Mildly ph-responsive supramolecular blackhead solubilizing compositions and methods of making same

Abstract

The present application relates to the field of skin cleaning products, in particular to a mild pH-responsive supramolecular blackhead-dissolving composition, a preparation method and application thereof, comprising an organic base, a lipid-soluble substance, a keratolytic agent and a porous material; the organic base at least comprises tromethamine; the lipid-soluble substance at least comprises a compound with an amide group and a carboxyl group; the keratolytic agent at least comprises a compound with a hydroxyl group and a carboxyl group; the hydroxyl group and the amino group of the tromethamine, the amide group and the carboxyl group of the lipid-soluble substance, and the hydroxyl group and the carboxyl group of the keratolytic agent jointly form a three-dimensional hydrogen bond network, thereby self-assembling to form a deep eutectic supramolecular substance; the deep eutectic supramolecular substance is distributed between layers and / or pores of the porous material. By using deep eutectic supramolecular technology, water-soluble tromethamine and keratolytic agent are co-assembled with water-insoluble lipid-soluble substances under a specific process, and through a strong three-dimensional hydrogen bond network between molecules, the originally water-insoluble lipid-soluble substances are clamped in the supramolecular inclusion body, achieving complete and uniform dissolution.

Description

[Technical Field]

[0001] This invention relates to the field of skin cleansing products, and more particularly to a mild pH-responsive supramolecular blackhead-dissolving composition and its preparation method. [Background Technology]

[0002] Blackheads and keratin plugs are formed by the oxidation of sebum secreted by sebaceous glands and shed keratin plugs that clog pores. Currently, the main mechanisms of action for blackhead removal products on the market fall into two categories: alkaline thrombolysis and strong acid exfoliation. Alkaline thrombolysis methods, such as blackhead removal solutions, rely on an alkaline system (pH typically 8-12) to forcefully dilate pores and induce a strong saponification reaction of sebum. Strong acid exfoliation methods, such as high-concentration fruit acids / salicylic acid, rely on the exfoliating effect of free acids, which usually require an extremely low pH (e.g., pH < 3.5) to ensure the free state and permeability of the acid.

[0003] Current mainstream blackhead removal products exhibit extreme pH levels, severely damaging the skin barrier. Alkaline blackhead removal products wash away the skin's slightly acidic sebum film, leading to irreversible loss of stratum corneum lipids and enlarged pores. Acidic blackhead removal products easily cause severe irritation such as erythema and peeling. Tromethamine and mandelic acid are water-soluble ingredients, while capryloyl glycine is poorly soluble in water. In traditional processes, adding capryloyl glycine to an aqueous system requires a large amount of surfactants or organic solvents for solubilization, which not only increases irritation but also easily causes crystallization at low temperatures, leading to formula instability. Existing technologies CN110494119A and CN110418633A's skin cleansers mainly contain tromethamine. To maintain the swelling activity of tromethamine against blackheads, the pH value needs to be between 8.0 and 12.5, which is incompatible with the slightly acidic physiological environment of human skin (pH 5.0 to 7.5). Long-term use can lead to skin microecological imbalance and lipid barrier damage. In order to balance exfoliation with a gentle pH level, the existing technology CN103857378A uses organic amines and specific acids, which form inactive salts that are difficult to dissociate, resulting in the loss of the swelling power of organic amines on keratin and the dissolving power of organic acids on intercellular lipids.

[0004] It is evident that existing tromethamine-based keratin plug dissolution methods have single-target limitations. Tromethamine, being a water-soluble molecule, lacks lipophilicity and struggles to penetrate the dense oxidized sebum film surrounding the keratin plug, resulting in low efficiency in directly dissolving keratin. Therefore, developing a keratin plug dissolution agent that can efficiently penetrate the sebum layer while gently targeting and dissolving the keratin plug structure, without surfactants and without disrupting the skin's microecology and barrier function, is of great significance for improving keratin plug problems. [Summary of the Invention]

[0005] Given that existing skin cleansers all use a single alkaline swelling or strong acid peeling method, it is difficult to break through the dense oxidized sebum film on the outer layer of keratin plugs and disrupt the skin's weakly acidic microecology and barrier function.

