A composition containing aluminum zirconium tetrapropanediol glycerine GLY complex and bacteriostatic deodorant antiperspirant and its application
By combining tetrachlorohydroxyaluminum zirconium (GLY) coordination compound with cetrimonium bromide, adding ingredients such as peony root bark extract, and using modified microcarriers, the shortcomings of existing antiperspirants in inhibiting body odor are overcome, achieving significant antibacterial, deodorizing, and antiperspirant effects.
Patent Information
- Application Number
- CN202411119569.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-14
- Publication Date
- 2025-11-18
- Estimated Expiration
- 2044-08-14
AI Technical Summary
Existing antiperspirants such as aluminum zirconium glycinate have limited effectiveness in suppressing body odor and cannot effectively prevent the decomposition of sweat by bacteria, which can lead to bromhidrosis or other body odor problems.
A combination of tetrachlorohydroxyaluminum zirconium (GLY) coordination compound and cetrimonium bromide was prepared by adding ingredients such as peony root bark extract, glyceryl glucoside, and oat β-glucan, extracting active substances through ultrasonication and alkaline amino acid enrichment precipitation technology, and using modified three-dimensional ordered macroporous metal-organic framework material as microcarrier to enrich the active substances, thus preparing an antibacterial, deodorizing and antiperspirant composition.
It significantly improves antiperspirant effects, reduces body odor, inhibits bacterial growth, and provides an effective solution for the treatment and deodorizing antiperspirant products for patients with hyperhidrosis.
Smart Images

Figure BDA0004995125760000171 
Figure BDA0004995125760000181 
Figure BDA0004995125760000182
Abstract
Description
Technical Field
[0001] This invention belongs to the field of daily chemical products technology, specifically, it relates to a composition containing tetrachlorohydroxyaluminum zirconium (GLY) coordination compound that has antibacterial, deodorizing and antiperspirant properties, and its application. Background Technology
[0002] Sweat secretion, controlled by temperature and emotions, is a crucial physiological function for maintaining and regulating body temperature and promotes metabolism, playing a vital role in maintaining human health. However, due to physiological reasons, some people have overactive sweat glands, making them prone to hyperhidrosis. They easily sweat profusely in slightly warm environments, under stress, or during mild exercise. In the hot summer, the decomposition of sweat by bacteria can cause body odor or body odor. All these inconveniences often cause embarrassment and affect normal social interactions and work.
[0003] ACH, Chinese name: Aluminum hydroxyl chloride, English name: Aluminum Chlorohydrate, molecular formula: Al2(OH)5Cl x •nH₂O. It is an inorganic polymer compound with a basicity (basicity) higher than polyaluminum chloride, second only to aluminum hydroxide. It undergoes cross-linking polymerization via hydroxyl groups, resulting in the highest number of hydroxyl groups in its molecule. It is a white powdery solid, and its solution is a colorless, transparent liquid. It has strong cross-linking adsorption properties, is readily soluble in water, and its hydrolysis is accompanied by physicochemical processes such as electrochemical processes, coagulation, adsorption, and precipitation.
[0004] In 1960, the commonly used ACH was modified by adding zirconium salts, along with a certain amount of glycine to further reduce irritation, resulting in glycine aluminum zirconium antiperspirant. Application results showed that glycine aluminum zirconium was much more effective at stopping sweat than ACH. However, even so, the antiperspirant effect of glycine aluminum zirconium remained limited, and it still could not prevent the social problems caused by the decomposition of sweat by bacteria, leading to body odor or sweat smell. Summary of the Invention
[0005] The purpose of this invention is to overcome the problems existing in the prior art and provide a composition containing tetrachlorohydroxyaluminum zirconium (GLY) coordination compound that has antibacterial, deodorizing, and antiperspirant properties, as well as its application. The composition provided by this invention not only has antiperspirant effects but also antibacterial efficacy.
[0006] The objective of this invention and the technical problem it solves are achieved by the following technical solutions.
[0007] In a first aspect, a composition containing tetrachlorohydroxyaluminum zirconium GLY coordination compound and possessing antibacterial, deodorizing, and antiperspirant properties is provided. The composition comprises, by weight percentage, the following components in the following amounts: 5-15% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.05-0.15% cetrimonium bromide, 0.1-0.5% peony root bark extract, 2-5% glyceryl glucoside, 1-5% oat β-glucan, 1-2% PEG-40 hydrogenated castor oil, 0.5-1% fragrance, 0.5-1.5% citric acid, and the balance being water.
[0008] As an alternative embodiment of the composition described in the first aspect, the peony root bark extract is prepared according to the following steps:
[0009] The dried root bark of peony is crushed, ground, and then passed through a 100-200 mesh sieve to obtain peony root bark powder;
[0010] The peony root bark powder and extraction solvent were mixed at a mass-volume ratio of 1g:20-40mL and ultrasonicated. Then, the mixture was soaked for 4-10 hours. Finally, the distillate was collected by reflux in a water bath to obtain the crude extract.
[0011] Add an alkaline amino acid / ethanol mixture to the crude extract at a volume ratio of 1:20-30 and stir continuously at 40-60℃ for 1-5 hours. After standing for 18-24 hours, filter and collect the precipitate. Freeze-dry the precipitate under vacuum to obtain the peony root bark extract.
