability: As can be seen from Fig. 4, when the size and dispersion values ​​of CB / PVP NPs stored in DIW and PBS were analyzed every 4 weeks, the CB / PVP NPs were maintained at a constant size and the dispersion value was stably maintained at less than 0.3. In particular, it was confirmed that the size and dispersion values ​​of CB / PVP10k NPs and CB / PVP10k NPs could be maintained at a constant level for 4 weeks.

[0105]

[0106] 1-2. Manufacturing and Characterization of PVP10k Coated Carbon Black Nanoparticles (CB / PVP10k NP) by Ratio

[0107] (1) Experimental method

[0108] Based on the characteristic evaluation according to Example 1, 10 kDa PVP, which was selected as the most optimal group among PVPs, was used to manufacture CB / PVP10k NPs at various ratios. First, in order to compare the characteristics of CB / PVP10k NPs at various PVP (10 kDa) ratios, PVP (10 kDa) solutions at different concentrations (10, 25, 50, 100, 250, and 500 mg) were prepared in 1 mL of DIW (the weight ratios of CB and PVP10k were 1:2, 1:5, 1:10, 1:20, 1:50, and 1:100). Then, CB / PVP10k NPs were manufactured by reacting with 5 mg of CB and using the same method as Example 1. In order to evaluate the characteristics of the manufactured nanoparticles, photographs were taken and UV-vis spectra, size, and dispersion values ​​were analyzed. To evaluate the stability of CB / PVP10k NPs by ratio, the color of the nanoparticles was photographed and the UV-Vis spectra were observed while storing them in DIW for 2 weeks. In addition, the size and dispersion values ​​of the nanoparticles before and after lyophilization were analyzed to assess whether the nanoparticles could be easily stored in a powder state before use. The changes in the size and dispersion values ​​of CB / PVP10k NPs in DIW or PBS at 37°C for 4 weeks were analyzed to evaluate the in vivo stability of the nanoparticles.

[0109] (2) Results

[0110] Characterization: As can be seen from Fig. 5, all CB / PVP10k NPs at different ratios were manufactured with CB well dispersed in a dark black color (Fig. 5A). In particular, the lower the polymer ratio, the better the CB yield, resulting in the highest intensity of the UV-Vis absorption peak (Fig. 5B). The size of the nanoparticles increased as the ratio of the coated PVP increased, and they were manufactured to be between 117 nm and 143 nm (Fig. 5C). The dispersion values ​​were all less than 0.3, confirming that the nanoparticles were manufactured uniformly in size (Fig. 5D).

[0111] Dispersion Stability: As can be seen from Fig. 6, all CB / PVP10k NPs at different ratios were stably dispersed after 2 weeks of storage in DIW, and no color change or precipitation was observed in the photograph. For a more accurate comparison, when UV-Vis spectra were analyzed, it was found that the higher the polymer ratio, the higher the CB yield. In the case of CB / PVP10k NP (1:100), the high polymer ratio made it difficult to confirm the UV-Vis absorption peak of CB, making accurate yield measurement impossible. CB / PVP10k NP (1:50) was confirmed to have the best dispersion stability.

[0112] Freeze-drying stability: As can be seen from Figure 7, when the freeze-drying stability of CB / PVP10k NPs by ratio was evaluated, it was confirmed that the size and dispersion values ​​of all groups were well maintained without change.

[0113] Storage stability: As can be seen from Fig. 8, when CB / PVP10k NPs were stored in DIW and PBS for 4 weeks, the dispersion values ​​were all confirmed to be stable at less than 0.3 without any change in size.

[0114]

[0115] 1-3. In vitro cytotoxicity and biocompatibility evaluation of CB / PVP10k NP (1:50)

[0116] (1) Experimental method

[0117] To evaluate the cytotoxicity of CB / PVP10k NP (1:50), fibroblasts and NIH 3T3 cells were cultured in Dulbecco's Modified Eagle's Medium (DMEM) supplemented with 10% fetal bovine serum (FBS) and 1% penicillin-streptomycin (PS). The cultured cells were seeded into each well of a 96-well plate at 10,000 cells / well and cultured in an incubator at 37°C and 5% CO2 for 12 h. Then, CB / PVP10k NP (1:50) was treated with various concentrations (10, 100, 200, 500 μg / mL) for 24 h, and cell viability was analyzed using a CCK-8 kit. The control group (0 μg / mL) was treated with cell culture fluid. In addition, to observe cell morphology after CB / PVP10k NP (1:50) treatment, NIH 3T3 cells were cultured and treated with 0.1 mg / mL and 1 mg / mL of CB / PVP10k NP (1:50) for 24 hours. At this time, cell culture medium was used as the negative control group, and 10% DMSO was used as the positive control group.

