Graphitic carbon nitride containing one oxygen atom as sunscreen, paint, or filler product

Abstract

To provide a chemically-functionalized graphitic carbon nitride, which can provide keratinous materials, especially a human keratin material, such as skin, and keratin fibers, such as hair, with UV A and / or B protection, and to provide carbon nitride having color variations that allow the composition to be adjusted to the desired tone for any application such as cosmetic or paint products or as fillers especially in plastics.SOLUTION: The present invention mainly relates to use of graphitic carbon nitride containing at least one oxygen atom, as a paint active, a pigment, a filler of plastics, a cosmetic active material, and / or a sunscreen, such as a UVA and / or B absorber. The graphitic carbon nitride can exhibit a UVA and / or B absorption property and white to yellow colors and thus is useful as a UV absorber for various products which require a coloring property and attractive appearance.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention mainly relates to graphitic carbon nitride containing at least one oxygen atom (especially graphitic carbon nitride functionalized with a hydroxyl group, preferably an N-oxide, or graphitic carbon nitride functionalized with a nitroso group and a hydroxyl group) for use as an ultraviolet (UVA and / or UVB) absorbing material in cosmetic or paint products, or especially as a filler in plastics.

Background Art

[0002] The UV protection effect is one of the important elements regarding cosmetics. Graphitic carbon nitride, which is an inorganic compound, is known to exhibit UV absorption characteristics. Several documents regarding graphitic carbon nitride have already been reported.

[0003] For example, CN104801326A discloses a surface hydroxylated nanoporous carbon nitride photocatalyst material. However, this document does not mention the use of carbon nitride as an ultraviolet absorbing material in cosmetics. The use of graphitic carbon nitride as a UV absorber has also been reported (WO2020 / 246715), but this graphitic carbon nitride does not contain at least one oxygen atom.

[0004] Furthermore, makeup cosmetics are used to provide a desired color appearance to keratinous substances such as the skin, especially facial skin. Graphitic carbon nitride that can be used as an ultraviolet absorbing material and can provide a desired color to keratinous substances is not known.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Non-Patent Literature

[0006]

Non-Patent Literature 1

Non-Patent Literature 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a chemically functionalized graphitic carbon nitride that can provide UVA and / or B protection to keratinous materials, particularly human keratinous materials such as skin and keratin fibers such as hair. Another object of the present invention is to provide a carbon nitride having a color variation that allows the composition to be adjusted to a desired color tone for any application, for example, for cosmetic or paint products or, in particular, as a filler in plastics.

[0008] Therefore, the main object of the present invention is the use of graphitic carbon nitride as a cosmetic or paint product or as a filler in plastics, preferably as a sunscreen, particularly as a UVA and / or B absorber.

Means for Solving the Problems

[0009] The above object of the present invention is achieved, inter alia, by graphitic carbon nitride containing at least one oxygen atom (preferably at least one hydroxy group and / or nitroso group and / or N-oxide group and / or N-hydroxy (N-OH)). According to one embodiment, the graphitic carbon nitride contains at least one oxygen atom, and preferably, the oxygen atom is bonded to one or more nitrogen atoms to form, in particular, a nitroso (-NO) and / or N-oxide group.

[0010] The graphitic carbon nitride of the present invention contains at least one heptazine unit in its structure, and the structure contains at least one oxygen atom. The heptazine is preferably represented by formula (I) defined later herein, its salts and its solvates, such as hydrates.

[0011] According to an embodiment of the present invention, the graphitic carbon nitride of the present invention contains one or more hydroxy (OH) groups in its structure.

[0012] According to one embodiment, the graphitic carbon nitride contains one or more nitroso (NO) groups.

[0013] According to one embodiment, the graphitic carbon nitride contains one or more N-oxide groups.

[0014] According to one embodiment, the graphitic carbon nitride contains one or more N-OH groups.

[0015] According to an embodiment of the present invention, the graphitic carbon nitride of the present invention contains one or more carboxy groups in its structure.

[0016] According to a specific embodiment of the present invention, the amount of oxygen atoms in the graphitic carbon nitride is in the range of 0.1 to 10 atom%, preferably 0.5 to 7.5 atom%, more preferably 1.0 to 5.0 atom% based on the total atomic weight of the graphitic carbon nitride of the present invention.

[0017] In particular, graphitic carbon nitride has a porous structure.

[0018] Graphitic carbon nitride can have a yellowness index in the range of 5 to 50, preferably 10 to 45, more preferably 15 to 40.

[0019] Graphitic carbon nitride can have an onset absorption edge value in the range of 390 to 480 nm, preferably 400 to 450 nm.

[0020] The present invention also relates to a method for producing graphitic carbon nitride according to the present invention, comprising: i) preparing at least one precursor compound; ii) heating the at least one precursor compound at 450 °C or higher for at least 1 minute The heating step ii) of the above method is understood to be carried out in the presence of oxygen-containing species such as O2 (especially by an oxygen flux) and / or humidity.