[0012] As an alternative embodiment of the composition described in the first aspect, the extraction solvent is a mixture of ethanol, chloroform, and water in a volume ratio of 1:0.5:10-30.
[0013] As an alternative embodiment of the composition described in the first aspect, the ultrasonic conditions are: frequency 80-120 kHz, ultrasonic time 40-60 min.
[0014] As an alternative embodiment of the composition described in the first aspect, the basic amino acid is selected from any one of lysine, arginine, and histidine.
[0015] As an alternative embodiment of the composition described in the first aspect, the alkaline amino acid / ethanol mixture is prepared by mixing alkaline amino acids and a 75% ethanol solution at a mass-volume ratio of 1g:50-150mL.
[0016] In a second aspect, a method for preparing a composition is provided, characterized in that the preparation method includes the following steps:
[0017] Preparation of peony root bark extract:
[0018] The dried root bark of peony is crushed, ground, and then passed through a 100-200 mesh sieve to obtain peony root bark powder;
[0019] The peony root bark powder and extraction solvent were mixed at a mass-volume ratio of 1g:20-40mL and ultrasonicated. Then, the mixture was soaked for 4-10 hours. Finally, the distillate was collected by reflux in a water bath to obtain the crude extract.
[0020] Add an alkaline amino acid / ethanol mixture to the crude extract at a volume ratio of 1:20-30 and stir continuously at 40-60℃ for 1-5 hours. After standing for 18-24 hours, filter and collect the precipitate. Vacuum freeze-dry the precipitate to obtain peony root bark extract.
[0021] Weigh the following raw materials according to weight percentage: 5-15% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.05-0.15% cetrimonium bromide, 0.1-0.5% peony root bark extract, 2-5% glyceryl glucoside, 1-5% oat β-glucan, 1-2% PEG-40 hydrogenated castor oil, 0.5-1% fragrance, 0.5-1.5% citric acid, and the balance being water;
[0022] First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound were stirred until completely dissolved in water. Then, citric acid was added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan were added in sequence and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance were added and stirred until completely homogeneous to obtain the composition.
[0023] As an optional embodiment of the preparation method described in the second aspect, the extraction solvent is a mixture of ethanol, chloroform, and water in a volume ratio of 1:0.5:10-30.
[0024] As an optional embodiment of the preparation method described in the second aspect, the ultrasonic conditions are: frequency 80-120kHz, ultrasonic time 40-60min.
[0025] As an optional embodiment of the preparation method described in the second aspect, the alkaline amino acid / ethanol mixture is prepared by mixing alkaline amino acids and a 75% ethanol solution at a mass-volume ratio of 1g:50-150mL.
[0026] As an optional embodiment of the preparation method described in the second aspect, the basic amino acid is selected from any one of lysine, arginine, and histidine.
[0027] By employing the above technical solution, the present invention has at least the following advantages:
[0028] 1. Tetrachlorohydroxyaluminum zirconium (THZ) GLY coordination compound is a common antiperspirant active ingredient with low skin irritation and is one of the metal salts with the best antiperspirant effect. Cetrimonium bromide is a white or light yellow crystalline to powdery substance, readily soluble in isopropanol and water, producing a large amount of foam upon shaking. It has good compatibility with cationic, nonionic, and amphoteric surfactants. It possesses excellent penetration, softening, emulsification, antistatic, biodegradability, and bactericidal properties. However, using THZ alone will limit its antiperspirant effect, and excessive sweating can promote bacterial growth and produce odor. Based on the above, this invention provides a composition containing THZ GLY coordination compound that is antibacterial, deodorizing, and antiperspirant, and its application. This antibacterial, deodorizing, and antiperspirant composition uses THZ and cetrimonium bromide as the main active ingredients. During the experimental process, this invention unexpectedly discovered that combining tetrachlorohydroxyzirconium GLY coordination compound with cetrimonium bromide not only synergistically reduces body odor, but also that cetrimonium bromide inhibits bacterial growth, thus reducing odor production. Verification showed that the combined use of tetrachlorohydroxyzirconium GLY coordination compound and cetrimonium bromide was significantly more effective than either compound alone. This invention provides direction for the treatment of hyperhidrosis and the development of deodorizing and antiperspirant products.
[0029] 2. Peony root bark is the dried root bark of the peony plant (Paeonia suffruticosa), belonging to the Ranunculaceae family. Studies have shown that peony root bark extract contains phenols and phenolic glycosides, monoterpenes and glycosides, triterpenes, sterols and their glycosides. Furthermore, the decoction of peony root bark extract has a strong inhibitory effect on some microorganisms such as Escherichia coli, Shigella dysenteriae, Staphylococcus aureus, and hemolytic streptococci. Its effects include clearing heat and cooling blood, promoting blood circulation and removing blood stasis, and possessing anti-inflammatory, anti-tumor, hypoglycemic, anti-allergic, and cardiovascular protective effects. Conventional peony root bark extraction uses solvents such as water and ethanol, combined with distillation techniques. However, the extract is rich in active substances, and the loss of these active substances during extraction can easily occur, significantly reducing the content of active substances in the extract and further reducing its efficacy. Therefore, this invention maximizes the extraction of active substances by combining ultrasound with solvents and distillation, and further increases the content of active substances by adding alkaline amino acids to enrich and precipitate them.
