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

Abstract

The present invention relates primarily to the use of graphitic carbon nitride containing at least one oxygen atom, as an active ingredient in paints, pigments, plastic fillers, active ingredients in cosmetics, and / or as a sunscreen, such as a UV A and / or UV B absorber. Graphitic carbon nitride can exhibit UV A and / or UV B absorption properties and a white to yellow color, and thus is useful as a UV absorber for various products requiring coloring properties and an attractive appearance.

Description

Technology Field

[0001] The present invention relates primarily to graphitic nitride containing at least one oxygen atom (particularly functionalized with a hydroxyl group, preferably N-oxide, or graphitic nitride functionalized with a nitroso group and a hydroxyl group) for use as an ultraviolet (UV A and / or UV B) absorbing material in cosmetic or paint products, or particularly as a filler in plastics. Background Technology

[0002] UV protection is one of the key factors in cosmetic products. Graphitic carbon nitride, an inorganic compound, is known to exhibit UV absorption properties. Some literature regarding graphitic carbon nitride has been previously reported.

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

[0004] In addition, makeup cosmetic products are used to impart a desired color appearance to keratinized materials on the skin, particularly facial skin. No graphitic carbon nitride is known that can be used as a UV-absorbing material and impart a desired color to keratinized materials. The problem to be solved

[0005] The object of the present invention is to provide chemically functionalized graphitic carbon nitride capable of imparting UV A and / or UV B protection to keratin materials, particularly human keratin materials such as skin, and keratin fibers such as hair. Another object of the present invention is to provide carbon nitride having a color change that enables the composition to be adjusted to a desired shade for any use, such as cosmetic or paint products, or particularly fillers in plastics.

[0006] Accordingly, 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, and preferably as a sunscreen, particularly as a UV A and / or UV B absorber. means of solving the problem

[0007] The above objective of the present invention is achieved in particular by graphitic carbon nitride containing at least one oxygen atom (preferably at least one hydroxyl 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.

[0008] The graphitic carbon nitride of the present invention contains at least one heptazine unit within its structure, and said structure contains at least one oxygen atom. The heptazine is preferably represented by formula (I) defined below, its salt, and its solvate, for example, a hydrate.

[0009] According to one embodiment of the present invention, the graphitic carbon nitride of the present invention contains one or more hydroxyl (OH) groups in its structure.

[0010] According to one embodiment, the graphitic carbon nitride contains one or more nitroso (NO) groups.

[0011] According to one embodiment, the graphitic carbon nitride contains one or more N-oxide groups.

[0012] According to one embodiment, the graphitic carbon nitride contains one or more N-OH groups.

[0013] According to one embodiment of the present invention, the graphitic carbon nitride of the present invention contains one or more carboxyl groups in its structure.

[0014] According to one specific embodiment of the present invention, the amount of oxygen atoms in the graphitic carbon nitride is within the range of 0.1 to 10 atomic%, preferably 0.5 to 7.5 atomic%, more preferably 1.0 to 5.0 atomic% with respect to the total atomic weight of the graphitic carbon nitride of the present invention.

[0015] In particular, graphitic carbon nitride has a porous structure.

[0016] Graphitic carbon nitride can have a yellowness index in the range of 5 to 50, preferably 10 to 45, more preferably 15 to 40.

[0017] Graphitic carbon nitride can have an onset absorption edge value in the range of 390 to 480 nm, preferably 400 to 450 nm.

[0018] The present invention also relates to a method for producing graphitic carbon nitride according to the present invention, comprising at least two steps:

[0019] i) a step of preparing at least one precursor compound; and

[0020] ii) a step of heating at least one precursor compound at 450°C or higher for at least 1 minute.

[0021] ii) In the above method, heating is understood to be performed in the presence of oxygen-containing species such as O2 (particularly, oxygen flux) and / or moisture.

[0022] The present invention also relates to a composition comprising graphitic carbon nitride containing at least one oxygen atom as defined above and below, preferably a cosmetic composition for keratin materials such as skin, particularly a sunscreen composition.

[0023] The composition may not contain TiO2 or ZnO, or may contain 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.