[0118] (2) Results

[0119] As can be seen from Fig. 9, the biocompatibility of CB / PVP10k NP (1:50) was excellent, no cytotoxicity was observed, and the cell viability was confirmed to be over 90% even at a high concentration of 500 μg / mL. In addition, as can be seen from Fig. 10, when compared to the control group after treatment with CB / PVP10k NP (1:50) with excellent biocompatibility, no change in cell morphology was observed, proving that it is a stable material for use in the fields of pharmaceuticals and cosmetics as a semi-permanent cosmetic carbon black.

[0120]

[0121] 1-4. Evaluation of oxidative stress by in vitro induction of reactive oxygen radicals by CB / PVP10k NP (1:50)

[0122] (1) Experimental method

[0123] NIH 3T3 cells were cultured in DMEM supplemented with 10% FBS and 1% PS, and 10,000 cells were seeded into each well of a 96-well plate. After 12 h of incubation, 200 μL of CB / PVP10k NP (1:50) was treated at various concentrations (100, 200, 500 μg / mL), and then cultured in an incubator for another day. The negative control group (0 μg / mL) was treated with cell culture medium, and the positive control group was treated with H2O2 (10 μM). The remaining samples were then washed with PBS to remove the remaining samples, and intracellular reactive oxygen radicals were analyzed using H2DCFDA (10 μM).

[0124] (2) Results

[0125] As can be seen from Fig. 11, when the amount of reactive oxygen radicals (ROS) existing in the existing cells was 100%, the ROS level of the positive control group treated with H2O2 was 124.8 ± 3.5%, indicating oxidative stress, whereas when treated with CB / PVP10k NP (1:50), it was confirmed that the ROS level did not increase.

[0126]

[0127] 1-5. In vivo carbon black properties evaluation of CB / PVP10k NP (1:50)

[0128] (1) Experimental method

[0129] To evaluate the in vivo carbon black properties of CB / PVP10k NP (1:50), 20 μL of CB / PVP10k NP (1:50) was intradermally administered to 8-week-old Sprague-Dawley rats. The original solution was administered to two sites on the left, and a 1 / 2 dilution was administered to two sites on the right. After 0 and 4 weeks, photographs were taken to observe the properties of the carbon black, and the presence of inflammation was determined through H&E staining.

[0130] (2) Results

[0131] As can be seen from Fig. 12, both the original solution (left) and the 1 / 2 dilution (right) of CB / PVP10k NP (1:50) were found to maintain their color well for 4 weeks without fading or change after intradermal administration. In addition, as can be seen from Fig. 13, the H&E staining results confirmed that CB / PVP10k NP (1:50) was a safe material that did not cause any inflammatory reaction intradermally for 4 weeks. Therefore, the excellent tattoo retention ability and biocompatibility of CB / PVP10k NP (1:50) were proven.

[0132]

[0133] Example 2

[0134] 2-1. Manufacturing and Characterization of Polymer-Coated Titanium Dioxide and Iron Oxide

[0135] (1) Experimental method

[0136] To develop a semi-permanent cosmetic dye with excellent biocompatibility and stability, polymer-coated titanium dioxide (TiO2) and three types of iron oxide nanoparticles (IONP) were prepared. TiO2 was developed for white cosmetic dyes, and the three types of iron oxides were developed for yellow, red, and black cosmetic dyes, respectively. First, PF127 and PVP (10 kDa) were each prepared at a concentration of 50 mg / mL in 1 mL of deionized water (DIW). The polymer solution was added to each of TiO2 and the three types of IONP (5 mg), followed by 4 mL of DIW, and the mixture was stirred with rotatory shaking for 1 hour. The reaction solution was then transferred to a 20 mL vial and homogenized for 1 hour using an ultrasonic homogenizer (amplitude = 20%, 5 s on / 15 s off). The prepared nanoparticles were freeze-dried for 3 days. The shape of the manufactured nanoparticles was photographed, and their absorbance was analyzed using UV-Vis spectroscopy. The size and dispersion values ​​of the nanoparticles were confirmed using a Zetasizer (ELSZ-2000, Otsuka). In addition, to evaluate the storage stability of the nanoparticles, the shape of the dispersed nanoparticles was photographed while they were stored in deionized water (DIW) at room temperature (25°C) for 11 days, and the changes in size and dispersion values ​​in DIW for 4 weeks were measured using a zetasizer.

[0137] (2) Results

[0138] Absorbance: As can be seen from Fig. 14, TiO2 and three types of IONPs coated with PF127 or PVP (10 kDa) after ultrasonic homogenization were well dispersed and manufactured, and a unique UV-Vis spectra was observed for each color of the nanoparticles.