[0030] 3. As a more preferred embodiment of the present invention, the composition of the present invention further includes a microcarrier capable of enriching the active ingredients in the composition. The microcarrier of the present invention uses a three-dimensional ordered macroporous metal-organic framework material as the carrier matrix. Through modification with sodium 2,3-dihydroxynaphthalene-6-sulfonate, a sulfonated modified three-dimensional ordered macroporous metal-organic framework material is obtained. Subsequently, coupling groups are added to the modified three-dimensional ordered macroporous metal-organic framework material under the action of a silane coupling agent. This allows organic and inorganic substances to be linked together through the coupling agent, thereby enabling the effective active ingredients in the composition to be enriched on the microcarrier and exert a greater effect. Experimental verification shows that the enrichment effect of the microcarrier can improve the efficacy of the effective active ingredients.
[0031] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below. Detailed Implementation
[0032] To make the technical means, creative features, achieved objectives, and effects of this invention readily understandable, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0033] Unless otherwise specified, the products used in the following examples were sourced from the following sources: tetrachloroaluminum zirconium phosphate (GLY) coordination compound was purchased from Guangzhou Tenus Chemical Co., Ltd.; cetrimonium bromide was purchased from Guangzhou Tenus Chemical Co., Ltd.; peony root bark and oat β-glucan were purchased from Guangzhou Tenus Chemical Co., Ltd.; PEG-40 hydrogenated castor oil was purchased from Evonik, Germany; fragrance was purchased from IFF; citric acid was purchased from Anhui Fengyuan Biochemical Co., Ltd.; other materials and reagents not specified in the source were commercially available.
[0034] Unless otherwise specified, the preparation method of the three-dimensional ordered macroporous metal-organic framework materials in Examples 4-7 below is as follows: Polystyrene emulsion is centrifuged at 5000 r / h for 6 h, and then the supernatant is removed to obtain the bottom precipitate. After drying at 90℃ overnight, an ordered polystyrene template is obtained. This template is immersed in a 0.05 g / mL zinc nitrate / methanol dispersion for 2 hours, then removed and dried overnight. The polystyrene template immersed in the zinc nitrate / methanol solution is then immersed in a 0.1 g / mL 2-methylimidazole / methanol solution and allowed to stand for 48 hours to obtain a polystyrene / organic framework composite material. The polystyrene / organic framework composite material is then immersed in N,N-dimethylformamide and stirred for 24 hours to remove the polystyrene, yielding the three-dimensional ordered macroporous metal-organic framework material.
[0035] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.
[0036] Example 1:
[0037] S1: Preparation of Peony Root Bark Extract: The dried root bark of peony was pulverized, ground, and passed through a 150-mesh sieve to obtain peony root bark powder. The peony root bark powder was mixed with the extraction solvent (composed of ethanol, chloroform, and water in a volume ratio of 1:0.5:20) at a mass-volume ratio of 1g:30mL and sonicated at 100kHz for 50min, followed by soaking for 7h. Finally, the distillate was collected by reflux in a water bath to obtain a crude extract. A histidine / ethanol mixture (composed of histidine and 75% ethanol solution in a mass-volume ratio of 1g:100mL) was added to the obtained crude extract at a volume ratio of 1:25 and stirred continuously at 50℃ for 3h. After standing for 21h, the precipitate was filtered and collected. The precipitate was then freeze-dried under vacuum to obtain the peony root bark extract.
[0038] S2: Weigh the following raw materials by weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 0.3% peony root bark extract, 3.5% glyceryl glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0039] S3: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound are stirred until completely dissolved in water. Then, citric acid is added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan are added sequentially and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0040] Example 2:
[0041] S1: Preparation of Peony Root Bark Extract: The dried root bark of peony was pulverized, ground, and passed through a 100-mesh sieve to obtain peony root bark powder. The peony root bark powder was mixed with the extraction solvent (composed of ethanol, chloroform, and water in a volume ratio of 1:0.5:30) at a mass-volume ratio of 1g:20mL and sonicated at 80kHz for 60min. The mixture was then soaked for 4h, and the distillate was collected by reflux in a water bath to obtain a crude extract. A lysine / ethanol mixture (composed of lysine and a 75% ethanol solution in a mass-volume ratio of 1g:50mL) was added to the crude extract at a volume ratio of 1:20. The mixture was stirred continuously at 60℃ for 1h, allowed to stand for 24h, filtered, and the precipitate was collected. The precipitate was then freeze-dried under vacuum to obtain the peony root bark extract.
[0042] S2: Weigh the following raw materials according to weight percentage: 15% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.15% cetrimonium bromide, 0.5% peony root bark extract, 2% glyceryl glucoside, 5% oat β-glucan, 2% PEG-40 hydrogenated castor oil, 0.5% fragrance, 1.5% citric acid, and the balance water.