[0021] The present invention also relates to a composition comprising graphitic carbon nitride containing at least one oxygen atom as defined hereinbefore and hereinafter, preferably a cosmetic composition for keratinous substances such as skin, in particular a sunscreen composition.

[0022] The composition may not contain TiO2 or ZnO, or may contain TiO2 and / or ZnO in an amount of 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the composition.

[0023] The present invention also relates to a method for treating a keratinous substance, preferably a cosmetic method, by applying the composition according to the present invention to a keratinous substance, especially a human keratinous substance such as skin, or a keratin fiber such as hair. BRIEF DESCRIPTION OF THE DRAWINGS

[0024]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Mode for Carrying Out the Invention

[0025] As a result of intensive research, the present inventors have surprisingly found that by incorporating an organic functional group into graphitic carbon nitride, it is possible to produce a desired color appearance suitable for various products, and thus the present invention has been completed.

[0026] Therefore, the present invention mainly relates to the use of graphitic carbon nitride containing at least one oxygen atom as a cosmetic or paint product, or as a filler in plastics, preferably as a sunscreen.

[0027] The graphite-like carbon nitride according to the present invention exhibits UV A and / or B absorption characteristics and a desired color, for example, an appearance from white to yellow, and thus it can provide desired coloring characteristics and an attractive appearance to products, and is therefore useful as a UV A and / or B absorber for various products. In particular, the graphite-like carbon nitride of the present invention can provide UV protection and a desired color tone to keratinous substances such as the skin, which is very useful as a UV A and / or B absorber for cosmetics because it contributes to improved color management.

[0028] Hereinafter, the present invention will be described in detail.

[0029] [Use] The present invention mainly relates to the use of the graphite-like carbon nitride of the present invention as a paint active substance, a pigment, a filler for plastics, a cosmetic active substance, and / or a sunscreen, for example, a UV A and / or B absorber.

[0030] In one embodiment, the present invention relates to the use of graphite-like carbon nitride containing at least one oxygen atom as a UV A and / or B absorber for protecting products from damage caused by UV A and / or B irradiation. For example, the UV A and / or B absorber of the present invention can be used in paints, plastics, coatings and cosmetics.

[0031] Since the graphite-like carbon nitride of the present invention can exhibit an appearance of a desired color, for example, an appearance from white to yellow, the use of the present invention can provide products that require desired coloring characteristics and an attractive appearance. In addition, the cosmetic composition can provide UV A and / or B protection and a desired color tone to keratinous substances such as the skin when graphite-like carbon nitride is used in the cosmetic composition.

[0032] The graphite-like carbon nitride of the present invention will be described in detail below.

[0033] [Graphite-like carbon nitride] The present invention also relates to graphite-like carbon nitride containing at least one oxygen atom.

[0034] Here, the term "graphite-like" in graphite-like carbon nitride means that the carbon nitride has a flat graphite-like structure. Thus, the graphite-like carbon nitride of the present invention has a layered or sheet structure.

[0035] The graphite-like carbon nitride of the present invention may contain at least one heptazine unit. As used herein, a heptazine unit means a hetero-condensed ring (triazine) consisting of three unsaturated heterocycles containing C atoms and N atoms represented by C6N7, and it is understood that at least one of the triazines of at least one heptazine unit contains at least one oxygen atom and may also contain a hydrogen atom. Preferably, the heptazine unit contains between 3 and 6 double bonds, more preferably 6 conjugated double bonds. Thus, the graphite-like carbon nitride of the present invention may have a monolayer structure based on heptazine. The graphite-like carbon nitride of the present invention may contain at least one heptazine unit, at least one triazine unit, and combinations thereof. The heptazine unit may have a substituent or group on a carbon atom. The substituent may be an oxygen-containing group that results in a further level or shift in occupancy and / or non-occupancy states, such as carboxyl, carbonyl, nitroso, nitro, hydroxy, and alkoxy groups. The presence of the heptazine unit can be determined by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR) analysis, and nuclear magnetic resonance spectroscopy (NMR) analysis.

[0036] In one embodiment of the present invention, the graphite-like carbon nitride of the present invention has a stacked structure of layered graphite-like carbon nitride sheets. In other words, the graphite-like carbon nitride of the present invention may have a multi-layer sheet structure of graphite-like carbon nitride. The stacked structure of the graphite-like carbon nitride sheets can be determined by X-ray diffraction (XRD) analysis and nuclear magnetic resonance spectroscopy (NMR) analysis.

[0037] The graphite-like carbon nitride of the present invention is composed of carbon atoms (C), nitrogen atoms (N), hydrogen atoms (H), and oxygen atoms (O). Preferably, the graphite-like carbon nitride of the present invention consists of or consists essentially of carbon atoms (C), nitrogen atoms (N), hydrogen atoms (H), and oxygen atoms (O).

[0038] The graphite-like carbon nitride of the present invention contains at least one oxygen atom in its structure. The amount of oxygen atoms in the graphite-like carbon nitride is not particularly limited, but generally, it is 0.1 atomic% or more, preferably 0.5 atomic% or more, more preferably 1.0 atomic% or more, and / or 10 atomic% or less, preferably 7.5 atomic% or less, more preferably 5.0 atomic% or less, based on the total atomic weight of the graphite-like carbon nitride. The atomic concentration of oxygen atoms in the graphite-like carbon nitride can be measured, for example, by generally known elemental analysis.