[0024] The present invention also relates to a method for treating keratin materials, particularly human keratin materials such as skin, or keratin fibers such as hair, by applying a composition according to the present invention onto a keratin material, preferably a cosmetic method. Brief explanation of the drawing

[0025] Figure 1 shows the XRD pattern of graphitic carbon nitride according to Example 2 of the present invention. Figure 2 shows the absorption spectra obtained through UV-vis diffuse reflection measurements of the synthesized powders of graphitic carbon nitride according to Examples 1 to 7. Figure 3 shows the absorption spectrum of a liquid sample in which graphitic carbon nitride according to Example 9 is suspended in water at 0.1 wt%. Figure 4 shows the relationship between the concentration of oxygen atoms (at.%) in graphitic carbon nitride, the measured onset absorption edge value (a), and the measured yellowness index (b). Figure 5 shows a model of the optimized crystal structure (left) and electronic state (right) of graphitic carbon nitride having heptazine units of the present invention. Figures 6 (A) and 6 (B) show models of the optimized crystal structure (left) and electronic state (right) of graphitic carbon nitride having heptazine units. Specific details for implementing the invention

[0026] As a result of the aforementioned research, the inventors surprisingly discovered that introducing organic functional groups into graphitic carbon nitride can produce a desired color appearance suitable for various products, thereby completing the present invention.

[0027] Accordingly, the present invention is mainly about the use of graphitic carbon nitride containing at least one oxygen atom, as a cosmetic or paint product, or as a filler in plastics, and preferably as a sunscreen.

[0028] The graphitic carbon nitride according to the present invention can exhibit UV A and / or UV B absorption characteristics and a desired color, such as a white to yellow appearance, and is therefore useful as a UV A and / or UV B absorber for various products, as it can impart 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 A and / or UV B absorber for cosmetic products, as it can impart a desired color tone that contributes to UV protection and enhanced color management for keratin materials such as skin.

[0029] The present invention will be described in detail below.

[0030] [use]

[0031] The present invention is primarily related to the use of the graphitic carbon nitride of the present invention as a paint active ingredient, a pigment, a plastic filler, a cosmetic active ingredient, and / or as a sunscreen such as a UV A and / or UV B absorber.

[0032] In one embodiment, the present invention relates to the use of graphitic carbon nitride containing at least one oxygen atom as a UV A and / or UV B absorber for protecting a product from damage caused by UV A and / or UV B radiation. For example, the UV A and / or UV B absorber of the present invention may be used in paints, plastics, coatings, and cosmetics.

[0033] Since the graphitic carbon nitride of the present invention can exhibit a desired color appearance, such as a white to yellow color appearance, the use of the present invention can provide products requiring desired coloring characteristics and an attractive appearance. Furthermore, when graphitic carbon nitride is used in a cosmetic composition, the cosmetic composition can provide UV A and / or UV B protection and a desired color tone to keratin materials such as skin.

[0034] The graphitic carbon nitride of the present invention will be described in detail below.

[0035] [Graphite carbon nitride]

[0036] The present invention also relates to graphitic carbon nitride containing at least one oxygen atom.

[0037] Here, the term "graphitic" in graphitic carbon nitride means that the carbon nitride has a planar graphite-like structure. Accordingly, the graphitic carbon nitride of the present invention has a layered structure or a sheet structure.

[0038] The graphitic carbon nitride of the present invention may comprise at least one heptazine unit. In this specification, a heptazine unit refers to a heterocondensed ring (triazine) composed of three unsaturated hetero rings containing a C atom and an N atom, represented as C6N7, and it is understood that at least one of the triazines of the at least one heptazine unit contains at least one oxygen atom and may also contain a hydrogen atom. Preferably, the heptazine unit contains 3 to 6 double bonds, more preferably 6 conjugated double bonds. Thus, the graphitic carbon nitride of the present invention may have a heptazine-based monolayer structure. The graphitic carbon nitride of the present invention may comprise 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 above substituent may be an oxygen-containing group, such as a carboxyl, carbonyl, nitroso, nitro, hydroxyl, and alkoxy group, providing additional or shifted levels of occupied and / or unoccupied states. The presence of heptazine units may be determined by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR) analysis, and nuclear magnetic resonance spectroscopy (NMR) analysis.

[0039] In one embodiment of the present invention, the graphitic carbon nitride of the present invention has a laminated structure of layered graphitic carbon nitride sheets. In other words, the graphitic carbon nitride of the present invention may have a multilayer sheet structure of graphitic carbon nitride. The laminated structure of the graphitic carbon nitride sheets can be determined by X-ray diffraction (XRD) analysis and nuclear magnetic resonance (NMR) analysis.

[0040] The graphitic carbon nitride of the present invention consists of carbon atoms (C), nitrogen atoms (N), hydrogen atoms (H), and oxygen atoms (O). Preferably, the graphitic carbon nitride of the present invention consists of or substantially consists of carbon atoms (C), nitrogen atoms (N), hydrogen atoms (H), and oxygen atoms (O).

[0041] The graphitic carbon nitride of the present invention contains at least one oxygen atom within its structure. The amount of oxygen atoms in the graphitic carbon nitride is not particularly limited, but generally, with respect to the total atomic weight of the graphitic carbon nitride, it may be 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. The atomic concentration of oxygen atoms in the graphitic carbon nitride can be measured, for example, by generally known elemental analysis.