[0043] S3: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound are stirred until completely dissolved in water. Then, citric acid is added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan are added sequentially and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0044] Example 3:
[0045] S1: Preparation of Peony Root Bark Extract: The dried root bark of peony was pulverized, ground, and passed through a 200-mesh sieve to obtain peony root bark powder. The peony root bark powder was mixed with the extraction solvent (composed of ethanol, chloroform, and water in a volume ratio of 1:0.5:10) at a mass-volume ratio of 1g:40mL and sonicated at 120kHz for 40min. The mixture was then soaked for 10h, and the distillate was collected by reflux in a water bath to obtain a crude extract. An arginine / ethanol mixture (composed of arginine and a 75% ethanol solution in a mass-volume ratio of 1g:150mL) was added to the crude extract at a volume ratio of 1:30. The mixture was stirred continuously at 40℃ for 5h, allowed to stand for 18h, filtered, and the precipitate was collected. The precipitate was then freeze-dried under vacuum to obtain the peony root bark extract.
[0046] S2: Weigh the following raw materials by weight percentage: 5% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.05% cetrimonium bromide, 0.1% peony root bark extract, 5% glyceryl glucoside, 1% oat β-glucan, 1% PEG-40 hydrogenated castor oil, 1% fragrance, 0.5% citric acid, and the balance water.
[0047] S3: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound are stirred until completely dissolved in water. Then, citric acid is added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan are added sequentially and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0048] Example 4:
[0049] In a more preferred embodiment of the present invention, the composition further includes microcarriers capable of enriching the active ingredients in the composition. Experimental verification has shown that the enrichment effect of the microcarriers can enhance the efficacy of the active ingredients. Therefore, by weight percentage, the composition comprises the following components in the following amounts: 5-15% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.05-0.15% cetrimonium bromide, 1-5% microcarriers, 0.1-0.5% peony root bark extract, 2-5% glyceryl glucoside, 1-5% oat β-glucan, 1-2% PEG-40 hydrogenated castor oil, 0.5-1% fragrance, 0.5-1.5% citric acid, and the balance being water.
[0050] The preparation method of this composition is as follows:
[0051] Preparation of peony root bark extract: The method is the same as described above, and will not be repeated here.
[0052] Preparation of microcarriers: Three-dimensional ordered macroporous metal-organic framework (MOF) materials were pulverized, ground, and passed through a 500-1000 mesh sieve to obtain ultrafine three-dimensional ordered macroporous MOF powder. The obtained ultrafine three-dimensional ordered macroporous MOF powder was then dispersed in N,N-dimethylformamide, and a sodium 2,3-dihydroxynaphthalene-6-sulfonate solution (prepared by mixing sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium chloride, and 10-30 wt% hydrochloric acid solution at a mass-to-volume ratio of 1 g: 0.05-0.1 g: 30-80 mL) was added. The mixture was stirred at 100-150 °C for 2-3 h. After the reaction, the mixture was filtered, washed, and dried to obtain modified three-dimensional ordered macroporous MOF. The modified three-dimensional ordered macroporous metal-organic framework material was immersed in an ethanol solution of 40-60 wt% silane coupling agent and stirred at room temperature for 10-12 h. After filtration, the resulting solid product was washed and dried to obtain a microcarrier. In the above reaction process, the three-dimensional ordered macroporous metal-organic framework material powder, N,N-dimethylformamide and sodium 2,3-dihydroxynaphthalene-6-sulfonate solution were added at a mass-volume ratio of 1 g: 5-10 mL: 10-30 mL. The silane coupling agent was selected from any one of methyltrimethoxysilane, tetramethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane and tetrapropoxysilane.
[0053] Weigh the following raw materials according to weight percentage: 5-15% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.05-0.15% cetrimonium bromide, 1-5% microcarrier, 0.1-0.5% peony root bark extract, 2-5% glyceryl glucoside, 1-5% oat β-glucan, 1-2% PEG-40 hydrogenated castor oil, 0.5-1% fragrance, 0.5-1.5% citric acid, and the balance being water;
[0054] First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound were stirred until completely dissolved in water. Then, peony root bark extract was added and stirred until homogeneous. Next, microcarriers were added and stirred continuously at 30-35°C for 1-3 hours. Citric acid, glycerol glucoside, and oat beta-glucan were added in sequence and stirred until homogeneous. Finally, PEG-40 hydrogenated castor oil and fragrance were added and stirred until completely homogeneous to obtain the composition.
[0055] Example 5:
[0056] S1: Preparation of peony root bark extract: as described in Example 1, and will not be repeated here.
[0057] S2: Preparation of Microcarriers: Three-dimensional ordered macroporous metal-organic framework (MOF) materials were pulverized, ground, and passed through an 800-mesh sieve to obtain ultrafine three-dimensional ordered macroporous MOF powder. The obtained ultrafine three-dimensional ordered macroporous MOF powder was then dispersed in N,N-dimethylformamide, and a sodium 2,3-dihydroxynaphthalene-6-sulfonate solution (prepared by mixing sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium chloride, and 20wt% hydrochloric acid solution at a mass-to-volume ratio of 1g:0.075g:55mL) was added. The mixture was stirred at 125℃ for 2.5h. After the reaction, the mixture was filtered, washed, and dried to obtain modified three-dimensional ordered macroporous MOF materials. The obtained modified three-dimensional ordered macroporous MOF materials were immersed in a 50wt% methyltrimethoxysilane ethanol solution and stirred at room temperature for 11h. After filtration, the resulting solid product was washed and dried to obtain microcarriers. In the above reaction process, three-dimensional ordered macroporous metal-organic framework material powder, N,N-dimethylformamide and sodium 2,3-dihydroxynaphthalene-6-sulfonate solution were added in a mass-volume ratio of 1g:7.5mL:20mL.