[0006] To address the above problems, the present invention provides a mild pH-responsive supramolecular blackhead-dissolving composition, comprising: Organic bases, fat-soluble substances, keratolytic agents, and porous materials; among them, The organic base includes at least tromethamine; The fat-soluble substances include at least compounds having amide and carboxyl groups; The keratin-removing agent includes at least compounds having hydroxyl and carboxyl groups; The hydroxyl and amino groups of the tromethamine, the amide and carboxyl groups of the lipid-soluble substance, and the hydroxyl and carboxyl groups of the keratolytic agent together form a three-dimensional hydrogen bond network, thereby self-assembling to form a deep eutectic supramolecular substance. The deep eutectic supramolecular material is distributed in the interlayer and / or pores of the porous material.

[0007] Preferably, the mass ratio of the organic base, the fat-soluble substance, the keratolytic agent, and the porous material is (5~40):(10~39.5):(5~20):(0.5~80).

[0008] Preferably, the organic base further includes at least one of methylglucosamine, arginine, and aminomethylpropanol; Alternatively, the fat-soluble substance includes at least one of capryloylglycine and undecenoylphenylalanine; Alternatively, the keratolytic agent may include at least one of mandelic acid, citric acid, succinic acid, lactic acid, malic acid, and tartaric acid.

[0009] Preferably, the porous material includes at least one of kaolin, volcanic mud, bentonite, white clay, and mesoporous silica.

[0010] On the other hand, the present invention provides a method for preparing a mildly pH-responsive supramolecular blackhead-dissolving composition, the preparation method comprising the following steps: S100: An organic base, a fat-soluble substance, and a keratolytic agent are placed in a reaction vessel and mixed. The mixture is heated and stirred at a first temperature condition, thereby causing the hydroxyl and amino groups of the organic base, the amide and carboxyl groups of the fat-soluble substance, and the hydroxyl and carboxyl groups of the keratolytic agent to form a three-dimensional hydrogen bond network, which self-assembles to form a deep eutectic supramolecular liquid; wherein the organic base includes at least tromethamine. S200: The deep eutectic supramolecular liquid is mixed with a porous material to obtain an initial mixture; S300: The initial mixture is aged and shaped so that the deep eutectic supramolecular liquid enters the interlayer and / or voids of the porous material through capillary action to obtain a supramolecular blackhead dissolving composition.

[0011] Preferably, the mass ratio of the organic base, the fat-soluble substance, the keratolytic agent, and the porous material is (5~40):(10~39.5):(5~20):(0.5~80).

[0012] Preferably, the organic base further includes at least one of methylglucosamine, arginine, and aminomethylpropanol; Alternatively, the fat-soluble substance includes at least one of capryloylglycine and undecenoylphenylalanine; Alternatively, the keratolytic agent may include at least one of mandelic acid, citric acid, succinic acid, lactic acid, malic acid, and tartaric acid.

[0013] Preferably, in S100, the first temperature condition is a temperature range of 70°C to 150°C; Alternatively, in S200, the deep eutectic supramolecular liquid is mixed with a porous material to obtain an initial mixture, specifically: The porous material is placed in a mixer, and while the porous material is being stirred, the deep eutectic supramolecular liquid is added to the porous material to obtain an initial mixture.

[0014] Preferably, after S300, the following is also included: The supramolecular blackhead-dissolving composition is ground and sieved. When the pH value of a 10% aqueous solution of the supramolecular blackhead-dissolving composition is detected to be between 4.0 and 8.0, the supramolecular blackhead-dissolving composition is confirmed to be qualified.