[0042] The amount of oxygen atoms in the graphitic carbon nitride may be in the range of 0.1 to 10 atomic%, preferably 0.5 to 7.5 atomic%, and more preferably 1.0 to 5.0 atomic% with respect to the total atomic weight of the graphitic carbon nitride.

[0043] The graphitic carbon nitride of the present invention comprises at least one nitroso group (-N=O). Accordingly, at least one oxygen atom contained in the graphitic carbon nitride of the present invention originates from the nitroso group present in the graphitic carbon nitride. The presence of the nitroso group in the graphitic carbon nitride can be measured, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0044] The graphitic carbon nitride of the present invention may include at least one hydroxyl group (-OH) in addition to a nitroso group (-NO). In other words, the graphitic carbon nitride of the present invention may include a combination of at least one nitroso group (-NO) and at least one hydroxyl group (-OH). Accordingly, at least one oxygen atom included in the graphitic carbon nitride of the present invention may also originate from the hydroxyl group present in the graphitic carbon nitride. The presence of the hydroxyl group in the graphitic carbon nitride can be measured, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0045] The graphitic carbon nitride of the present invention may have a porous structure. More specifically, the graphitic carbon nitride of the present invention may have a nanoporous structure. Pores may exist on the layered structure of the graphitic carbon nitride between heptazine units and triazine units.

[0046] The heptazine unit is preferably represented by formula (I), its salt, and its solvate, e.g., hydrate:

[0047]

[0048] In Equation (I), R 1 , R 2 , and R 3 ...is identical or different, and represents the following:

[0049] i) hydrogen atom,

[0050] ii) Halogen atom,

[0051] iii) Oxygen-containing groups such as carboxyl groups, nitro groups, or nitroso groups,

[0052] iv) a hydrocarbon chain containing 1 to 10 carbon atoms, which is saturated or unsaturated, acyclic linear or branched, and / or cyclic, aromatic or non-aromatic, wherein the hydrocarbon chain may potentially be interrupted by one or more heteroatoms such as O, S, N, or N(O);

[0053] v) Hydroxy,

[0054] vi) Amino R 4 R 5 N- (here, R 4 and R 5 is 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)

[0055]

[0056] It represents, where R 1 and R 2 is as previously defined);

[0057] vii) R 4 R 5 N(O)- (here, R 4 and R 5 is identical or different, as previously defined); and

[0058] viii) R 4 -N(O)- or (where, R 4 is as previously defined);

[0059] However, it is understood as follows:

[0060] - R 1 , R 2 , or R 3 At least one of the groups represents v) a hydroxyl group, and more preferably R 1 represents v) a hydroxyl group, and R 2 and R 3 ...is the same or different, preferably the same, and represents iii) a nitroso group selected from vi) to viii), more preferably viii), and

[0061] - One or more nitrogen atoms in the ring can be oxidized (N-oxide or N-OH).

[0062] ii) Halogens can be selected from Cl and Br.

[0063] iii) The hydrocarbon chain may be a saturated or unsaturated, preferably saturated, acyclic linear or branched, preferably acyclic linear hydrocarbon chain. iii) The hydrocarbon chain may contain 1 to 6, preferably 1 to 4 carbon atoms. Thus, iii) the hydrocarbon chain may be a saturated acyclic linear 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).

[0064] More preferably, R 1 , R 2, and R 3 is, identical or different, i) hydrogen, v) hydroxyl, vi) amino R 4 R 5 N-(here, R 4 and R 5 is identical or different, a hydrogen atom, or another monovalent heptazine group (II)(where, R 1 and R 2 represents (as previously defined); and viii) nitroso R 4 -N(O)-(where, R 4 represents an atom or group selected from (as previously defined).

[0065] Preferably R 1 , R 2 , or R 3 At least one of the groups represents v) a hydroxyl group.

[0066] Preferably, the graphitic carbon nitride according to the present invention contains at least one heptazine unit represented by formula (I) defined below, its salt, and its solvate, for example, a hydrate, wherein the heptazine unit is again R 1 , R 2 and / or R 3 having a continuous heptazine group (II) through vi) to viii), particularly vi) or viii), preferably R 1 , R 2 , or R 3 At least one of the groups represents v) a hydroxyl group.

[0067] According to one embodiment of the present invention, the graphitic carbon nitride contains a continuous heptazine unit consisting of a subunit of one ring of formula (I) and two rings of formula (II) coupled through a condensed tri-s-triazine (amino group vi) or nitroso group vii), or vii), more suitably viii).