[0058] S3: Weigh the following raw materials according to weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 3% microcarrier, 0.3% peony root bark extract, 3.5% glycerol glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0059] S4: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium GLY coordination compound are stirred until completely dissolved in water. Then, peony root bark extract is added and stirred evenly. Next, microcarrier is added and stirred continuously at 32°C for 2 hours. Then, citric acid, glycerol glucoside, and oat beta-glucan are added in sequence and stirred evenly. Finally, PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0060] Example 6:
[0061] S1: Preparation of peony root bark extract: as described in Example 1, and will not be repeated here.
[0062] S2: Preparation of microcarriers: The three-dimensional ordered macroporous metal-organic framework material was crushed, ground and passed through a 1000-mesh sieve to obtain ultrafine three-dimensional ordered macroporous metal-organic framework material powder. The obtained ultrafine three-dimensional ordered macroporous metal-organic framework material powder was then dispersed in N,N-dimethylformamide, and a sodium 2,3-dihydroxynaphthalene-6-sulfonate solution (obtained by mixing sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium chloride, and 10wt% hydrochloric acid solution in a mass-volume ratio of 1g:0.1g:80mL) was added. The mixture was stirred at 100℃ for 3 hours. After the reaction, the mixture was filtered, washed, and dried to obtain the modified three-dimensional ordered macroporous metal-organic framework material. The obtained modified three-dimensional ordered macroporous metal-organic framework material was then immersed in a 40wt% tetramethoxysilane ethanol solution and stirred at room temperature for 12 hours. After filtration, the obtained solid product was washed and dried to obtain the microcarrier. In the above reaction process, the three-dimensional ordered macroporous metal-organic framework material powder, N,N-dimethylformamide, and sodium 2,3-dihydroxynaphthalene-6-sulfonate solution were added in a mass-volume ratio of 1g:5mL:10mL.
[0063] S3: Weigh the following raw materials according to weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 3% microcarrier, 0.3% peony root bark extract, 3.5% glycerol glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0064] S4: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium GLY coordination compound are stirred until completely dissolved in water. Then, peony root bark extract is added and stirred evenly. Next, microcarrier is added and stirred continuously at 32°C for 2 hours. Then, citric acid, glycerol glucoside, and oat beta-glucan are added in sequence and stirred evenly. Finally, PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0065] Example 7:
[0066] S1: Preparation of peony root bark extract: as described in Example 1, and will not be repeated here.
[0067] S2: Preparation of microcarriers: The three-dimensional ordered macroporous metal-organic framework material was crushed, ground and passed through a 500-mesh sieve to obtain ultrafine three-dimensional ordered macroporous metal-organic framework material powder. The obtained ultrafine three-dimensional ordered macroporous metal-organic framework material powder was then dispersed in N,N-dimethylformamide, and a sodium 2,3-dihydroxynaphthalene-6-sulfonate solution (prepared by mixing sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium chloride, and 30wt% hydrochloric acid solution in a mass-volume ratio of 1g:0.05g:30mL) was added. The mixture was stirred at 150℃ for 2 hours. After the reaction, the mixture was filtered, washed, and dried to obtain the modified three-dimensional ordered macroporous metal-organic framework material. The obtained modified three-dimensional ordered macroporous metal-organic framework material was then immersed in a 60wt% methyltriethoxysilane ethanol solution and stirred at room temperature for 10 hours. After filtration, the obtained solid product was washed and dried to obtain the microcarrier. In the above reaction process, the three-dimensional ordered macroporous metal-organic framework material powder, N,N-dimethylformamide, and sodium 2,3-dihydroxynaphthalene-6-sulfonate solution were added in a mass-volume ratio of 1g:10mL:30mL.
[0068] S3: Weigh the following raw materials according to weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 3% microcarrier, 0.3% peony root bark extract, 3.5% glycerol glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0069] S4: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium GLY coordination compound are stirred until completely dissolved in water. Then, peony root bark extract is added and stirred evenly. Next, microcarrier is added and stirred continuously at 32°C for 2 hours. Then, citric acid, glycerol glucoside, and oat beta-glucan are added in sequence and stirred evenly. Finally, PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0070] Comparative Example 1:
[0071] S1: Preparation of Peony Root Bark Extract: The dried root bark of peony was pulverized, ground, and passed through a 150-mesh sieve to obtain peony root bark powder. The peony root bark powder was mixed with the extraction solvent (composed of ethanol, chloroform, and water in a volume ratio of 1:0.5:20) at a mass-volume ratio of 1g:30mL and sonicated at 100kHz for 50min, followed by soaking for 7h. Finally, the distillate was collected by reflux in a water bath to obtain a crude extract. 75% ethanol solution was added to the crude extract at a volume ratio of 1:25 and stirred continuously at 50℃ for 3h. After standing for 21h, the precipitate was filtered and collected. The precipitate was then freeze-dried under vacuum to obtain the peony root bark extract.