[0139] Size and dispersion values: As can be seen in Fig. 15, the size of TiO2 coated with PF127 (TiO2 / PF127) was 2096 nm, and the size of TiO2 coated with PVP (10 kDa) (TiO2 / PVP10) was smaller at 763 nm. IONPs were manufactured with similar sizes regardless of the polymer type. The sizes of yellow IONP / PF127 and yellow IONP / PVP10k were 385 nm and 390 nm, respectively, and the sizes of red IONP / PF127 and red IONP / PVP10k were 316 nm and 258 nm, respectively. Black IONPs were manufactured large, but with a size of approximately 2800 nm regardless of the polymer type (Fig. 15a). The dispersion value of the nanoparticles was lower when coated with PVP (10 kDa), so the sizes were manufactured more uniformly (Fig. 15b).

[0140] Storage stability: As can be seen from Fig. 16, the nanoparticles coated with PF127 showed poor stability and all sank after 11 days. When coated with PVP (10 kDa), TiO2 and Black IONP precipitated after 3 days, but Yellow IONP and Red IONP maintained dispersion stability for up to 11 days. As can be seen from Fig. 17, the size and dispersion values ​​of the nanoparticles coated with PF127 and PVP (10 kDa) coated TiO2, Yellow IONP, and Black IONP increased after 4 weeks of storage, but Red IONP / PVP10k showed no change in size and was stably maintained with a dispersion value of less than 0.3.

[0141]

[0142] 2-2. Manufacturing and Characterization of PVP-Coated Red Iron Oxide (Red IONP / PVP) by Molecular Weight

[0143] (1) Experimental method

[0144] In order to compare the characteristics of Red IONP / PVP according to PVP molecular weight, 50 mg of PVP solution (molecular weight = 10, 40, 360, 1300 kDa) was prepared in 1 mL of DIW, and 5 mg of Red IONP was mixed, and Red IONP / PVP was prepared in the same manner as in Example 1. As a control, Red IONP was also prepared without polymer coating in the same manner. In order to evaluate the characteristics of the prepared nanoparticles, photographs were taken, and the UV-Vis spectra, size, and dispersion values ​​were analyzed. In addition, the size and dispersion values ​​of the nanoparticles before and after freeze-drying were measured to evaluate whether the nanoparticles could be easily stored in a powder state before use. In addition, in order to evaluate the storage stability of the nanoparticles, the changes in the size and dispersion values ​​of Red IONP / PVP in DIW were measured at 25 ℃ and 37 ℃ for 2 weeks and 4 weeks, respectively.

[0145] (2) Results

[0146] Photo, size, and dispersion values: As can be seen from Fig. 18, all Red IONP / PVPs of different molecular weights were manufactured with iron oxide well dispersed in their own red color (Fig. 18a), and in particular, when the molecular weight of PVP was 40 kDa, iron oxide was well dispersed and the intensity of the UV-Vis absorption peak was the highest (Fig. 18b). The size of the nanoparticles increased as the molecular weight of the coated PVP increased, ranging from 233 nm to 334 nm (Fig. 18c), and the dispersion values ​​were all less than 0.3, confirming that the sizes were manufactured uniformly (Fig. 18d).

[0147] Freeze-drying stability: As can be seen from Fig. 19, Bare Red IONP, Red IONP / PVP10k and Red IONP / PVP1300k manufactured without polymer coating showed poor stability and increased size and dispersion values, whereas Red IONP / PVP40k and Red IONP / PVP360k were confirmed to exist stably with dispersion values ​​less than 0.3 without any change in size.

[0148] Storage stability: As can be seen from Figure 20, when Red IONP / PVP by molecular weight was stored in DIW at 25°C for 2 weeks or at 37°C for 4 weeks, it was confirmed that the dispersion values ​​were all stably maintained at less than 0.3 without any change in size.

[0149]

[0150] 2-3. In vitro cytotoxicity and biocompatibility evaluation of Red IONP / PVP40k

[0151] (1) Experimental method

[0152] To evaluate the cytotoxicity of Red IONP / PVP40k, fibroblasts and NIH 3T3 were cultured in Dulbecco's Modified Eagle's Medium (DMEM) supplemented with 10% fetal bovine serum (FBS) and 1% penicillin-streptomycin (PS). The cultured cells were seeded into each well of a 96-well plate at 10,000 cells / well and cultured in an incubator at 37°C and 5% CO2 for 12 hours. Then, the cells were treated with various concentrations of Red IONP / PVP40k (10, 100, 200, 500 μg / mL) for 24 hours, and the cell viability was analyzed using a CCK-8 kit. At this time, the control group (0 μg / mL) was treated with cell culture fluid. In addition, to observe cell morphology after Red IONP / PVP40k treatment, NIH 3T3 cells were cultured and treated with 0.1 mg / mL and 1 mg / mL of Red IONP / PVP40k for 24 hours. The negative control group was treated with cell culture medium, and the positive control group was treated with 10% DMSO.