[0015] The present invention also provides the application of the above-described mild pH-responsive supramolecular blackhead-dissolving composition or the supramolecular blackhead-dissolving composition obtained by the above-described mild pH-responsive supramolecular blackhead-dissolving composition preparation method in cosmetics or topical skin preparations.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The mild pH-responsive supramolecular blackhead-dissolving composition and its preparation method of the present invention include an organic base, a lipid-soluble substance, a keratolytic agent, and a porous material; the organic base includes at least glycerol; the lipid-soluble substance includes at least a compound having amide and carboxyl groups; the keratolytic agent includes at least a compound having hydroxyl and carboxyl groups; the hydroxyl and amino groups of glycerol, the amide and carboxyl groups of the lipid-soluble substance, and the hydroxyl and carboxyl groups of the keratolytic agent together form a three-dimensional hydrogen bond network, thereby self-assembling to form a deep eutectic supramolecular substance; the deep eutectic supramolecular substance is distributed in the interlayer and / or pores of the porous material. Using deep eutectic supramolecular technology, water-soluble glycerol and the keratolytic agent are co-assembled with water-insoluble lipid-soluble substances under specific processes. Through a strong three-dimensional hydrogen bond network between molecules, the originally water-insoluble lipid-soluble substance is bound within the supramolecular inclusions, achieving thorough and uniform dissolution without the need for additional emulsifiers.

[0017] The mild pH-responsive supramolecular blackhead-dissolving composition and its preparation method of the present invention have the following advantages: First, the supramolecular blackhead-dissolving composition of the present invention overcomes the technical bottleneck of oil-soluble substances being insoluble in water, and breaks the limitation of traditional blackhead removal products that must rely on a highly alkaline (pH value of 8~12) or strongly acidic environment. It can achieve targeted thrombolysis within a pH range close to the physiological pH of human skin (pH value of 4~8), thus preventing damage to the skin barrier and acid-base stimulation.

[0018] Secondly, this invention can achieve highly efficient thrombolysis with a wide pH response. The resulting supramolecular structure has a unique acid-base buffering capacity and high permeability. Unlike blackhead removal products on the market that rely on strong alkalinity to open pores, this supramolecular structure can automatically penetrate and fuse with lipid-rich blackheads through its lipophilic network in an extremely mild and skin-friendly environment with a pH of 4 to 8, achieving targeted dissolution. The formula system does not require a large amount of surfactants, is clear and stable, and does not precipitate at low temperatures.

[0019] Third, this invention introduces porous mud as a physical carrier. Porous mud has excellent sebum adsorption and ion exchange capacity, which is used to carry the supramolecular thrombolytic complex. When it comes into contact with the skin, the porous mud absorbs the waste oil floating on the surface of the pores like a sponge, while releasing the supramolecular thrombolytic complex in the pores into the depths of the pores, forming a perfect closed loop of "external oil absorption and internal thrombolysis". Its strong physical oil absorption and supramolecular deep chemical dissolving power work synergistically, and the blackhead removal rate is far greater than that of single chemical acid or alkali or single cleansing mud. [Attached Image Description]

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein: Figure 1 It is a component of the mild pH-responsive supramolecular blackhead-dissolving composition provided by the present invention.

[0021] Figure 2 This is a flowchart of a method for preparing a mildly pH-responsive supramolecular blackhead-dissolving composition provided by the present invention.

[0022] Figure 3 This is the 1H Fourier transform infrared spectrum of tromethamine.

[0023] Figure 4 This is the 1H Fourier transform infrared spectrum of capryloylglycine.

[0024] Figure 5 This is the 1H Fourier transform infrared spectrum of mandelic acid.

[0025] Figure 6 This is the Fourier transform infrared (FTIR) hydrogen spectrum of the supramolecular blackhead-dissolving composition corresponding to Example 1 of the present invention.

[0026] Figure 7 This is the Fourier transform infrared hydrogen spectrum of the physical mixture corresponding to Comparative Example 1 of the present invention.