[0039] The amount of oxygen atoms in the graphite-like carbon nitride can be in the range of 0.1 to 10 atomic%, preferably 0.5 to 7.5 atomic%, more preferably 1.0 to 5.0 atomic%, based on the total atomic weight of the graphite-like carbon nitride.

[0040] The graphite-like carbon nitride of the present invention contains at least one nitroso group (-N=O). Therefore, at least one oxygen atom contained in the graphite-like carbon nitride of the present invention is derived from the nitroso group present in the graphite-like carbon nitride. The presence of the nitroso group in the graphite-like carbon nitride can be measured, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0041] The graphite-like carbon nitride of the present invention may contain at least one hydroxy group (-OH) in addition to a nitroso group (-NO). In other words, the graphite-like carbon nitride of the present invention may contain a combination of at least one nitroso group (-NO) and at least one hydroxy group (-OH). Therefore, at least one oxygen atom contained in the graphite-like carbon nitride of the present invention may also be derived from the hydroxy group present in the graphite-like carbon nitride. The presence of the hydroxy group in the graphite-like carbon nitride can be measured, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0042] The graphite-like carbon nitride of the present invention may have a porous structure. More specifically, the graphite-like carbon nitride of the present invention may have a nanoporous structure. The pores may be present in the layer structure of the graphite-like carbon nitride between heptazine units and triazine units.

[0043] The heptazine unit preferably has the formula (I):

[0044] [Chemical formula]

[0045] (In formula (I), R 1 , R 2 , and R 3 are the same or different and are i) a hydrogen atom, ii) a halogen atom, iii) an oxygen-containing group, such as a carboxy, nitro, or nitroso group, iv) a saturated or unsaturated, acyclic straight-chain or branched, and / or cyclic, aromatic or non-aromatic hydrocarbon chain containing 1 to 10 carbons and potentially interrupted by one or more heteroatoms such as O, S, N, or N(O), v) hydroxy, vi) amino R 4 R 5 N-(wherein R 4 and R 5is the same or different and is a hydrogen atom, a (C1-C6) alkyl group or another monovalent heptazine group, preferably a monovalent heptazine group (II)

[0046]

Chemical formula

[0047] represents, and R 1 and R 2 are as defined previously herein), vii) R 4 R 5 N(O)- (wherein R 4 and R 5 are the same or different and are as defined previously herein), and viii) R 4 -N(O)- (wherein R 4 is as defined previously herein), represents, -R 1 , R 2 , or R 3 at least one of the groups represents v) a hydroxy group, more preferably, R1 represents v) a hydroxy group, and R 2 and R 3 are the same or different, preferably the same, and represent a nitroso group selected from iii) vi) to viii), more preferably the nitroso group of viii), - One or more nitrogens in the ring may be oxidized (N-oxide or N-OH) It is understood that) it is represented by its salts and its solvates, such as hydrates.

[0048] ii) The halogen may be selected from Cl and Br.

[0049] iii) The hydrocarbon chain may be a saturated or unsaturated, preferably saturated, acyclic straight-chain or branched-chain, preferably acyclic straight-chain hydrocarbon chain. iii) The hydrocarbon chain may contain 1 to 6, preferably 1 to 4 carbon atoms. Accordingly, iii) the hydrocarbon chain may be a saturated acyclic straight-chain hydrocarbon chain containing 1 to 6, preferably 1 to 4 carbon atoms, which may be interrupted by one or more heteroatoms such as O, S, N or N(O).

[0050] More preferably, R 1 , R 2 , and R 3 are the same or different and are i) hydrogen, v) hydroxy, vi) amino R 4 R 5 N-(wherein R 4 and R 5 are the same or different and represent a hydrogen atom or another monovalent heptazine group (II), and R 1 and R 2 are as defined previously herein), and viii) nitroso R 4 -N(O)-(wherein R 4 is as defined previously herein), representing an atom or group selected therefrom.

[0051] Preferably, at least one of the R 1 , R 2 , or R 3 groups represents a v) hydroxy group.

[0052] Preferably, the graphitic carbon nitride according to the present invention contains at least one heptazine unit represented by formula (I) defined later herein, its salt and its solvate, such as hydrate, which in turn has a series of heptazine groups (II) by the vi) to viii) groups of R 1 , R 2 , and / or R 3 , especially the vi) or viii) groups, and preferably at least one of R 1 , R 2 , or R 3 represents a v) hydroxy group.

[0053] According to an embodiment of the present invention, the graphitic carbon nitride contains a series of heptazine units consisting of one ring of formula (I) and two ring subunits of formula (II) coupled by condensed tri-s-triazine (amino group vi) or nitroso group vii) or vii), more preferably viii).