[0072] S2: Weigh the following raw materials by weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 0.3% peony root bark extract, 3.5% glyceryl glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0073] S3: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound are stirred until completely dissolved in water. Then, citric acid is added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan are added sequentially and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0074] Comparative Example 2:
[0075] S1: Preparation of Peony Root Bark Extract: The dried root bark of peony was pulverized, ground, and passed through a 150-mesh sieve to obtain peony root bark powder. The peony root bark powder was mixed with the extraction solvent (composed of ethanol, chloroform, and water in a volume ratio of 1:0.5:20) at a mass-volume ratio of 1g:30mL and sonicated at 100kHz for 50min, followed by soaking for 7h. Finally, the distillate was collected by reflux in a water bath to obtain a crude extract. A histidine / ethanol mixture (composed of histidine and 75% ethanol solution in a mass-volume ratio of 1g:100mL) was added to the obtained crude extract at a volume ratio of 1:25 and stirred continuously at 50℃ for 3h. After standing for 21h, the precipitate was filtered and collected. The precipitate was then freeze-dried under vacuum to obtain the peony root bark extract.
[0076] S2: Weigh the following ingredients by weight percentage: 0.1% cetrimonium bromide, 0.3% peony root bark extract, 3.5% glyceryl glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the remainder water.
[0077] S3: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound are stirred until completely dissolved in water. Then, citric acid is added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan are added sequentially and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0078] Comparative Example 3:
[0079] S1: Preparation of Peony Root Bark Extract: The dried root bark of peony was pulverized, ground, and passed through a 150-mesh sieve to obtain peony root bark powder. The peony root bark powder was mixed with the extraction solvent (composed of ethanol, chloroform, and water in a volume ratio of 1:0.5:20) at a mass-volume ratio of 1g:30mL and sonicated at 100kHz for 50min, followed by soaking for 7h. Finally, the distillate was collected by reflux in a water bath to obtain a crude extract. A histidine / ethanol mixture (composed of histidine and 75% ethanol solution in a mass-volume ratio of 1g:100mL) was added to the obtained crude extract at a volume ratio of 1:25 and stirred continuously at 50℃ for 3h. After standing for 21h, the precipitate was filtered and collected. The precipitate was then freeze-dried under vacuum to obtain the peony root bark extract.
[0080] S2: Weigh the following raw materials by weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.3% peony root bark extract, 3.5% glyceryl glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0081] S3: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound are stirred until completely dissolved in water. Then, citric acid is added and stirred until completely dissolved. Subsequently, peony root bark extract, glyceryl glucoside, and oat beta-glucan are added sequentially and stirred until homogeneous. Finally, pre-mixed PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0082] Comparative Example 4:
[0083] S1: Preparation of peony root bark extract: as described in Example 1, and will not be repeated here.
[0084] S2: Preparation of microcarriers: The three-dimensional ordered macroporous metal-organic framework material was pulverized, ground, and passed through an 800-mesh sieve to obtain ultrafine three-dimensional ordered macroporous metal-organic framework material powder. The obtained three-dimensional ordered macroporous metal-organic framework material powder was immersed in a 50wt% methyltrimethoxysilane ethanol solution and stirred at room temperature for 11 hours. After filtration, the obtained solid product was washed and dried to obtain microcarriers.
[0085] S3: Weigh the following raw materials according to weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 3% microcarrier, 0.3% peony root bark extract, 3.5% glycerol glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0086] S4: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium GLY coordination compound are stirred until completely dissolved in water. Then, peony root bark extract is added and stirred evenly. Next, microcarrier is added and stirred continuously at 32°C for 2 hours. Then, citric acid, glycerol glucoside, and oat beta-glucan are added in sequence and stirred evenly. Finally, PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0087] Comparative Example 5:
[0088] S1: Preparation of peony root bark extract: as described in Example 1, and will not be repeated here.
[0089] S2: Preparation of microcarriers: The three-dimensional ordered macroporous metal-organic framework material was pulverized, ground, and passed through an 800-mesh sieve to obtain ultrafine three-dimensional ordered macroporous metal-organic framework material powder. Then, the obtained ultrafine three-dimensional ordered macroporous metal-organic framework material powder was dispersed in N,N-dimethylformamide, and a sodium 2,3-dihydroxynaphthalene-6-sulfonate solution (prepared by mixing sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium chloride, and 20wt% hydrochloric acid solution at a mass-to-volume ratio of 1g:0.075g:55mL) was added. The mixture was stirred at 125℃ for 2.5h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain the microcarriers.
[0090] S3: Weigh the following raw materials according to weight percentage: 10% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.1% cetrimonium bromide, 3% microcarrier, 0.3% peony root bark extract, 3.5% glycerol glucoside, 3% oat β-glucan, 1.5% PEG-40 hydrogenated castor oil, 0.75% fragrance, 0.1% citric acid, and the balance water.
[0091] S4: First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium GLY coordination compound are stirred until completely dissolved in water. Then, peony root bark extract is added and stirred evenly. Next, microcarrier is added and stirred continuously at 32°C for 2 hours. Then, citric acid, glycerol glucoside, and oat beta-glucan are added in sequence and stirred evenly. Finally, PEG-40 hydrogenated castor oil and fragrance are added and stirred until completely homogeneous to obtain the composition.