[0068] The graphitic carbon nitride according to the present invention may have a characteristic porous structure having a large pore volume of pores having a non-pore diameter. For example, the graphitic carbon nitride according to the present invention has a 0.0006 cm pore originating from pores having a non-pore diameter. 3 / g, 0.0010cm 3 / g, 0.0020cm 3 / g, 0.0030cm 3 / g, or 0.0040cm 3 It may have a pore volume greater than / g. Additionally, the graphitic carbon nitride according to the present invention is derived from a first type of pore having a non-pore diameter in the range of 1 nm or more and less than 15 nm, and from a second type of pore having a non-pore diameter in the range of 15 nm or more, for example, 20 nm or more and 50 nm or less, 0.0006 cm 3 / g, 0.0010cm 3 / g, 0.0020cm 3 / g, 0.0030cm 3 / g, or 0.0040cm 3 It can have a work volume exceeding / g.

[0069] The amount of non-porous pores contained in graphitic carbon nitride can be determined by using the Barrett-Joyner-Halenda (BJH) method on the obtained pore size distribution plot.

[0070] The graphitic carbon nitride of the present invention can exhibit various color appearances, which are suitable and desirable for cosmetic products. For example, the color of the graphitic carbon nitride is selected from white, pale yellow, and yellow. In a preferred embodiment of the present invention, the graphitic carbon nitride can exhibit a yellowish color that can provide enhanced tone care to keratin materials, such as skin, particularly facial skin.

[0071] The yellowness of graphitic carbon nitride can be defined by a yellowness index, which is an index of yellowness. The yellowness index can be measured using a UV-vis diffuse reflectance spectrometer. The yellowness index of graphitic carbon nitride may be in the range of 5 to 50, preferably 10 to 45, and more preferably 15 to 40. In some embodiments of the present invention, graphitic carbon nitride exhibits a yellowness index of 20 or higher, preferably 25 or higher, and more preferably 30 or higher. A higher yellowness index indicates that the appearance of the graphitic carbon nitride is more yellow.

[0072] The graphitic carbon nitride of the present invention may exhibit UV A and / or UV B absorption characteristics. Preferably, the graphitic carbon nitride has an absorption effect for both regions of UV-B and UV-A rays. Here, UV-B rays refer to UV rays having a wavelength between 280 and 320 nm. Here, UV-A rays refer to UV rays having a wavelength between 320 and 400 nm.

[0073] The UV absorption characteristics of the graphitic carbon nitride of the present invention can be expressed as an onset absorption edge value (nm). The onset absorption edge value can be defined as the wavelength (nm) at the intersection of a straight line drawn along the region where the absorbance curve drops sharply from the shorter wavelength side of the absorbance curve, and a straight line drawn along the absorbance curve in the wavelength range of 500 to 550 nm where the absorbance curve drops steadily.

[0074] Example 7 of FIG. 2 illustrates an example in which the onset absorption edge value is 407 nm, which is the wavelength at the intersection of (1) a straight line drawn along the region where the absorbance curve drops sharply from the shorter wavelength side of the absorbance curve, and (2) a straight line drawn along the absorbance curve in the wavelength range of 500 to 550 nm.

[0075] Absorption curves in the ultraviolet and visible light ranges can be measured, for example, by ultraviolet-visible (UV-vis) diffuse reflection spectroscopy. A higher onset absorption edge value indicates that the wavelength of light that graphitic carbon nitride can filter is longer.

[0076] The graphitic carbon nitride of the present invention may have an onset absorption edge value of 390 nm or more, preferably 400 nm or more, generally 480 nm or less, preferably 450 nm or less.

[0077] The graphitic carbon nitride of the present invention may have an onset absorption edge value in the range of 390 to 480 nm, preferably 400 to 450 nm.

[0078] In some embodiments of the present invention, the graphitic carbon nitride has an onset absorption edge value of 410 nm or more, preferably 415 nm or less, more preferably 420 nm or more.

[0079] The graphitic carbon nitride of the present invention may or may not be surface-treated with a surface treatment agent.

[0080] FIG. 5 shows the optimized crystal structure (left) and electronic state (right) of graphitic carbon nitride having heptazine units of the present invention. In this modeled structure, one of the nitrogen atoms (labeled as N97) forms an -N(O) group. The occupied and unoccupied state levels of O2p and N2p derived from the -N(O) group appear in an energy region located slightly below the midpoint of the fundamental bandgap region and an energy region located close to the top of the valence band. In particular, the contribution of the unoccupied state level to light absorption leads to absorption in the visible wavelength range, which causes coloration such as a yellow appearance.