[0054] The graphitic carbon nitride according to the present invention may have a characteristic porous structure having a large pore volume of pores having a specific pore diameter. For example, the graphitic carbon nitride according to the present invention has a pore volume of 0.0006 cm 3 / g, 0.0010 cm 3 / g, 0.0020 cm 3 / g, 0.0030 cm 3 / g, or more than 0.0040 cm 3 / g derived from pores having a specific pore diameter. Further, the graphitic carbon nitride according to the present invention is derived from pores of a first type having a specific pore diameter in the range of 1 nm or more and less than 15 nm, and pores of a second type having a specific pore diameter in the range of 15 nm or more, for example, 20 nm or more and 50 nm or less, and has a pore volume of 0.0006 cm 3 / g, 0.0010 cm 3 / g, 0.0020 cm 3 / g, 0.0030 cm 3 / g, or more than 0.0040 cm 3 / g.

[0055] The amount of pores having a specific pore diameter contained in the graphitic carbon nitride can be determined by using the Barrett-Joyner-Halenda (BJH) method for the obtained pore diameter distribution plot.

[0056] The graphite-like carbon nitride of the present invention can exhibit various colors of appearance, which is suitable and desirable for cosmetics. For example, the color of the graphite-like carbon nitride is selected from white, light yellow, and yellow. In a preferred embodiment of the present invention, the graphite-like carbon nitride can exhibit a yellowish color, which can provide improved color management for keratin substances such as skin, especially facial skin.

[0057] The yellowness of the graphite-like carbon nitride can be defined by the yellowness index, which is an index of yellow. The yellowness index can be measured using a UV-vis diffuse reflectance spectrometer. The yellowness index of the graphite-like carbon nitride can be in the range of 5 to 50, preferably 10 to 45, more preferably 15 to 40. In some embodiments of the present invention, the graphite-like carbon nitride exhibits a yellowness index of 20 or more, preferably 25 or more, more preferably 30 or more. The higher the yellowness index, the more yellowish the appearance of the graphite-like carbon nitride indicates.

[0058] The graphite-like carbon nitride of the present invention can exhibit UV A and / or B absorption characteristics. Preferably, the graphite-like carbon nitride has an absorption effect on both the UV-B and UV-A wavelength regions. Here, UV-B rays mean UV rays having wavelengths between 280 and 320 nm. Here, UV-A rays mean UV rays having wavelengths between 320 and 400 nm.

[0059] The UV absorption characteristics of the graphite-like carbon nitride of the present invention can be represented by the starting absorption end value (nm). The starting absorption end value can be defined by the wavelength (nm) at the intersection of a straight line drawn to match the region where the absorbance curve rapidly decreases from the short wavelength side of the absorbance curve and a straight line drawn to match the absorbance curve in the wavelength range of 500 to 650 nm where the absorbance curve remains constant and low.

[0060] Example 7 in Fig. 2 shows an example of the starting absorption characteristics at 407 nm, which is the wavelength at the intersection of (1) a straight line drawn to match the region where the absorbance curve rapidly decreases from the shorter wavelength side of the absorbance curve, and (2) a straight line drawn to match the absorbance curve in the wavelength range of 500 - 550 nm where the absorbance curve remains constantly low.

[0061] Absorption curves in the ultraviolet and visible light ranges can be measured, for example, by ultraviolet - visible (UV - vis) diffuse reflectance spectroscopy. The higher the starting absorption edge value, the more it means that graphitic carbon nitride can block light of longer wavelengths.

[0062] The graphitic carbon nitride of the present invention can have a starting absorption edge value of 390 nm or more, preferably 400 nm or more, generally 480 nm or less, preferably 450 nm or less.

[0063] The graphitic carbon nitride of the present invention can have a starting absorption edge value in the range of 390 - 480 nm, preferably 400 - 450 nm.

[0064] In some embodiments of the present invention, the graphitic carbon nitride has a starting absorption edge value of 410 nm or more, preferably 415 nm or less, and more preferably 420 nm or more.

[0065] The graphitic carbon nitride of the present invention may or may not be surface - treated with a surface - treating agent.

[0066] Figure 5 shows the optimized crystal structure (left) and electronic state (right) of graphite-like carbon nitride having heptazine units according to the present invention. In this modeled structure, one of the nitrogen atoms (labeled N97) forms a -N(O) group. The levels of occupied and unoccupied states of O2p and N2p derived from the -N(O) group appear in the energy region located slightly below the center of the fundamental bandgap region and in the energy region located near the top of the valence band. In particular, the contribution of the unoccupied state levels to light absorption results in absorption in the visible wavelength range, and as a result, coloration such as a yellow appearance is brought about.

[0067] Also, FIGS. 6(A) and 6(B) show the optimized crystal structure (left) and electronic state (right) of graphite-like carbon nitride having heptazine units. In the modeled structure (A), one of the nitrogen atoms (labeled N97) is bonded to an OH group and two carbon atoms of the C6N7 structure at the end of the heptazine unit. The nitrogen atom at a similar site without functionalization of the -OH group is labeled N123. In the modeled structure (B), one of the nitrogen atoms (labeled N128) is bonded to an -OH group and a proton. The nitrogen atom at a similar site without functionalization of the -OH group and the proton is labeled N121. Both the highest occupied levels of N97 and N128 shift to higher energies compared to the energy of the nitrogen atoms at similar sites without functionalization. This energy shift has a relatively large effect on the local electronic structure, narrowing the bandgap as indicated by the red circles and shifting the absorption edge value to a higher wavelength.