Detailed Implementation Methods

[0027] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only for explaining the present invention and not for limiting the present invention. Furthermore, it should be noted that, for ease of description, only the parts related to the present invention are shown in the accompanying drawings, not all structures. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of the present invention.

[0028] The terms "comprising" and "having," and any variations thereof, used in this invention are intended to cover non-exclusive inclusion. For example, a process, method, product, or apparatus that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or units inherent to such process, method, product, or apparatus.

[0029] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0030] Please see Figure 1 As shown, the present invention provides a mild pH-responsive supramolecular blackhead-dissolving composition, the mild pH-responsive supramolecular blackhead-dissolving composition comprising: Organic bases, fat-soluble substances, keratolytic agents, and porous materials; among them, Organic bases include at least tromethamine; Lipid-soluble substances include at least compounds having amide and carboxyl groups; Keratin exfoliants include at least compounds having hydroxyl and carboxyl groups; The hydroxyl and amino groups of tromethamine, the amide and carboxyl groups of lipid-soluble substances, and the hydroxyl and carboxyl groups of keratolytic agents together form a three-dimensional hydrogen bond network, thereby self-assembling to form deep eutectic supramolecular substances. Deep eutectic supramolecular substances are distributed in the interlayer and / or pores of porous materials.

[0031] Furthermore, the mass ratio of organic alkali, fat-soluble substance, keratolytic agent, and porous material is (5~40):(10~39.5):(5~20):(0.5~80).

[0032] Furthermore, the organic base also includes at least one of methylglucosamine, arginine, and aminomethylpropanol; Alternatively, the fat-soluble substances include at least one of capryloylglycine and undecenoylphenylalanine; Alternatively, the exfoliating agent may include at least one of mandelic acid, citric acid, succinic acid, lactic acid, malic acid, and tartaric acid.

[0033] Furthermore, the porous material includes at least one of kaolin, volcanic mud, bentonite, white clay, and mesoporous silica.

[0034] Please see Figure 2 As shown, the present invention provides a method for preparing a mild pH-responsive supramolecular blackhead-dissolving composition, the method comprising the following steps: S100: An organic base, a fat-soluble substance, and a keratinizing agent are placed in a reaction vessel and mixed. The mixture is heated and stirred at a first temperature condition, so that the hydroxyl and amino groups of the organic base, the amide and carboxyl groups of the fat-soluble substance, and the hydroxyl and carboxyl groups of the keratinizing agent together form a three-dimensional hydrogen bond network, which self-assembles to form a deep eutectic supramolecular liquid; wherein, the organic base includes at least tromethamine. S200: The deep eutectic supramolecular liquid is mixed with a porous material to obtain an initial mixture; S300: The initial mixture is matured and shaped so that the deep eutectic supramolecular liquid enters the interlayers and / or pores of the porous material through capillary action, resulting in a supramolecular blackhead-dissolving composition. For example, the above-mentioned deep eutectic supramolecular liquid is continuously stirred for 1 to 3 hours. During stirring, the deep eutectic supramolecular liquid enters the interlayers and / or pores of the porous mud through capillary forces.

[0035] It is understandable that tromethamine has a dense network of hydroxyl (-OH) and amino (-NH2) groups, fat-soluble substances (such as capryloyl glycine) have amide (-NH-CO-) and carboxyl (-COOH) groups, and keratolytic agents (such as organic acids) have hydroxyl (-OH) and carboxyl (-COOH) groups. These groups form an extremely complex three-dimensional hydrogen bond network (such as -OH···O=C-).

[0036] When a lipid-soluble substance contains capryloylglycine and a keratolytic agent contains mandelic acid (i.e., almond acid), the long carbon chain of capryloylglycine (i.e., capryloyl group) and the benzene ring of mandelic acid are both highly hydrophobic. In water, the hydrophobic forces force the above-mentioned hydrophobic groups to fold inward and cluster together, while the large number of hydrophilic hydroxyl groups of tromethamine itself are broken and turned towards the external aqueous phase, thus forming the dynamics of "molecular cabins" and completely changing the hydration dynamics of the original substance.