[0081] Additionally, Figures 6(A) and 6(B) show the optimized crystal structure (left) and electronic state (right) of graphitic carbon nitride having a heptazine unit. In the modeled structure (A), one of the nitrogen atoms (labeled N97) is bonded to the -OH group and two carbon atoms of the C6N7 structure at the edge of the heptazine unit. The nitrogen atom in the pseudo-site not functionalized by the -OH group is labeled N123. In the modeled structure (B), one of the nitrogen atoms (labeled N128) is bonded to the -OH group and a proton. The nitrogen atom in the pseudo-site not functionalized by the -OH group and a proton is labeled N121. The occupied highest energy levels of both N97 and N128 shift to higher energy compared to the occupied highest energy level of the nitrogen atom in the pseudo-site not functionalized. This energy shift has a relatively large effect on the local electronic structure and narrows the band gap, as indicated by the red circle, shifting the absorption edge to a higher wavelength.

[0082] Although not wishing to be constrained by theory, the mechanism by which graphitic carbon nitride acquires a yellow color appearance through functionalization with oxygen-containing functional groups such as -N(O) and -OH groups is proposed through first-principles calculations using the Local Density Approximation (LDA).

[0083] [Manufacturing Method]

[0084] The present invention also relates to a method for producing graphitic carbon nitride according to the present invention.

[0085] Specifically, the present invention also relates to a method for producing graphitic carbon nitride of the present invention, comprising the following:

[0086] i) a step of preparing at least one precursor compound; and

[0087] ii) a step of heating at least one precursor compound at 450°C or higher for at least 1 minute.

[0088] Graphitic carbon nitride can be produced by heating at least one precursor compound of graphitic carbon nitride. As a raw material for the graphitic carbon nitride of the present invention, one precursor compound may be used, or two or more precursor compounds may be used in combination.

[0089] The precursor compound may be selected from precursors known to those skilled in the art, for example, from urea, thiourea, melamine, guanidine, arginine, cyanamide, dicyandiamide, and salts thereof, and combinations thereof (Chem. Rev. 2016, 116, 7159-7329, Ong, WJ; Tan, LL; Ng, YH; Yong, ST; Chai, SP, 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 thereof, and combinations thereof.

[0090] The salt of the precursor compound is not particularly limited, but examples include salts with carbonic acid and inorganic acids such as HalH (where Hal represents a halogen atom such as chloride (hydrochloric acid)).

[0091] In one preferred embodiment of the present invention, only one precursor compound is used as a raw material in the production of graphitic carbon nitride.

[0092] The temperature for heating at least one precursor compound is at least 450°C. Preferably, heating is performed at 500°C or higher, and more preferably at 525°C or higher.

[0093] The heating time of at least one precursor compound is at least 1 minute. Preferably, the heating time is at least 10 minutes, more preferably at least 20 minutes, and / or within 30 hours, more preferably within 25 hours.

[0094] Heating of the precursor compound may be performed 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, heating of the precursor compound is performed in air or in argon.

[0095] In one preferred embodiment, the heating process may be carried out in the presence of an oxygen-containing species, such as O2, water, O3, O atoms, and / or oxygen ions, as an oxidizing agent. Without being bound by theory, it is believed that when heating is carried out in the presence of an oxygen-containing species, a more porous graphitic carbon nitride can be obtained. In a preferred embodiment, heating is carried out in air, or in a noble gas or inert gas containing an oxygen-containing species.

[0096] In a preferred embodiment, in addition to oxygen in the air, the heating process is carried out in the presence of oxygen-containing species such as O2, moisture, ozone, O3, O atoms and / or oxygen ions as an oxidizing agent.

[0097] In a preferred embodiment, the heating process is carried out in the presence of an oxygen-containing species, which is O2, particularly an oxygen flux, and / or water. As specified herein, the term "oxygen flux" may mean an oxygen flow.

[0098] Preferably, the oxidizing agent used during the heating step is in gaseous form.

[0099] According to one embodiment, the oxygen source does not originate from permanganate or hydrogen peroxide.

[0100] In one embodiment of the present invention, the heating process comprises at least two heating steps at the same or different temperatures. Accordingly, in one embodiment, the heating process may comprise a first heating step of at least one minute at 450°C or higher for at least one precursor compound, and a second heating step of at least one minute at 450°C or higher for at least one precursor compound. 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 temperatures and times of the first and second heating steps are as described above.

[0101] In one embodiment of the present invention, a cooling step exists between the heating steps. Accordingly, 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 is cooled to, for example, room temperature (about 25°C). The time of the cooling step is not particularly limited, but is, for example, about 1 minute to 24 hours.

[0102] [Composition]

[0103] The present invention also relates to a composition comprising graphitic carbon nitride according to the present invention. Preferably, the composition according to the present invention is a cosmetic composition, in particular a cosmetic composition for keratinized materials such as skin. In one preferred embodiment, the composition according to the present invention is a sunscreen composition.