[0068] Although not wishing to be bound by theory, the mechanism for providing graphite-like carbon nitride having a yellow appearance by functionalization with oxygen-containing functional groups such as -N(O) and -OH groups is proposed by first-principles calculations using the local density approximation (LDA).

[0069] [Manufacturing Method] The present invention also relates to a method for manufacturing the graphite-like carbon nitride of the present invention.

[0070] Specifically, the present invention also relates to a method for producing graphitic carbon nitride of the present invention, comprising: i) preparing at least one precursor compound; ii) heating the at least one precursor compound at 450 °C or higher for at least 1 minute; and relates to a method comprising the above steps.

[0071] Graphitic carbon nitride can be prepared by heating at least one precursor compound of graphitic carbon nitride. One precursor compound may be used as a raw material for the graphitic carbon nitride of the present invention, or two or more precursor compounds may be used in combination.

[0072] The precursor compound can be selected from precursors known to those skilled in the art, such as urea, thiourea, melamine, guanidine, arginine, cyanamide, dicyandiamide, and salts thereof, and combinations thereof (Chem. Rev. 2016, 116, 7159 - 7329, Ong, W.J.; Tan, L.L.; Ng, Y.H.; Yong, S.T.; Chai, S.P., Catalysts 2019, 9(10), 805, Seong Jun Mun and Soo-Jin Park; https: / / doi.org / 10.3390 / catal9100805). Preferably, the precursor compound is selected from urea, melamine, guanidine, arginine, and salts and combinations thereof.

[0073] The salt of the precursor compound is not particularly limited, and examples thereof include salts with inorganic acids such as carboxylic acids and HalH (wherein Hal represents a halogen atom such as chlorine (hydrochloric acid)).

[0074] In a preferred embodiment of the present invention, in the preparation of graphitic carbon nitride, only one precursor compound is used as a raw material.

[0075] The temperature of the heating step of at least one precursor compound is at least 450 °C. Preferably, the heating step is carried out at 500 °C or higher, more preferably 525 °C or higher.

[0076] The time of the heating step of at least one precursor compound is at least 1 minute. Preferably, the time of the heating step is at least 10 minutes, more preferably at least 20 minutes, and / or within 30 hours, more preferably within 25 hours.

[0077] The heating of the precursor compound can be carried out in air, in a noble gas such as argon or helium, or in an inert gas such as nitrogen. In a preferred embodiment of the present invention, the heating of the precursor compound is carried out in air or in argon.

[0078] In a preferred embodiment, the heating process can be carried out in the presence of an oxygen-containing species as an oxidizing agent, such as O2, humidity, O3, atomic O, and / or oxygen ions. Without wishing to be bound by theory, it is believed that when heating is carried out in the presence of an oxygen-containing species, more porous graphite-like carbon nitride can be obtained. In a preferred embodiment, the heating is carried out in air or in a noble gas or inert gas containing an oxygen-containing species.

[0079] In a preferred embodiment, in addition to oxygen in the air, the heating process is carried out in the presence of an oxygen-containing species as an oxidizing agent, such as O2, humidity, ozone O3, O atoms, and / or oxygen ions.

[0080] In a preferred embodiment, the heating process is carried out in the presence of an oxygen-containing species of O2, particularly an oxygen flux, and / or humidity. The term "oxygen flux" can mean an oxygen flow herein.

[0081] Preferably, the oxidizing agent used during the heating step is gaseous.

[0082] According to one embodiment, the oxygen source is not derived from permanganate or hydrogen peroxide.

[0083] In one embodiment of the present invention, the heating process includes at least two heating steps at the same or different temperatures. Thus, in one embodiment, the heating process may include a first heating step of at least one precursor compound at 450 °C or higher for at least 1 minute, and then a second heating step of at least one precursor compound at 450 °C or higher for at least 1 minute. The temperature of the first heating step and the temperature of the second heating step may be the same or different, but generally, the temperature of the second heating step is equal to or higher than the temperature of the first heating step. The temperature and time of the first and second heating steps are as described above.

[0084] In one embodiment of the present invention, there is a cooling step between the heating steps. Thus, in one embodiment, the cooling step is included between the first heating step and the second heating step. The temperature of the cooling step is not particularly limited, but for example, the temperature is cooled to room temperature (about 25 °C). The time of the cooling step is not particularly limited, but for example, it is about 1 minute to 24 hours.

[0085] [Composition] The present invention also relates to a composition containing the graphitic carbon nitride of the present invention. Preferably, the composition according to the present invention is a cosmetic composition, particularly a cosmetic composition for keratin substances such as the skin. In a preferred embodiment, the composition according to the present invention is a sunscreen composition.