[0037] Furthermore, when the carbon chain (-CH2-) of capryloylglycine and the benzene ring of mandelic acid approach each other inside the molecular compartment, CH-π interactions and π-π stacking occur, thereby increasing the affinity for keratin plugs.

[0038] Furthermore, the mass ratio of organic alkali, fat-soluble substance, keratolytic agent, and porous material is (5~40):(10~39.5):(5~20):(0.5~80).

[0039] Furthermore, the organic base also includes at least one of methylglucosamine, arginine, and aminomethylpropanol; Alternatively, the fat-soluble substances include at least one of capryloylglycine and undecenoylphenylalanine; Alternatively, the exfoliating agent may include at least one of mandelic acid, citric acid, succinic acid, lactic acid, malic acid, and tartaric acid.

[0040] Furthermore, in S100, the first temperature condition is a temperature range of 70°C to 150°C; Alternatively, in S200, the deep eutectic supramolecular liquid is mixed with a porous material to obtain an initial mixture, specifically: A porous material is placed in a mixer, and a deep eutectic supramolecular liquid is added to the porous material while it is being stirred to obtain an initial mixture. For example, the porous material is placed in a mixer equipped with a high-shear or spraying device, and the aforementioned deep eutectic supramolecular liquid is slowly added dropwise or sprayed into the porous powder while it is being stirred.

[0041] Furthermore, following the S300, it also includes: The supramolecular blackhead-dissolving composition is ground and sieved. When the pH value of a 10% aqueous solution of the supramolecular blackhead-dissolving composition is detected to be between 4.0 and 8.0, the supramolecular blackhead-dissolving composition is considered qualified. For example, the above supramolecular blackhead-dissolving composition is ground and sieved (e.g., through a 100-200 mesh sieve), and the pH value of a 10% aqueous solution of the supramolecular blackhead-dissolving composition is tested to see if it is between 4.0 and 8.0. If so, the powdered or slightly damp sand-like supramolecular blackhead-dissolving composition is used as the final product.

[0042] The present invention provides the following Example 1 and Comparative Examples 1-3 for comparison, and the specific schemes are as follows: Example 1: A mild pH-responsive supramolecular blackhead-dissolving composition is provided, with the following mass ratio components: Tromethamine: Capryloylglycine: Mandelic acid: Mesoporous silica = 20g: 13.5g: 10.5g: 55g Accordingly, the mild pH-responsive supramolecular blackhead-dissolving composition of Example 1 is prepared as follows: The components of tromethamine, capryloyl glycine, and mandelic acid in the above-mentioned mass ratio were placed in a reaction vessel and heated at 80°C for 45 min to form a homogeneous and transparent deep eutectic supramolecular liquid. This deep eutectic supramolecular liquid was sprayed into 55 g of mesoporous silica (porous mud) and stirred in a mixer for 2 h. The mixture was then sieved to obtain 100 g of powdered microparticles as the initial mixture (i.e., the raw material for the supramolecular blackhead-dissolving composition). 20 g of the initial mixture was dissolved in 80 g of deionized water to obtain the test aqueous solution corresponding to Example 1, and the pH was adjusted to 5.8.

[0043] Comparative Example 1: A composition is provided that is a conventionally physically mixed composition without supramolecular treatment, and its mass ratio components are as follows: Tromethamine: Capryloylglycine: Mandelic acid: Mesoporous silica = 20g: 13.5g: 10.5g: 55g Accordingly, the preparation method of the composition of Comparative Example 1, which is a conventional physical mixture without supramolecular treatment, is as follows: The components of tromethamine, capryloyl glycine, and mandelic acid in the above mass ratio were physically mixed in a reaction vessel (without heating, melting, or stirring) to obtain a conventional physical mixture. This conventional physical mixture was then sprayed into 55g of mesoporous silica (porous mud) and stirred in a mixer for 2 hours. The mixture was then sieved to obtain 100g of a powdered conventional composition. 20g of this conventional composition was dissolved in 80g of deionized water to obtain the test aqueous solution corresponding to Comparative Example 1. The pH value of the test aqueous solution of Comparative Example 1 was measured to be 5.8. Because capryloyl glycine in the formulation was insoluble, there was a noticeable floating particle texture, and a large amount of crystals precipitated under low-temperature conditions.

