CN113318071A - Gel for treating foot and knee pain and preparation method thereof - Google Patents

Gel for treating foot and knee pain and preparation method thereof Download PDF

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Publication number
CN113318071A
CN113318071A CN202110671037.7A CN202110671037A CN113318071A CN 113318071 A CN113318071 A CN 113318071A CN 202110671037 A CN202110671037 A CN 202110671037A CN 113318071 A CN113318071 A CN 113318071A
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gel
zinc oxide
parts
knee pain
wollastonite
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Chinese (zh)
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凌晓南
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Guangzhou Tekobiti Technology Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/06Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/06Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/24Heavy metals; Compounds thereof
    • A61K33/30Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/10Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/14Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0012Galenical forms characterised by the site of application
    • A61K9/0014Skin, i.e. galenical aspects of topical compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00Drugs for skeletal disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00Drugs for skeletal disorders
    • A61P19/06Antigout agents, e.g. antihyperuricemic or uricosuric agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
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  • Pharmacology & Pharmacy (AREA)
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  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Rheumatology (AREA)
  • Pain & Pain Management (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Dermatology (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention discloses a gel for treating foot and knee pain and a preparation method thereof, wherein the gel comprises the following components: zinc oxide, wollastonite, bisabolol, ethylparaben, deionized water and carbomer. The preparation method of the gel for treating the pain of the feet and the knees comprises the steps of adding zinc oxide, wollastonite, bisabolol and ethylparaben into deionized water according to the weight ratio, fully dispersing, then adding the mixture into carbomer, uniformly stirring, standing and sterilizing to obtain the gel for treating the pain of the feet and the knees. The gel for treating foot and knee pains is used for auxiliary cold compress physical therapy of cervical vertebra, lumbar vertebra, shoulder, tendon sheath, heel pain, gout and the like, has high stability, and can effectively relieve soreness and swelling pain.

Description

Gel for treating foot and knee pain and preparation method thereof
Technical Field
The invention belongs to the field of medical care, and particularly relates to a gel for treating foot and knee pain and a preparation method thereof.
Background
Under certain conditions, colloidal particles or macromolecules in a sol or solution are connected with each other to form a spatial network structure, and the structural voids are filled with a liquid (in a xerogel, a gas can be used, and the xerogel is also called an aerogel) serving as a dispersion medium, so that a special dispersion system is called a gel. It has no fluidity. The interior often contains a large amount of liquid. For example, the water content of blood gel and agar can reach more than 99%.
The gel is used as a common preparation form in medicine, and the gel added with the effective analgesic component can be used for relieving local pain, such as muscle pain, joint pain, and pain and swelling caused by strain, sprain and sports injury, and can also be used for symptomatic treatment of osteoarthritis.
However, the currently used gel has the disadvantages of poor stability and slow onset of action.
Disclosure of Invention
The invention aims to provide a gel for treating foot and knee pains, which is used for auxiliary cold compress physiotherapy of cervical vertebra, lumbar vertebra, shoulder, tendon sheath, heel pain, gout and the like, has high stability and can effectively relieve the ache and the pain.
It is necessary to provide a preparation method of the gel for treating the foot and knee pain.
A gel for treating foot and knee pain comprises the following components:
zinc oxide, wollastonite, bisabolol, ethylparaben, deionized water and carbomer.
Preferably, the gel for treating the foot and knee pain comprises the following components in parts by weight:
50-54 parts of zinc oxide;
58-60 parts of wollastonite;
5-6 parts of bisabolol;
47-50 parts of ethylparaben;
100 parts of deionized water;
carbomer 733 and 738 parts.
More preferably, the gel for treating the foot and knee pain comprises the following components in parts by weight:
52 parts of zinc oxide;
58 parts of wollastonite;
5 parts of bisabolol;
47 parts of ethylparaben;
100 parts of deionized water;
and 738 parts of carbomer.
Preferably, the zinc oxide has a particle size in the range of 20-60um, more preferably in the range of 20-50um, as measured by electron microscopy.
Preferably, the angle of repose of the zinc oxide is 30 to 35 degrees, and the angle of repose is measured by transferring the powder into a funnel, allowing the sample to fall on a round flat plate with a radius of R below the round flat plate through the funnel, gradually stacking the powder until the stacking height cannot be continuously increased, measuring the stacking height h of the powder, and calculating the angle of repose A according to the formula (1), wherein tanA is h/R.