[0086] Also, the composition according to the present invention can be used as a paint active substance, a pigment, a filler for plastics, a cosmetic active substance, and / or a sunscreen, for example, as a UVA and / or B absorber.

[0087] The composition according to the present invention preferably does not contain TiO2 or ZnO.

[0088] In another embodiment, the composition according to the invention comprises TiO2 and / or ZnO in an amount of 5% by weight or less, more preferably 1% by weight or less, based on the total weight of the composition. The graphitic carbon nitride of the present invention can be used in the composition instead of TiO2 and ZnO known as traditional inorganic UV blockers.

[0089] Since the graphitic carbon nitride according to the present invention can exhibit a white to yellow appearance, the cosmetic composition according to the present invention can provide a desired coloring and attractive appearance to keratinous substances, as well as usefulness in color management.

[0090] [Treatment method] Another object of the present invention is a method or process for treating a keratinous substance, in particular a human keratinous substance such as the skin or a keratin fiber such as hair, by applying a composition as defined above, preferably the cosmetic composition of the present invention, to the keratinous substance.

[0091] Therefore, the method or process according to the present invention can be a non-therapeutic cosmetic method or process for treating keratinous substances.

Examples

[0092] The present invention will be described in more detail by way of examples. However, these examples should not be construed as limiting the scope of the present invention.

[0093] [Preparation] Powdery graphitic carbon nitride according to the present invention was prepared in Examples 1 to 10 below.

[0094] (Example 1) 10 g of urea powder as a precursor compound was heated in air at 550 °C for 2 hours to obtain graphitic carbon nitride according to Example 1.

[0095] (Example 2) 10 g of urea powder was used as a precursor and subjected to heating at 550 °C for 1 hour in air and subsequently heating at 600 °C for 30 minutes in air to obtain graphite-like carbon nitride according to Example 2.

[0096] (Example 3) 10 g of urea powder was used as a precursor compound and subjected to heating at 600 °C for 2 hours in air to obtain graphite-like carbon nitride according to Example 3.

[0097] (Example 4) 10 g of urea powder was used as a precursor and subjected to heating at 600 °C for 2 hours in air, cooling to room temperature, and then heating at 600 °C for 1 hour in air to obtain graphite-like carbon nitride according to Example 4.

[0098] (Example 5) 10 g of urea powder was used as a precursor compound and subjected to (a) heating at 600 °C for 1 hour in air and (b) cooling to room temperature in three consecutive processes to obtain graphite-like carbon nitride according to Example 5.

[0099] (Example 6) 10 g of urea powder was used as a precursor compound and subjected to heating at 600 °C for 2 hours in air, cooling to room temperature, and then (a) heating at 600 °C for 1 hour in air and (b) cooling to room temperature in two consecutive processes to obtain graphite-like carbon nitride according to Example 6.

[0100] (Example 7) 12 g of urea powder was used as a precursor compound and subjected to (a) heating at 600 °C for 1 hour in air and (b) cooling to room temperature in three consecutive processes to obtain graphite-like carbon nitride according to Example 7.

[0101] (Example 8) 10 g of urea powder was used as a precursor compound and heated at 600 - 605 °C for 2 hours in air to obtain graphite-like carbon nitride according to Example 8.

[0102] (Example 9) 3 g of melamine powder was used as a precursor compound and heated in air at 550 °C for 5 hours to obtain graphitic carbon nitride according to Example 9.

[0103] (Example 10) 20 g of guanidine carbonate powder was used as a precursor and heated in air at 600 °C for 2 hours to obtain graphitic carbon nitride according to Example 10.

[0104] [Evaluation] (Crystal Structure) The crystal structure of each of the graphitic carbon nitrides was identified using X-ray diffraction (XRD) analysis. In the XRD pattern, the peak at 13° was assigned to the (100) of graphitic carbon nitride having a heptazine unit, and the peak at 27° was assigned to the (002) plane of the c-axis in the stacked sheet of graphitic carbon nitride. Figure 1 shows the XRD pattern of graphitic carbon nitride according to Example 2 as a representative example.

[0105] According to the XRD analysis of each of the graphitic carbon nitrides of Examples 1 to 10, it was confirmed that each of the graphitic carbon nitrides according to Examples 1 to 10 has a multi-layer sheet of graphitic carbon nitride having a heptazine unit.

[0106] (Elemental Composition Analysis) The elemental composition of each of the graphitic carbon nitrides was estimated using CNHO elemental analysis based on the combustion of the sample.

[0107] (Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) Analysis) TOF-SIMS analysis was performed to analyze whether functional groups are present in each of the graphitic carbon nitrides. For the TOF-SIMS analysis, TOF.SIMS 5 (ION-TOF GmbH, Germany) was used. The primary ion irradiated was 209 Bi3 ++ as follows.

[0108] The TOF-SIMS spectrum of Example 2 (analysis area: 90,000 μm2 ) In this case, the intensity of m / z = 17 that can contribute to OH ions was 1460, and the intensity of m / z = 30 that can contribute to NO ions was 92.