[0044] Comparative Example 2: A test aqueous solution of a traditional high-alkaline blackhead removal solution formula is provided, which adopts the basic formula of commercially available blackhead removal solution (the main components are triethanolamine and a strong surfactant), and the pH value is adjusted to 9.5.

[0045] Comparative Example 3: A test aqueous solution with a traditional strong acid formulation was provided, which used only 13.5g of mandelic acid dissolved in 86.5g of deionized water, without the addition of tromethamine and capryloylglycine, and the pH was adjusted to 3.0.

[0046] The solubility and formulation stability of the test aqueous solution of Example 1 and Comparative Example 1 were tested below. The specific process is as follows: The test aqueous solutions of Example 1 and Comparative Example 1 were placed in a 4°C refrigerator environment and a 45°C incubator environment, respectively, for a one-month heat and cold resistance test.

[0047] The test results are as follows: The test aqueous solution of Example 1 contained porous mud precipitate, with no crystallization (the supramolecular network firmly locked capryloylglycine); the test aqueous solution of Comparative Example 1 contained porous mud precipitate, and a large number of needle-like crystals (i.e., capryloylglycine precipitation) appeared on the third day after being placed in a 4°C refrigerator environment.

[0048] The following is a detailed in vitro blackhead plug dissolution test (i.e., wide pH response verification) of the test aqueous solutions of Example 1, Comparative Example 2, and Comparative Example 3. Real hard keratin plugs were collected from the nasal cavity of volunteers and immersed in test aqueous solutions of Example 1 (pH 5.8), Comparative Example 2 (pH 9.5), and Comparative Example 3 (pH 3.0), respectively. The dissolution was observed under a microscope after 2 hours.

[0049] The test results are as follows: In the test aqueous solution of Example 1, the keratin plug structure was completely loosened, the lipid shell was emulsified and dissolved by supramolecular inclusions, and the volume of the keratin plug structure was reduced by more than 85%. In the test aqueous solution (strongly alkaline) of Comparative Example 2, the keratin plug structure swelled and loosened, with a solubility of approximately 70%. In the test aqueous solution (strongly acidic) of Comparative Example 3, only a small portion of the keratin plug structure at the edges dissolved, with a solubility of approximately 30%. It is evident that the supramolecular blackhead-dissolving composition of the present invention, under a mild environment with a pH of 5.8, has a thrombolytic effect that far exceeds that of traditional free acids (Comparative Example 3) and also surpasses that of highly alkaline environments (Comparative Example 2), which are extremely damaging to the skin.

[0050] The transdermal water loss rate (TEWL) test (i.e., barrier damage / irritation evaluation) was performed on the test aqueous solutions of Example 1, Comparative Example 2, and Comparative Example 3. The specific process is as follows: Thirty volunteers used the sample in different areas, applying it for 15 minutes each time. The transdermal water loss rate was tested immediately after washing and 24 hours later (the higher the transdermal water loss rate, the more severe the skin barrier damage).

[0051] The test results are as follows: For the test aqueous solution used in Example 1, there was no significant change in transdermal water loss rate, the skin barrier remained intact and there was no redness; For the test aqueous solution used in Comparative Example 2, the transdermal water loss rate increased by 42% immediately after washing, and the skin experienced tightness, dryness, and slight redness. For the test aqueous solution used in Comparative Example 3, the transdermal water loss rate increased by 28% 24 hours after washing, accompanied by stinging and peeling reactions. It is evident that the supramolecular blackhead-dissolving composition of the present invention perfectly solves the serious defect of traditional blackhead removal products that sacrifice the skin barrier in pursuit of effectiveness.