[0104] In addition, the composition according to the present invention can be used as a paint active ingredient, a pigment, a plastic filler, a cosmetic active ingredient, and / or a sunscreen such as a UV A and / or UV B absorber.

[0105] The composition according to the present invention preferably does not contain TiO2 or ZnO.

[0106] In another embodiment, the composition according to the present 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 may be used in the composition instead of TiO2 and ZnO, which are known as traditional inorganic UV filters.

[0107] Since the graphitic carbon nitride of the present invention can exhibit a white to yellow color appearance, the cosmetic composition according to the present invention can impart not only a desired colored and attractive appearance to keratin materials but also usefulness in color management.

[0108] [Treatment Method]

[0109] Another object of the present invention is a method for treating keratin materials, particularly human keratin materials such as skin, or keratin fibers such as hair, by applying at least one composition of the present invention, preferably a cosmetic composition, onto a keratin material as defined above.

[0110] Accordingly, the method or process according to the present invention may be a non-therapeutic cosmetic method or process for treating keratin substances.

[0111] Examples

[0112] The present invention will be explained in more detail by way of examples. However, these examples should not be interpreted as limiting the scope of the present invention.

[0113] [manufacturing]

[0114] The graphitic carbon nitride in powder form according to the present invention was prepared in the following Examples 1 to 10.

[0115] Example 1

[0116] 10g 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.

[0117] Example 2

[0118] 10g of urea powder as a precursor was heated in air at 550°C for 1 hour, and then subsequently heated in air at 600°C for 30 minutes to obtain graphitic carbon nitride according to Example 2.

[0119] Example 3

[0120] 10g of urea powder as a precursor compound was heated in air at 600°C for 2 hours to obtain graphitic carbon nitride according to Example 3.

[0121] Example 4

[0122] 10g of urea powder as a precursor was heated in air at 600°C for 2 hours, cooled to room temperature, and then heated in air at 600°C for 1 hour to obtain graphitic carbon nitride according to Example 4.

[0123] Example 5

[0124] 10g of urea powder as a precursor compound was subjected to a sequential process three times of (a) heating in air at 600°C for 1 hour and (b) cooling to room temperature to obtain graphitic carbon nitride according to Example 5.

[0125] Example 6

[0126] 10g of urea powder as a precursor compound was heated in air at 600°C for 2 hours and cooled to room temperature, and then subjected to a sequential process twice in which (a) it was heated in air at 600°C for 1 hour and (b) it was cooled to room temperature to obtain graphitic carbon nitride according to Example 6.

[0127] Example 7

[0128] 12g of urea powder as a precursor compound was subjected to a sequential process three times of (a) heating in air at 600°C for 1 hour and (b) cooling to room temperature to obtain graphitic carbon nitride according to Example 7.

[0129] Example 8

[0130] 10g of urea powder as a precursor compound was heated in air at 600–605°C for 2 hours to obtain graphitic carbon nitride according to Example 8.

[0131] Example 9

[0132] 3g of melamine powder as a precursor compound was heated in air at 550°C for 5 hours to obtain graphitic carbon nitride according to Example 9.

[0133] Example 10

[0134] 20g of guanidine carbonate powder as a precursor was heated in air at 600°C for 2 hours to obtain graphitic carbon nitride according to Example 10.

[0135] [evaluation]

[0136] (Crystal structure)

[0137] The crystal structure of each graphitic carbon nitride was characterized using X-ray diffraction (XRD) analysis. In the XRD pattern, the 13° peak was assigned to (100) of the graphitic carbon nitride having a heptazine unit, and the 27° peak was assigned to the (002) plane of the c-axis in the stacked sheet of graphitic carbon nitride. Fig. 1 shows the XRD pattern of graphitic carbon nitride according to Example 2 as a representative example.

[0138] According to XRD analysis of the graphitic carbon nitride of Examples 1 to 10, it was confirmed that each graphitic carbon nitride according to Examples 1 to 10 had a multilayer sheet of graphitic carbon nitride having heptazine units.

[0139] (Elemental composition analysis)

[0140] The elemental composition of each graphitic carbon nitride was estimated using CNHO elemental analysis based on the combustion of the sample.

[0141] (Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) Analysis)

[0142] TOF-SIMS analysis was performed to determine whether functional groups were present in each graphitic carbon nitride. TOF.SIMS 5 (ION-TOF GmbH, Germany) was used for the TOF-SIMS analysis. The investigated primary ions were 209 Bi3 ++ was.

[0143] TOF-SIMS spectrum of Example 2 (analysis area: 90,000 µm) 2 In ), OH - The intensity at m / z=17 attributed to ions was 1460, and NO - The intensity of m / z=30 attributable to was 92.

[0144] TOF-SIMS spectrum of Example 4 (analysis area: 90,000 µm) 2 In ), OH - The intensity at m / z=17 attributed to ions was 764, and NO - The intensity of m / z=30 attributable to was 59.