[0109] The TOF-SIMS spectrum of Example 4 (analysis area: 90,000 μm 2 ) In this case, the intensity of m / z = 17 that can contribute to OH ions was 764, and the intensity of m / z = 30 that can contribute to NO ions was 59.

[0110] The TOF-SIMS spectrum of Example 8 (analysis area: 40,000 μm 2 ) In this case, the intensity of m / z = 17 that can contribute to OH ions was 1195, and the intensity of m / z = 30 that can contribute to NO ions was 86.

[0111] The TOF-SIMS spectrum of Example 9 (analysis area: 40,000 μm 2 ) In this case, the intensity of m / z = 17 that can contribute to OH ions was 1342, and the intensity of m / z = 30 that can contribute to NO ions was 88.

[0112] The TOF-SIMS spectrum of Example 10 (analysis area: 40,000 μm 2 ) In this case, the intensity of m / z = 17 that can contribute to OH ions was 1671, and the intensity of m / z = 30 that can contribute to NO ions was 73.

[0113] According to the TOF-SIMS analysis of each of the graphite-like carbon nitrides of Examples 1 to 10, it was confirmed that each of the graphite-like carbon nitrides contains nitroso groups and hydroxy groups.

[0114] (UV absorption characteristics and yellowness index) The light absorption performance of each of the graphite-like carbon nitrides in the wavelength range of ultraviolet and visible light was evaluated using ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy (UV2500PC, Shimadzu Corporation) connected to an integrating sphere.

[0115] The UV-vis absorption spectra of each aqueous dispersion (medium: water) of 0.1 mass% of graphitic carbon nitride in a fine quartz cell (two transparent sides, 2 mm (optical path length) × 10 mm × H 45 mm, Tokyo Garasu Kikai Co., Ltd.) were collected using a UV-visible spectrophotometer (V750, Jasco Inc.) connected with an integrating sphere. The onset absorption edge was estimated from the UV-vis diffuse reflectance spectra of each sample.

[0116] Figure 2 shows the absorption spectra obtained by measuring the UV-vis diffuse reflectance of the as-synthesized powders of graphitic carbon nitride according to Examples 1 to 7. All graphitic carbon nitrides showed absorption in the UV range where the wavelength is less than 400 nm.

[0117] Figure 3 shows, as a representative example, the absorption spectrum of a liquid sample in which 0.1 mass% of graphitic carbon nitride according to Example 9 was suspended in water. The aqueous suspension showed absorption in the UV wavelength range less than 400 nm.

[0118] The yellowness index, which is an index of yellowness, was also evaluated from the UV-vis diffuse reflectance spectra of each powder sample. The calculation of the yellowness index and the white value was performed using the software of Shimadzu Corporation installed in the device with light source C as the standard light source and the viewing angle set to 10°. A BaSO4 standard white plate was used as a reference.

[0119] The results are summarized in Table 1 below. Also, the relationship between the concentration (atomic%) of oxygen atoms in graphitic carbon nitride and the onset absorption edge value is summarized in Fig. 4(a), and the relationship between the concentration (atomic%) of oxygen atoms in graphitic carbon nitride and the measured value of the yellowness index is summarized in Fig. 4(b).

[0120]

Table 1

[0121] Table 1 (Table 1) and Fig. 4(a) show that the larger the amount of oxygen atoms, the greater the tendency for the onset absorption edge value of graphitic carbon nitride to increase.

[0122] Also, the graph in Fig. 4(b) clearly shows that the higher the concentration (atomic %) of oxygen atoms in graphitic carbon nitride, the more graphitic carbon nitride with a higher yellowness index is produced. This indicates that the higher the oxygen atom concentration of graphitic carbon nitride, the more graphitic carbon nitride can exhibit a more yellowish appearance.

[0123] Therefore, the graphitic carbon nitride according to the present invention has a very remarkable effect, and it is possible to change and design the desired color appearance and UV absorption characteristics by functionalizing the graphitic carbon nitride with an oxygen-containing group which is a nitroso group.

[0124] Therefore, it can be concluded that the graphitic carbon nitride of the present invention is very useful as a UV absorber for various products because it can bring about the desired coloring characteristics and an attractive appearance to the products. In particular, the graphitic carbon nitride of the present invention is very useful as a UV absorber for cosmetics because it can provide a desired color tone that contributes to UV protection and improved color management for keratinous substances such as the skin.

Claims

1. Use of graphitic carbon nitride containing at least one oxygen atom as a coating active substance, as a pigment, especially as a filler for plastics, or as a cosmetic active substance.

2. Use of the graphitic carbon nitride according to claim 1 as a cosmetic, preferably as a sunscreen.

3. Use of the graphitic carbon nitride according to claim 1 or 2 as a UVA and / or B absorber.

4. Use of graphitic carbon nitride having, in its structure, preferably at least one hydroxy group, nitroso group, N-oxide group, and / or N-hydroxy (N-OH) group, and preferably having at least one heptazine unit having at least one hydroxy group and at least one nitroso group, according to any one of claims 1 to 3.