[0092] Experimental Example 1: Testing the antiperspirant and deodorant effects of different compositions
[0093] Test subjects: Compositions from Examples 1-3, Examples 5-7, and Comparative Examples 1-5
[0094] Experimental Methods: 110 subjects with excessive axillary sweating and odor were randomly recruited, half male and half female, aged 18-40 years. The physical health of the volunteers did not affect the test results. The volunteers were divided into 11 groups of 10 each, numbered 1-11. No topical medications were used for 3 days prior to the test.
[0095] 3. Test method: After the subjects' bodies were cleaned and dried, the compositions of Examples 1-3, Examples 5-7 and Comparative Examples 1-5 were sprayed evenly and in equal amounts onto the armpits of subjects in groups 1-11. Subjects were tested for 8 hours at 28-30℃ under normal activity conditions. The subjects' perception of the antiperspirant and deodorant effect of the antiperspirant and deodorant liquid was recorded, and the antiperspirant effect score was calculated. The scoring criteria are shown in Table 1. The deodorization rate was calculated according to the odor scoring criteria (see Table 2), and the average value of the results was taken. The statistical results are shown in Table 3.
[0096] Deodorization rate = (Score before use of the composition - Score after use of the sample) / Score before use of the sample × 100%.
[0097] Table 1 Scoring Criteria for Antiperspirant Efficacy
[0098]
[0099]
[0100] Table 2 Odor Scoring Criteria
[0101] score level of stench 0 No odor within 1 meter social distance 1 There was a slight, faint odor within a 1-meter social distance. 2 There was an odor within a 1-meter social distance. 3 Strong odor within 1 meter social distance 4 Strong odor within 1 meter social distance 5 The stench was very strong even within a 1-meter social distance.
[0102] Table 3. Statistics on the antiperspirant and deodorant effects of different compositions.
[0103]
[0104]
[0105] Groups 1-11 in Table 3 correspond to the compositions sprayed in Examples 1-3, Examples 5-7, and Comparative Examples 1-5, respectively. As can be seen from the results in Table 3, compared with the test groups sprayed with the compositions of Comparative Examples 1-5, the test groups sprayed with the compositions of Examples 1-3 and Examples 5-7 of this invention exhibited more significant antiperspirant effects and higher deodorization rates. Furthermore, compared with the test groups sprayed with the compositions of Examples 1-3, the subjects sprayed with the compositions of Examples 5-7 showed better antiperspirant and deodorization effects, indicating that the presence of microcarriers can improve the antiperspirant and deodorization effects of the combinations.
[0106] Experimental Example 2: Detection of Antibacterial Effects of Different Compositions
[0107] Experimental subjects: Compositions of Examples 1 and 5 and Comparative Examples 1-5
[0108] Experimental method: The antibacterial effect was tested using the inhibition zone method. The specific steps are as follows:
[0109] One day in advance, Staphylococcus aureus CMCC(B)26112, Escherichia coli CMCC 44102, and Candida albicans ATCC14053 were activated and diluted to 10⁻⁶. 7 Prepare a cfu / mL concentration. Take 100 μL of each bacterium and add it to LB nutrient agar medium, spreading it evenly.
[0110] Sterilized and dried filter paper was added to the compositions of Examples 1 and 5 and Comparative Examples 1-5 and soaked for 1 hour. The soaked filter paper was placed on the culture medium that had been inoculated with bacteria and allowed to stand for 30 minutes, and then placed in an incubator for constant temperature and humidity incubation (36°C for bacteria, 24 hours; 30°C for fungi, 24 hours).
[0111] Remove the petri dishes after the incubation time has been reached, and measure the diameter (mm) of the transparent inhibition zone around the filter paper using calipers. Repeat the experiment three times, and the results are shown in Table 4.
[0112] Table 4. Statistics on the antibacterial effects of different compositions
[0113]
[0114] As can be seen from the results in Table 4, the compositions of Examples 1 and 5 of the present invention have better antibacterial effects compared with comparative Examples 1-5.