[0145] TOF-SIMS spectrum of Example 8 (analysis area: 40,000 µm) 2 In ), OH - The intensity at m / z=17 attributed to ions was 1195, and NO - The intensity of m / z=30 attributable to was 86.

[0146] TOF-SIMS spectrum of Example 9 (analysis area: 40,000 µm) 2 In ), OH - The intensity at m / z=17 attributed to ions was 1342, and NO - The intensity of m / z=30 attributable to was 88.

[0147] TOF-SIMS spectrum of Example 10 (analysis area: 40,000 µm) 2 In ), OH - The intensity at m / z=17 attributed to ions was 1671, and NO - The intensity of m / z=30 attributable to was 73.

[0148] According to TOF-SIMS analysis of the graphitic carbon nitrides of Examples 1 to 10, it was confirmed that each graphitic carbon nitride contained a nitroso group and a hydroxyl group.

[0149] (UV absorption characteristics and yellowness index)

[0150] The light absorption performance of each graphitic carbon nitride in the ultraviolet and visible light wavelength ranges was evaluated using ultraviolet-visible (UV-vis) diffuse reflection spectroscopy coupled with an integrating sphere (UV2500PC, Shimadzu Corporation).

[0151] The UV-vis absorption spectrum of an aqueous dispersion (medium: water) containing 0.1 wt% of each graphitic carbon nitride was collected using a UV-visible spectrophotometer (V750, Jasco Inc.) combined with an integrating sphere inside a fine quartz cell (two-sided transparent, 2 mm (path length) × 10 mm × H45 mm, Tokyo Garasu Kikai Co., Ltd.).

[0152] The onset absorption edge was estimated from the UV-vis diffuse reflection spectrum of each sample.

[0153] Figure 2 shows the absorption spectra obtained by measuring the UV-vis diffuse reflection of the synthesized powders of graphitic carbon nitride according to Examples 1 to 7. All graphitic carbon nitrides exhibited absorption in the UV range with wavelengths lower than 400 nm.

[0154] Figure 3 shows the absorption spectrum of a liquid sample in which graphitic carbon nitride according to Example 9 is suspended in water at 0.1 wt% as a representative example. The aqueous suspension exhibited absorption in the UV wavelength range lower than 400 nm.

[0155] 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 whiteness values ​​was performed using software from Shimadzu installed on the device, with light source C used as the standard light source and the viewing angle set to 10°. A BaSO4 standard white plate was used as the reference.

[0156] The results are summarized in Table 1 below. In addition, the relationship between the concentration of oxygen atoms (at.%) in graphitic carbon nitride and the onset absorption edge value is summarized in Figure 4 (a), and the relationship between the concentration of oxygen atoms (at.%) in graphitic carbon nitride and the measured yellowness index is summarized in Figure 4 (b).

[0157]

[0158] Table 1 and Figure 4 (a) show that as the amount of oxygen atoms increases, the onset absorption edge value of graphitic carbon nitride tends to increase.

[0159] In addition, the graph in Fig. 4(b) clearly shows that the higher the concentration (at.%) of oxygen atoms in the graphitic carbon nitride, the higher the yellowness index of the graphitic carbon nitride. This indicates that the higher the concentration of oxygen atoms in the graphitic carbon nitride, the more yellow the graphitic carbon nitride can appear.

[0160] Therefore, the graphitic carbon nitride according to the present invention has a very excellent effect in that it is possible to modify and design not only the UV absorption characteristics but also the desired color appearance by functionalizing the graphitic carbon nitride with oxygen-containing functional groups that are nitroso groups.

[0161] Therefore, it can be concluded that the graphitic carbon nitride of the present invention is highly useful as a UV absorber for various products, as it can impart desired coloring characteristics and an attractive appearance to the products. In particular, the graphitic carbon nitride of the present invention is highly useful as a UV absorber for cosmetic products, as it can impart a desired color tone to keratin materials such as skin, contributing to UV protection and enhanced color management.