5. The heptazine unit is of formula (I): 【Chemical 1】 (In formula (I), R 1 , R 2 , and R 3 are the same or different, i) a hydrogen atom, ii) a halogen atom, iii) an oxygen-containing group, such as a carboxy, nitro, or nitroso group, iv) a saturated or unsaturated, acyclic straight-chain or branched, and / or cyclic, aromatic or non-aromatic hydrocarbon chain containing 1 to 10 carbons, potentially interrupted by one or more heteroatoms such as O, S, N or N(O), v) hydroxy, vi) Amino R 4 R 5 N-(wherein R 4 and R 5 are the same or different and are a hydrogen atom, a (C 1 -C 6 ) alkyl group or another monovalent heptazine group, preferably a monovalent heptazine group (II) 【Chemical 2】 represents, and R 1 and R 2 are as defined earlier in this specification), vii) R 4 R 5 N(O)- (wherein R 4 and R 5 are the same or different and are as defined earlier herein), and viii) R 4 -N(O)-(wherein R 4 is as defined earlier in this specification) represents, - R 1 , R 2 , or R 3 Among the groups of at least one of them, v) represents a hydroxy group, more preferably, R1 represents a v) hydroxy group, R 2 and R 3 are the same or different, preferably the same, and represent a nitroso group selected from iii) vi) to viii), more preferably the nitroso group of viii). - One or more nitrogens in the ring may be oxidized (N-oxide or N-OH) It is understood) represented by its salts and its solvates, such as hydrates, of the graphitic carbon nitride according to claim 4.

6. R 1 、R 2 、and R 3 are the same or different and are i) hydrogen, v) hydroxy, vi) amino R 4 R 5 N-(wherein R 4 and R 5 are the same or different and represent a hydrogen atom or another monovalent heptazine group (II), and R 1 and R 2 are as defined previously herein), and viii) nitroso R 4 -N(O)-(wherein R 4 is as defined previously herein), and represent an atom or group selected from, preferably, at least one of the R 1 、R 2 、or R 3 groups represents a v) hydroxy group, Use of the graphitic carbon nitride according to claim 5.

7. The heptazine unit is R as defined in claim 5 or 6 1 , R 2 , and / or R 3 has a series of heptazine groups (II) via any one of vi) to viii) of, in particular, via the group of vi) or viii), preferably at least one of the groups of R 1 , R 2 , or R 3 represents a hydroxy group, Use of the graphitic carbon nitride according to claim 5 or 6

8. The amount of oxygen atoms in the graphitic carbon nitride is in the range of 0.1 to 10 atomic %, preferably 0.5 to 7.5 atomic %, more preferably 1.0 to 5.0 atomic %, based on the total atomic weight of the graphitic carbon nitride, according to any one of claims 1 to 7.

9. Use of the graphitic carbon nitride according to any one of claims 1 to 8, wherein the graphitic carbon nitride has a porous structure.

10. Use of the graphitic carbon nitride according to any one of claims 1 to 9, wherein the graphitic carbon nitride has a yellowness index in the range of 5 to 50, preferably 10 to 45, more preferably 15 to 40.

11. Use of the graphitic carbon nitride according to any one of claims 1 to 10, wherein the graphitic carbon nitride has an onset absorption edge value in the range of 390 to 480 nm, preferably 400 to 450 nm.

12. Graphitic carbon nitride containing at least one oxygen atom as defined in any one of claims 1 to 11, wherein the oxygen atom is present in at least one nitroso group (NO).

13. Graphitic carbon nitride as defined in any one of claims 1 to 12, having at least one heptazine unit in the structure.

14. Graphitic carbon nitride according to any one of claims 1 to 13, having at least one hydroxy group and / or at least one nitroso group, or an N-oxide in the structure, preferably having at least one hydroxy group and at least one nitroso group in at least one heptazine unit.

15. A composition comprising graphitic carbon nitride as defined in any one of claims 1 to 14, and water and / or at least one organic medium.

16. A composition containing graphitic carbon nitride as defined in any one of claims 1 to 15, preferably a cosmetic, preferably a sunscreen composition.

17. TiO in an amount of 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the composition 2 and / or ZnO, and more preferably, the composition according to claim 15 or 16, containing neither TiO 2 nor ZnO

18. A method for preparing graphitic carbon nitride as defined in any one of claims 12 to 14, comprising: i) a step of preparing at least one precursor compound; ii) A step of heating the at least one precursor compound at 450 °C or higher for at least 1 minute, preferably in the presence of an oxygen-containing species as an oxidizing agent, such as O 2 , humidity, O 3 , O atoms, and / or oxygen ions; preferably, the oxidizing agent used during the heating step is gaseous; more preferably, the oxygen-containing species is not derived from permanganate or hydrogen peroxide, the step of heating A method comprising.

19. A method for treating a keratinous substance, particularly a human keratinous substance such as skin or keratin fibers such as hair, by applying the composition according to any one of claims 15 to 17 to the keratinous substance.

Images