Preferably, the manganese content of the wollastonite is 0.05 to 0.08 weight percent, and the content of the manganese element is measured by proton x-ray fluorescence analysis.
Preferably, the mesh powder of the wollastonite is more than 800 meshes.
Preferably, the zinc oxide is pretreated by the following method:
washing zinc oxide with deionized water for three times, and then, using water and ethanol in a weight ratio of (2-3): 1, washing for 3 times, drying for 6-7h at 50-60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2h at 500 ℃, and then cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain the zinc oxide.
A method for preparing the gel for treating the pain of feet and knees as described above, comprising the steps of:
adding zinc oxide, wollastonite, bisabolol and ethylparaben into deionized water according to the weight ratio, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel for treating foot and knee pain.
Wherein the zinc oxide is pretreated by the following method:
washing the zinc oxide with deionized water for three times, and then, using water and ethanol in a weight ratio of (2-3): 1, washing for 3 times, drying for 6-7h at 50-60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2h at 500 ℃, and then cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain zinc oxide;
the particle size range of the tested zinc oxide is 20-60um, and the angle of repose is 30-35 degrees.
The gel for treating the foot and knee pains, provided by the invention, consists of zinc oxide, wollastonite, bisabolol, ethylparaben, deionized water and carbomer, wherein the gel system is more stable due to the specific particle size range and the flowing zinc oxide, the stability of the product is high, the onset time of the analgesic gel is more favorably prolonged, the gel is particularly suitable for auxiliary cold compress physical therapy of cervical vertebra, lumbar vertebra, shoulder, tendon sheath, heel pain, gout and the like, and the acid swelling pain can be effectively relieved.
Detailed Description
The core of the invention is to provide a gel for treating foot and knee pain and a preparation method thereof. The present invention will be described in further detail with reference to specific embodiments in order to make the technical field better understand the scheme of the present invention.
Description of the raw materials
Zinc oxide: medical grade, Shanxi brocade pharmaceutic adjuvant Limited
Wollastonite A: the mineral powder processing factory of Lingshou county Fengxin, the specification is 800 meshes, and the manganese element content is 0.05 wt%;
wollastonite B: the mineral powder processing factory of the Lingshou county Fengxin, the specification is 200 meshes, and the manganese element content is 0.12 wt%;
bisabolol: medical grade, Wuhan Hua Zhi scientific Biotech limited
Ethyl paraben: medical grade, Xianhao Nature engineering Co Ltd
Carbomer: medical grade, Xian Tianzheng pharmaceutic adjuvant, Co Ltd
The particle size test of the zinc oxide is carried out by an electron microscope test, and the determination of the content of the manganese element is carried out by a proton x-ray fluorescence analysis method.
The test method of the angle of repose is as follows: the powder is transferred into a funnel, a sample is dropped on a round flat plate with the radius of R at the lower part through the funnel, and the powder is gradually stacked until the powder cannot be continuously stacked. The stacking height h of the powder was measured, and the angle of repose a was calculated by the formula (1), and tanA was h/R.
Example 1
Analytically pure zinc oxide was washed three times with deionized water, dried and then treated with water and ethanol in a weight ratio of 2.5: 1, washing for 3 times, drying for 6 hours at 60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2 hours at 500 ℃, cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain a zinc oxide material, and testing to obtain a zinc oxide material with the particle size of 20-50um and the angle of repose of 30 degrees;
adding zinc oxide, wollastonite A, bisabolol and ethylparaben into deionized water according to the weight ratio shown in Table 1, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel for treating foot and knee pain.
Example 2
Analytically pure zinc oxide was washed three times with deionized water, dried and then treated with water and ethanol in a weight ratio of 2: 1, washing for 3 times, drying for 7 hours at 50 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting the obtained product into a high-temperature furnace, preserving heat for 2 hours at 500 ℃, cooling at 30 ℃/10min until the product is cooled to room temperature to obtain a zinc oxide material, and testing to obtain the zinc oxide material with the particle size of 40-60um and the angle of repose of 35 degrees.
Adding zinc oxide, wollastonite A, bisabolol and ethylparaben into deionized water according to the weight ratio shown in Table 1, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel for treating foot and knee pain.