Claims

Claim 1 Use of graphitic carbon nitride containing at least one oxygen atom, as an active ingredient in paints, as a pigment, particularly as a filler in plastics, or as an active ingredient in cosmetics. Claim 2 In claim 1, the use of graphitic carbon nitride as a cosmetic, preferably as a sunscreen. Claim 3 The use of graphitic carbon nitride as a UV A and / or UV B absorber in claim 1 or 2. Claim 4 Use of graphitic carbon nitride according to any one of claims 1 to 3, wherein the graphitic carbon nitride has, preferably, at least one heptazine unit having at least one hydroxyl group, a nitroso group, an N-oxide group, and / or an N-hydroxy(N-OH) group in its structure, and preferably at least one heptazine unit having at least one hydroxyl group and at least one nitroso group. Claim 5 In claim 4, the use of graphitic carbon nitride, wherein the heptazine unit is represented by formula (I), its salt and its solvate, e.g., hydrate: In Equation (I), R 1 , R 2 , and R 3 ...is identical or different and represents the following: i) a hydrogen atom; ii) a halogen atom; iii) an oxygen-containing group such as a carboxyl group, a nitro group, or a nitroso group; iv) a hydrocarbon chain containing 1 to 10 carbon atoms, which is saturated or unsaturated, acyclic linear or branched, and / or cyclic, aromatic or non-aromatic, wherein the hydrocarbon chain may potentially be interrupted by one or more heteroatoms such as O, S, N, or N(O); v) a hydroxyl group; vi) an amino R 4 R 5 N- (here, R 4 and R 5 is 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) (Here, R 1 and R 2 represents as previously defined);vii) R 4 R 5 N(O)- (here, R 4 and R 5 is identical or different, as previously defined); and viii) R 4 -N(O)- or (where, R 4 is as previously defined); however, it is understood as follows:- R 1 , R 2 , or R 3 At least one of the groups represents v) a hydroxyl group, and more preferably R 1 represents v) a hydroxyl group, and R 2 and R 3 iii) a nitroso group selected from vi) to viii), more preferably viii), which is identical or different, preferably identical, and represents one or more nitrogen atoms in the ring may be oxidized (N-oxide or N-OH). Claim 6 In Article 5, R 1 , R 2 , and R 3 is, identical or different, i) hydrogen, v) hydroxyl, vi) amino R 4 R 5 N-(here, R 4 and R 5 is identical or different, a hydrogen atom, or another monovalent heptazine group (II)(where, R 1 and R 2 represents (as previously defined); and viii) nitroso R 4 -N(O)-(where, R 4 represents an atom or group selected from (as previously defined), preferably R 1 , R 2 , or R 3 Use of graphitic carbon nitride, in which at least one of the groups v) represents a hydroxyl group. Claim 7 In claim 5 or 6, the heptazine unit is R as defined in claim 5 or 6. 1 , R 2 , and / or R 3 Having a continuous heptazine group (II) through any one of groups vi) to viii), particularly through group vi) or viii), preferably R 1 , R 2 , or R 3 Use of graphitic carbon nitride, in which at least one of the groups v) represents a hydroxyl group. Claim 8 Use of graphitic carbon nitride according to any one of claims 1 to 7, wherein 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% with respect to the total atomic weight of the graphitic carbon nitride. Claim 9 In any one of claims 1 to 8, the graphitic carbon nitride has a porous structure. Claim 10 In any one of claims 1 to 9, the graphitic carbon nitride has a yellowness index in the range of 5 to 50, preferably 10 to 45, more preferably 15 to 40, and the graphitic carbon nitride is used. Claim 11 In any one of claims 1 to 10, the graphitic carbon nitride has an onset absorption edge value in the range of 390 to 480 nm, preferably 400 to 450 nm, and the use of graphitic carbon nitride. Claim 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). Claim 13 A graphitic carbon nitride defined in any one of claims 1 to 12, wherein the graphitic carbon nitride has at least one heptazine unit in its structure. Claim 14 A graphitic carbon nitride defined in any one of claims 1 to 13, wherein the graphitic carbon nitride has, within its structure, at least one hydroxyl group and / or at least one nitroso group or N-oxide, and preferably at least one heptazine unit having at least one hydroxyl group and at least one nitroso group. Claim 15 A composition comprising graphitic carbon nitride and water and / or at least one organic medium as defined in any one of claims 1 to 14. Claim 16 A composition containing at least one type of graphitic carbon nitride as defined in any one of claims 1 to 15, preferably as a cosmetic, wherein the composition is preferably a sunscreen composition. Claim 17 A composition according to claim 15 or 16, comprising 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, and more preferably not comprising either TiO2 or ZnO. Claim 18 A method for producing graphitic carbon nitride as defined in any one of claims 12 to 14, wherein the method comprises: i) a step of preparing at least one precursor compound; and ii) a step of heating the at least one precursor compound at 450°C or higher for at least 1 minute; preferably, the heating step ii) is performed in the presence of an oxygen-containing species such as O2, water, O3, O atoms, and / or oxygen ions as an oxidizing agent; preferably, the oxidizing agent used during the heating step is in gaseous form; and more preferably, the oxygen-containing species does not originate from permanganate or hydrogen peroxide. Claim 19 A method for treating a keratin material, particularly a human keratin material such as skin, or a keratin fiber such as hair, by applying a composition of any one of claims 15 to 17 onto a keratin material.

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