[0052] Please see Figures 3-5 The corresponding Fourier transform infrared (FTIR) spectra of tromethamine, octanoyl glycine, and mandelic acid are 1H NMR; among them, Figure 3 At 3000cm -1 ~3500cm -1 The wavenumber range corresponds to the characteristic peak regions of amino and hydroxyl groups; Figure 4 At 1700cm -1 The wavenumber ranges around the left and right correspond to sharp, strong absorption peaks of free carboxyl carbonyl groups (C=0) and amide bonds; Figure 5 At 1700cm -1 The wavenumber ranges to the left and right correspond to the sharp, strong absorption peak of the free carboxyl carbonyl group (C=0) and the broad hydroxyl association peak to its left.

[0053] contrast Figure 6 and Figure 7It can be determined whether the supramolecular blackhead-dissolving composition prepared in this invention (corresponding to Example 1 above) undergoes chemical bonding / supramolecular reconstruction compared to the composition of conventional physical mixing without supramolecular treatment (corresponding to Comparative Example 1 above). Specifically, from Figure 7 As can be seen, its Fourier transform infrared hydrogen spectrum is basically as described above. Figures 3-5 The linear superposition of the three components, tromethamine, capryloyl glycine, and mandelic acid, are relatively independent, especially at a wavenumber of 1700 cm⁻¹. -1 The absorption peak of the nearby free carboxyl group remains sharp and prominent, and the peak at 3300 cm⁻¹ to its left is also significant. -1 The nearby peaks also retain their original spiky, pointed shape. From Figure 6 It can be seen that its Fourier transform infrared hydrogen spectrum is compared to Figure 7 A decisive variation in infrared signature occurred, specifically as follows: at wavenumber 1700 cm⁻¹ -1 The strong peak of the nearby free carboxyl group decreased sharply / disappeared and shifted to lower frequencies, proving that the carboxyl groups of capryloylglycine and mandelic acid had transferred protons to tromethamine to form a carboxylate (-COO-) base structure; at a wavenumber of 3000 cm⁻¹ -1 ~3500cm -1 The regions completely merged into a flat, wide "bundle," and the original free peaks disappeared, proving the formation of an extremely high-density three-dimensional hydrogen bond network within the system. In summary, Example 1 of this invention forms a supramolecular substance, while Comparative Example 1 above forms a salt.

[0054] The present invention also provides the application of the above-described mild pH-responsive supramolecular blackhead-dissolving composition or the supramolecular blackhead-dissolving composition obtained by the above-described mild pH-responsive supramolecular blackhead-dissolving composition preparation method in cosmetics or topical skin preparations.

[0055] Furthermore, the aforementioned cosmetics or topical skin preparations are preparations for removing blackheads, clearing pores, exfoliating, or treating acne.

[0056] Furthermore, the above-mentioned preparations are aqueous solutions, serums, gels, lotions, creams, sheet masks, mud masks, cleansing creams, cleansing mousses, or cleansing honeys.

[0057] Furthermore, the above-mentioned multi-component supramolecular keratin plug dissolving agent accounts for 0.5% to 20.0% of the mass of the above-mentioned cosmetic or topical skin preparation.

[0058] Through the above description of the embodiments, those skilled in the art can clearly understand that each embodiment can be implemented by means of a necessary general-purpose hardware platform, or by a combination of hardware and software. Based on this understanding, the above technical solutions, in essence or the part that contributes to the prior art, can be embodied in the form of a computer product. The present invention can take the form of a computer program product implemented on one or more computer-usable storage media (including but not limited to disk storage, CD-ROM, optical storage, etc.) containing computer-usable program code.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Other embodiments may also be used. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A mild pH-responsive supramolecular blackhead-dissolving composition, characterized in that, include: Organic bases, fat-soluble substances, keratolytic agents, and porous materials; among them, The organic base includes at least tromethamine; The fat-soluble substances include at least compounds having amide and carboxyl groups; The keratin-removing agent includes at least compounds having hydroxyl and carboxyl groups; The hydroxyl and amino groups of the tromethamine, the amide and carboxyl groups of the lipid-soluble substance, and the hydroxyl and carboxyl groups of the keratolytic agent together form a three-dimensional hydrogen bond network, thereby self-assembling to form a deep eutectic supramolecular substance. The deep eutectic supramolecular material is distributed in the interlayer and / or pores of the porous material.