Example 3
Analytically pure zinc oxide was washed three times with deionized water, dried and then treated with water and ethanol in a weight ratio of 3: 1, washing for 3 times, drying for 6h at 60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2h at 500 ℃, then cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain a zinc oxide material, and testing to obtain the zinc oxide material with the particle size of 30-60um and the angle of repose of 33 degrees.
Adding zinc oxide, wollastonite A, bisabolol and ethylparaben into deionized water according to the weight ratio shown in Table 1, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel for treating foot and knee pain.
Comparative example 1
Washing analytically pure zinc oxide with deionized water for three times, drying, washing with ethanol for 3 times, drying in a constant-temperature vacuum drying oven at 60 ℃ for 6 hours, fully grinding, placing in a high-temperature furnace at 500 ℃ for 2 hours, cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain a zinc oxide material, and testing shows that the zinc oxide material has a particle size of 80-110 mu m and an angle of repose of 23 degrees.
Adding zinc oxide, wollastonite A, bisabolol and ethylparaben into deionized water according to the weight ratio shown in Table 1, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel.
Comparative example 2
Washing analytically pure zinc oxide with ethanol for 3 times, drying in a constant-temperature vacuum drying oven at 60 ℃ for 6 hours, fully grinding, putting into a high-temperature furnace, preserving heat for 2 hours at 500 ℃, then cooling at 50 ℃/10min until the temperature is cooled to room temperature to obtain a zinc oxide material, and testing to obtain the zinc oxide material with the particle size of 10-20um and the angle of repose of 45 degrees.
Adding zinc oxide, wollastonite A, bisabolol and ethylparaben into deionized water according to the weight ratio shown in Table 1, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel.
Comparative example 3
Analytically pure zinc oxide was washed three times with deionized water, dried and then treated with water and ethanol in a weight ratio of 2.5: 1, washing for 3 times, drying for 6 hours at 60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2 hours at 500 ℃, cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain a zinc oxide material, and testing to obtain a zinc oxide material with the particle size of 20-50um and the angle of repose of 30 degrees;
adding zinc oxide, wollastonite B, bisabolol and ethylparaben into deionized water according to the weight ratio shown in Table 1, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel.
TABLE 1 gel formulation tables for examples and comparative examples
Figure BDA0003118783790000051
Gel Performance testing of examples and comparative examples
Stability test
After the gels prepared in the examples and the comparative examples are stored for 3 months, the gels are placed in an oven with the temperature of 30 ℃ for 3 hours, the time is recorded, and the properties of the gels are observed at 1 hour, 2 hours and 3 hours respectively and recorded in the table 2.
Evaluation of gel efficacy in relieving pain
20 patients with rheumatalgia were selected, and at onset the time of marked pain relief (onset time) was recorded using the cold gels of comparative and example, respectively, and the average value was recorded in Table 2.
TABLE 2 gel Property test Table
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Properties (1 hour) Gel form Gel form Gel form Gel form Gel form Gel form
Properties (2 hours) Gel form Gel form Gel form Gel form With water exudation With water exudation
Trait (3 hours) Gel form Gel form Gel form Little water exudation More water exudes More water exudes
Onset time 14min 15min 15min 21min 18min 25min
As can be seen from the experimental results in Table 2, the gels of the examples and the comparative examples have analgesic effect, the onset time of the gels of the examples 1 to 3 is faster, the stability of the gels of the examples 1 to 3 is obviously improved compared with the stability of the gels of the comparative examples 1 to 3, and meanwhile, the wollastonite with specific particle size contains a limited amount of manganese element, which also has obvious influence on the onset time of the product.
The zinc oxide with specific particle size and fluidity has obviously improved comprehensive performance on the gel for treating foot and knee pains
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A gel for treating foot and knee pain is characterized by comprising the following components:
zinc oxide, wollastonite, bisabolol, ethylparaben, deionized water and carbomer.
2. The gel for treating foot and knee pain according to claim 1, comprising the following components in parts by weight:
50-54 parts of zinc oxide;
58-60 parts of wollastonite;
5-6 parts of bisabolol;
47-50 parts of ethylparaben;
100 parts of deionized water;
carbomer 733 and 738 parts.