[0115] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the methods and techniques disclosed above without departing from the scope of the present invention to create equivalent embodiments. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A composition containing tetrachlorohydroxyaluminum zirconium (GLY) coordination compound and possessing antibacterial, deodorizing, and antiperspirant properties, characterized in that, The composition comprises, by weight percentage, the following components in the following amounts: 5-15% tetrachlorohydroxyaluminum zirconium GLY coordination compound, 0.05-0.15% cetrimonium bromide, 1-5% microcarrier, 0.1-0.5% peony root bark extract, 2-5% glyceryl glucoside, 1-5% oat β-glucan, 1-2% PEG-40 hydrogenated castor oil, 0.5-1% fragrance, 0.5-1.5% citric acid, and the balance being water; The microcarrier is prepared as follows: Three-dimensional ordered macroporous metal-organic framework (MOF) material is pulverized, ground, and passed through a 500-1000 mesh sieve to obtain ultrafine three-dimensional ordered macroporous MOF powder; then, the obtained ultrafine three-dimensional ordered macroporous MOF powder is dispersed in N,N-dimethylformamide, and a sodium 2,3-dihydroxynaphthalene-6-sulfonate solution is added. The sodium 2,3-dihydroxynaphthalene-6-sulfonate solution is obtained by mixing sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium chloride, and 10-30 wt% hydrochloric acid solution at a mass-to-volume ratio of 1 g: 0.05-0.1 g: 30-80 mL. The mixture is stirred at 100-150 °C for 2-3 h. After the reaction is complete, the mixture is filtered, washed, and dried. A modified three-dimensional ordered macroporous metal-organic framework material was obtained. The obtained modified three-dimensional ordered macroporous metal-organic framework material was immersed in an ethanol solution of 40-60 wt% silane coupling agent and stirred at room temperature for 10-12 h. After filtration, the obtained solid product was washed and dried to obtain a microcarrier. In the above reaction process, the three-dimensional ordered macroporous metal-organic framework material powder, N,N-dimethylformamide and sodium 2,3-dihydroxynaphthalene-6-sulfonate solution were added at a mass-volume ratio of 1 g: 5-10 mL: 10-30 mL. The silane coupling agent was selected from any one of methyltrimethoxysilane, tetramethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane and tetrapropoxysilane. The preparation method of the three-dimensional ordered macroporous metal-organic framework material is as follows: Polystyrene emulsion is centrifuged at 5000 r / h for 6 h, and the supernatant is removed to obtain the bottom precipitate; after drying at 90℃ overnight, an ordered polystyrene template is obtained; this template is immersed in a 0.05 g / mL zinc nitrate / methanol solution for 2 hours, and then the polystyrene template is removed and dried overnight; the polystyrene template immersed in the zinc nitrate / methanol solution is immersed in a 0.1 g / mL 2-methylimidazole / methanol solution and allowed to stand for 48 hours to obtain a polystyrene / organic framework composite material; the polystyrene / organic framework composite material is immersed in N,N-dimethylformamide, stirred for 24 hours, and then the polystyrene is removed to obtain the three-dimensional ordered macroporous metal-organic framework material. The peony root bark extract was prepared according to the following steps: The dried root bark of peony is crushed, ground, and then passed through a 100-200 mesh sieve to obtain peony root bark powder; The peony root bark powder and extraction solvent were mixed at a mass-volume ratio of 1g:20-40mL and ultrasonicated. Then, the mixture was soaked for 4-10 hours. Finally, the distillate was collected by reflux in a water bath to obtain the crude extract. Add an alkaline amino acid / ethanol mixture to the crude extract at a volume ratio of 1:20-30 and stir continuously at 40-60℃ for 1-5 hours. After standing for 18-24 hours, filter and collect the precipitate. Vacuum freeze-dry the precipitate to obtain peony root bark extract. The extraction solvent is a mixture of ethanol, chloroform, and water in a volume ratio of 1:0.5:10-30. The alkaline amino acid / ethanol mixture is prepared by mixing alkaline amino acids with a 75% ethanol solution at a mass-volume ratio of 1g:50-150mL; the alkaline amino acids are selected from any one of lysine, arginine, and histidine.
2. The composition according to claim 1, characterized in that, The ultrasonic conditions are: frequency 80-120kHz, ultrasonic time 40-60min.
3. A method for preparing the composition according to any one of claims 1-2, characterized in that, The preparation method includes the following steps: Preparation of peony root bark extract: The dried root bark of peony is crushed, ground, and then passed through a 100-200 mesh sieve to obtain peony root bark powder; Peony root bark powder and extraction solvent were mixed at a mass-volume ratio of 1g:20-40mL and sonicated. The mixture was then soaked for 4-10 hours. Finally, the distillate was collected by reflux in a water bath to obtain a crude extract. The extraction solvent was a mixture of ethanol, chloroform and water at a volume ratio of 1:0.5:10-30. Add a basic amino acid / ethanol mixture to the crude extract at a volume ratio of 1:20-30 and stir continuously at 40-60℃ for 1-5 hours. After standing for 18-24 hours, filter and collect the precipitate. Freeze-dry the precipitate under vacuum to obtain peony root bark extract. The basic amino acid / ethanol mixture is prepared by mixing basic amino acids with a 75% ethanol solution at a mass-volume ratio of 1 g: 50-150 mL. The basic amino acids are selected from lysine, arginine, and histidine. Weigh the following raw materials according to weight percentage: 5-15% tetrachlorohydroxyaluminum zirconium (GLY) coordination compound, 0.05-0.15% cetrimonium bromide, 1-5% microcarrier, 0.1-0.5% peony root bark extract, 2-5% glyceryl glucoside, 1-5% oat β-glucan, 1-2% PEG-40 hydrogenated castor oil, 0.5-1% fragrance, 0.5-1.5% citric acid, and the balance being water; First, cetrimonium bromide and tetrachlorohydroxyaluminum zirconium (GLY) coordination compound were stirred until completely dissolved in water. Then, peony root bark extract was added and stirred until homogeneous. Next, microcarriers were added and stirred continuously at 30-35°C for 1-3 hours. Citric acid, glycerol glucoside, and oat beta-glucan were added in sequence and stirred until homogeneous. Finally, PEG-40 hydrogenated castor oil and fragrance were added and stirred until completely homogeneous to obtain the composition.
4. The preparation method according to claim 3, characterized in that, The ultrasonic conditions are: frequency 80-120kHz, ultrasonic time 40-60min.
Citation Information
Patent Citations
Tree peony bark extract and application thereof to preparation of medicines for treating pulmonary fibrosis
CN104983816A
Low-sensitization improved hidroschesis and deodorization composition with antibacterial effect
CN117883350A