2. The mild pH-responsive supramolecular blackhead-dissolving composition according to claim 1, characterized in that, The mass ratio of the organic base, the fat-soluble substance, the keratinizing agent, and the porous material is (5~40):(10~39.5):(5~20):(0.5~80).

3. The mild pH-responsive supramolecular blackhead-dissolving composition according to claim 1, characterized in that, The organic base also includes at least one of methylglucosamine, arginine, and aminomethylpropanol; Alternatively, the fat-soluble substance includes at least one of capryloylglycine and undecenoylphenylalanine; Alternatively, the keratolytic agent may include at least one of mandelic acid, citric acid, succinic acid, lactic acid, malic acid, and tartaric acid.

4. The mild pH-responsive supramolecular blackhead-dissolving composition according to claim 1, characterized in that, The porous material includes at least one of kaolin, volcanic mud, bentonite, white clay, and mesoporous silica.

5. A method for preparing a mildly pH-responsive supramolecular blackhead-dissolving composition, characterized in that, The preparation method includes the following steps: S100: An organic base, a fat-soluble substance, and a keratolytic agent are placed in a reaction vessel and mixed. The mixture is heated and stirred at a first temperature condition, thereby causing the hydroxyl and amino groups of the organic base, the amide and carboxyl groups of the fat-soluble substance, and the hydroxyl and carboxyl groups of the keratolytic agent to form a three-dimensional hydrogen bond network, which self-assembles to form a deep eutectic supramolecular liquid; wherein the organic base includes at least tromethamine. S200: The deep eutectic supramolecular liquid is mixed with a porous material to obtain an initial mixture; S300: The initial mixture is aged and shaped so that the deep eutectic supramolecular liquid enters the interlayer and / or voids of the porous material through capillary action to obtain a supramolecular blackhead dissolving composition.

6. The preparation method according to claim 5, characterized in that, The mass ratio of the organic base, the fat-soluble substance, the keratinizing agent, and the porous material is (5~40):(10~39.5):(5~20):(0.5~80).

7. The preparation method according to claim 6, characterized in that, The organic base also includes at least one of methylglucosamine, arginine, and aminomethylpropanol; Alternatively, the fat-soluble substance includes at least one of capryloylglycine and undecenoylphenylalanine; Alternatively, the keratolytic agent may include at least one of mandelic acid, citric acid, succinic acid, lactic acid, malic acid, and tartaric acid.

8. The preparation method according to claim 7, characterized in that, In S100, the first temperature condition is a temperature range of 70°C to 150°C; Alternatively, in S200, the deep eutectic supramolecular liquid is mixed with a porous material to obtain an initial mixture, specifically: The porous material is placed in a mixer, and while the porous material is being stirred, the deep eutectic supramolecular liquid is added to the porous material to obtain an initial mixture.

9. The preparation method according to claim 8, characterized in that, Following the S300, it also includes: The supramolecular blackhead-dissolving composition is ground and sieved. When the pH value of a 10% aqueous solution of the supramolecular blackhead-dissolving composition is detected to be between 4.0 and 8.0, the supramolecular blackhead-dissolving composition is confirmed to be qualified.

10. The use of the mild pH-responsive supramolecular blackhead-dissolving composition according to any one of claims 1-4 or the supramolecular blackhead-dissolving composition according to any one of claims 5-9 in cosmetics or topical skin preparations.

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