3. The gel for treating foot and knee pain according to claim 1, comprising the following components in parts by weight:
52 parts of zinc oxide;
58 parts of wollastonite;
5 parts of bisabolol;
47 parts of ethylparaben;
100 parts of deionized water;
and 738 parts of carbomer.
4. The gel for treating foot and knee pain of claim 1, 2 or 3, wherein:
the particle size range of the zinc oxide is 20-60 um.
5. The gel for treating foot and knee pain of claim 1, 2 or 3, wherein:
the repose angle of the zinc oxide is 30-35 degrees, and the testing method of the repose angle is that powder is transferred into a funnel, a sample is dropped on a round flat plate with the radius of R below the sample through the funnel, the powder is gradually stacked until the stacking height cannot be continuously increased, the stacking height h of the powder is measured, and the repose angle A is calculated according to a formula (1), and tanA is h/R.
6. The gel for treating foot and knee pain of claim 1, 2 or 3, wherein:
the manganese content of the wollastonite is 0.05 to 0.08 percent.
7. The gel for treating foot and knee pain of claim 1, 2 or 3, wherein:
the mesh powder of the wollastonite is more than 800 meshes.
8. The gel for treating foot and knee pain according to claim 4, wherein said zinc oxide is pretreated by:
washing zinc oxide with deionized water for three times, and then, using water and ethanol in a weight ratio of (2-3): 1, washing for 3 times, drying for 6-7h at 50-60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2h at 500 ℃, and then cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain the zinc oxide.
9. A method for preparing a gel for treating pain in the feet and knees according to any one of claims 1-8, comprising the steps of:
adding zinc oxide, wollastonite, bisabolol and ethylparaben into deionized water according to the weight ratio, fully dispersing, then adding into carbomer, uniformly stirring, standing, and sterilizing to obtain the gel for treating foot and knee pain.
10. The method of preparing a gel for the treatment of foot and knee pain according to claim 9, wherein said zinc oxide is pre-treated by the following method:
washing the zinc oxide with deionized water for three times, and then, using water and ethanol in a weight ratio of (2-3): 1, washing for 3 times, drying for 6-7h at 50-60 ℃ in a constant-temperature vacuum drying oven, fully grinding, putting into a high-temperature furnace, preserving heat for 2h at 500 ℃, and then cooling at 30 ℃/10min until the temperature is cooled to room temperature to obtain zinc oxide;
the particle size range of the tested zinc oxide is 20-60um, and the angle of repose is 30-35 degrees.
CN202110671037.7A 2021-06-17 2021-06-17 Gel for treating foot and knee pain and preparation method thereof Pending CN113318071A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2274588A (en) * 1993-02-02 1994-08-03 Orna Levin Analgesic gel compositions
CN107412432A (en) * 2017-08-10 2017-12-01 杭州仁德医药有限公司 One kind is used to treat arthralgia and arthritis external plaster and preparation method thereof
CN108686165A (en) * 2018-07-10 2018-10-23 贵州东仪医疗器械有限公司 A kind of patch and its preparation method and application for pain therapy
CN110624041A (en) * 2019-10-22 2019-12-31 成都六然医疗科技有限公司 Cold compress gel for relieving gout and preparation method thereof
US20210046040A1 (en) * 2018-07-11 2021-02-18 Innocan Pharma Ltd. Pain-relieving topical compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2274588A (en) * 1993-02-02 1994-08-03 Orna Levin Analgesic gel compositions
CN107412432A (en) * 2017-08-10 2017-12-01 杭州仁德医药有限公司 One kind is used to treat arthralgia and arthritis external plaster and preparation method thereof
CN108686165A (en) * 2018-07-10 2018-10-23 贵州东仪医疗器械有限公司 A kind of patch and its preparation method and application for pain therapy
US20210046040A1 (en) * 2018-07-11 2021-02-18 Innocan Pharma Ltd. Pain-relieving topical compositions
CN110624041A (en) * 2019-10-22 2019-12-31 成都六然医疗科技有限公司 Cold compress gel for relieving gout and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王建新 主编: "《精细有机合成》", 30 April 2007, 中国轻工业出版社 *
王恩德 等编著: "《结晶学与矿物学教程》", 31 October 2019, 冶金工业出版社 *

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Application publication date: 20210831