[0153] (2) Results

[0154] As can be seen from Fig. 21, Red IONP / PVP40k has excellent biocompatibility and did not cause any cytotoxicity, and the cell viability was found to be over 90% even at a concentration of 500 μg / mL. In addition, as can be seen from Fig. 22, no change in cell morphology was observed compared to the control group even after treatment with Red IONP / PVP40k, which has excellent biocompatibility. Therefore, Red IONP / PVP40k is expected to be safely utilized as a semi-permanent cosmetic dye in the pharmaceutical and cosmetic fields.

[0155]

[0156] 2-4. Evaluation of oxidative stress by in vitro induction of reactive oxygen radicals by Red IONP / PVP

[0157] (1) Experimental method

[0158] NIH 3T3 cells were cultured in DMEM supplemented with 10% FBS and 1% PS, and 10,000 cells were seeded into each well of a 96-well plate. After 12 hours of incubation, 200 μL of Red IONP / PVP40k (100, 200 μg / mL) were treated, and the cells were incubated in the incubator for another day. The negative control group (0 μg / mL) was treated with cell culture medium, and the positive control group was treated with H2O2 (10 μM). After washing with PBS to remove any remaining samples, intracellular reactive oxygen radicals were analyzed using H2DCFDA (10 μM).

[0159] (2) Results

[0160] As can be seen from Figure 23, when the amount of reactive oxygen radicals (ROS) existing in the existing cells was 100%, the ROS level of the positive control group treated with H2O2 was 134.9 ± 4.9%, indicating oxidative stress, whereas the ROS level did not increase when treated with Red IONP / PVP40k.

[0161]

[0162] 2-5. In vivo dye properties of red IONP / PVP

[0163] (1) Experimental method

[0164] To evaluate the in vivo dye properties of Red IONP / PVP40k, 20 μL of Red IONP / PVP40k was administered intradermally to 8-week-old Sprague-Dawley rats. The original solution was administered to two sites on the left, and a 1 / 2 dilution was administered to two sites on the right. After 0, 4, and 8 weeks, photographs were taken to observe the dye properties, and the presence of inflammation was assessed by H&E staining.

[0165] (2) Results

[0166] As can be seen from Fig. 24, both the original solution (left) and the 1 / 2 dilution (right) showed good color retention for 8 weeks after intradermal administration of Red IONP / PVP40k without color fading or change. In addition, as can be seen from Fig. 25, the H&E staining results confirmed that Red IONP / PVP40k is a safe material that did not cause any inflammatory reaction intradermally for 8 weeks. Therefore, it is believed that Red IONP / PVP40k has excellent tattoo retention ability and biocompatibility.

[0167]

[0168] While specific aspects of the present invention have been described in detail above, it should be apparent to those skilled in the art that these specific descriptions are merely preferred implementation examples and are not intended to limit the scope of the present invention. Therefore, the substantial scope of the present invention is defined by the appended claims and their equivalents.

[0169] It is expected that the dye composition according to the present invention can be usefully used in cosmetic compositions, ink compositions (e.g., tattoos), paint compositions, resin compositions, food compositions, etc.

Claims

1. Dye nanoparticles, and A dye composition having improved stability and color retention, comprising polyvinylpyrrolidone (PVP) coated on the surface of the dye nanoparticles.

2. In paragraph 1, A dye composition having improved stability and color retention, characterized in that the dye nanoparticles include carbon black, titanium dioxide, iron oxide black, iron oxide yellow, iron oxide red, or a combination thereof.

3. In paragraph 2, A dye composition having improved stability and color retention, characterized in that the weight ratio of the carbon black nanoparticles and polyvinyl pyrrolidone is 1:1 to 100.

4. In paragraph 2, A dye composition having improved stability and color retention, characterized in that the polyvinylpyrrolidone-coated carbon black nanoparticles comprise carbon black and 10 kDa polyvinylpyrrolidone in a weight ratio of 1:

50.

5. In paragraph 2, A dye composition having improved stability and color retention, characterized in that the weight ratio of the titanium dioxide, iron oxide black, iron oxide yellow or iron oxide red and polyvinyl pyrrolidone is 1:1 to 20.

6. In paragraph 2, A dye composition having improved stability and color retention, characterized in that the dye composition comprises iron oxide red and 40 kDa polyvinylpyrrolidone in a weight ratio of 1:

10.

7. In paragraph 1, A dye composition having improved stability and color retention, characterized in that the dye composition is used for hair, skin, eyes, eyebrows or eyelashes.

8. In paragraph 1, A dye composition having improved stability and color retention, characterized in that the dye composition is used in a cosmetic composition, an ink composition, a paint composition, a resin composition or a food composition.

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