CN110279889A - A kind of beauty pharmaceutical composition containing sodium hyaluronate - Google Patents
A kind of beauty pharmaceutical composition containing sodium hyaluronate Download PDFInfo
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- CN110279889A CN110279889A CN201910743459.3A CN201910743459A CN110279889A CN 110279889 A CN110279889 A CN 110279889A CN 201910743459 A CN201910743459 A CN 201910743459A CN 110279889 A CN110279889 A CN 110279889A
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- sodium hyaluronate
- buffer solution
- poly
- peo
- sodium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/06—Flowable or injectable implant compositions
Abstract
The invention discloses a kind of beautifying drug composition containing sodium hyaluronate, including following components: sodium hyaluronate or poly- (the propylene glycol)-poly(ethylene glycol) (PEO-PPO-PEO) of its physiologically acceptable salt, mannitol, poly(ethylene glycol)-, sodium carboxymethylcellulose, buffer solution, water for injection.Sodium hyaluronate gel combination of the invention is prepared by self assembly mode, it avoids through chemical reaction bring complicated technology problem, performance is stablized simultaneously, it is able to maintain more permanent filling capacity after injection, (- 30-40 DEG C) are gel under certain temperature, thus show better stability.
Description
Technical field
The invention belongs to aesthetic medicine technical fields, more particularly, to a kind of beautifying drug composition containing sodium hyaluronate.
Background technique
Sodium hyaluronate (hyaluronic acid) is that one kind is widely present in humans and animals body, by dissacharide units (glucuronic acid-N-
Second sulphur aminoglucose composition straight chain polymer polysaccharide), widely exist in connective tissue, the mucous tissue of vertebrate with
And in bacterium folder film, the content in epidermis, corium, umbilical cord, synovia and cartilaginous tissue is also higher.Since 1934, beauty
Since state Meyer etc. isolates sodium hyaluronate from bovine vitreous body first, good bio-compatible gradually has been found to have by the people
The important performances such as property, height viscoplasticity, plasticity and permeability.To be obtained in fields such as medical treatment, beauty and bioengineering
It is widely applied.
In the past 10 years, sodium hyaluronate is widely used in medical cosmetology field as dermal filler, and injecting under corium can make
The direct volume of subcutaneous tissue increases, and plays the role of " padding ", while can also absorb the moisture of surrounding tissue, to reach expansion body
Long-pending effect keeps relaxation, the skin of recess again full, and this injection treatment has been widely used for reparation and aging
Recess caused by relevant skinfold and some congenital or posteriori disease.
Although sodium hyaluronate has the desirable properties as tissue filling agent in the recovery of young skin property, however, working as
When being injected the facial area with increase smooth with facial wrinkles, since sodium hyaluronate and the crosslinking of itself reduce its these injections simultaneously
It is not able to maintain persistence.If it is intended to keeping lasting effect, it is necessary to periodically be injected again.In addition, in the prior art
Sodium hyaluronate product there is another problem: it is in injection, it is difficult to form uniform distribution.
To solve the above-mentioned problems, used technological means is by adding crosslinking agent in sodium hyaluronate injection.Mesh
The crosslinking agent of preceding sodium hyaluronate mainstream has 2 kinds, and one is DVS (divinylsulfones), this sensitization is high, is easy redness;There are also one
A is BDDE (1,4-butanediol diglycidyl ether (BDDE)), this is the crosslinking agent of present mainstream, Small side effects.
United States Patent (USP) US8357795 discloses a kind of sodium hyaluronate that can squeeze out injection single phase property by fine needle and fills out
Agent is filled, however, there are problems for the safety of this sodium hyaluronate filler injected by fine needle in vivo;United States Patent (USP)
US5827937 discloses a kind of Bipolar sodium hyaluronate filler.
Pluronic F-127 (poloxamer) is a kind of nonionic surface active agent, it with 100% activity simultaneously
And to cell relative non-toxicity, permitted by U.S. FDA clinical use, document TW1413535B discloses one kind and urinated by glass
The copolymer that acid is formed by chemical bonding mode with Pluronic F-127, by using crosslinking agent by Pluronic F-
Hydroxyl in 127 structures is formed by group with methyl, amino, carboxyl or the hydroxyl on sodium hyaluronate skeleton and is combined, from
And it is capable of forming artificial vitreous's material with superperformance.
However, on the one hand, the gel rubber material is bonded by chemical reaction, because regardless of from cost or operating procedure
There is certain defect;On the other hand, due in PEO-PPO-PEO structure simultaneously containing with hydrophilic segment polyethylene glycol and
Hydrophobic patch polypropylene glycol, under certain environment, being formed by active force by water-wet side and hydrophobic side be can produce in performance
Change.For example, the hydrogel that is formed at this time is liquid when forming aqueous solution and being placed in 25 DEG C or less environment, when being placed in internal ring
When border (36 DEG C, pH=7.2-7.5), hydrogel is glue at this time.Cold district winter makes outdoor temperature be -20 DEG C hereinafter,
When room temperature is 20 DEG C, then big inconvenience can be brought for beauty person.
The pleasantly surprised discovery of the present invention, when being added to sodium carboxymethylcellulose in the composition as crosslinking agent, formation
Gel is at a certain temperature (- 30-40 DEG C) gel, thus shows better stability.
Sodium hyaluronate gel combination of the invention is prepared by self assembly mode, is avoided through chemical reaction band
The complicated technology problem come, while performance is stablized, and is able to maintain more permanent filling capacity after injection.
Summary of the invention
Sodium hyaluronate composition provided by the invention includes following components: sodium hyaluronate or its physiologically acceptable salt, sweet dew
Poly- (the propylene glycol)-poly(ethylene glycol) (PEO-PPO-PEO) of alcohol, poly(ethylene glycol)-, sodium carboxymethylcellulose, buffer solution, injection
Use water.
In sodium hyaluronate composition provided by the present invention, wherein the sodium hyaluronate or its physiologically acceptable salt has
Molecular weight is 500-2500kDa, preferably 800-2000kDa, more preferably 1000-1500kDa;
In sodium hyaluronate composition provided by the present invention, wherein the PEO-PPO-PEO has the following structure:
Wherein x, z are the number within 2-100, the number within preferably 10-80;Y is the number within 15-60, preferably 20-
Number within 50.
In sodium hyaluronate composition provided by the present invention, wherein when sodium hyaluronate forming salt, preferably its sodium salt.
In sodium hyaluronate composition provided by the present invention, in which: with mass fraction ratio, sodium hyaluronate or its be physiologically subjected to
Salt and poly- (the propylene glycol)-poly(ethylene glycol) of poly(ethylene glycol)-ratio be (100-500): (10-50)
In sodium hyaluronate composition provided by the present invention, with mass fraction ratio, wherein sodium carboxymethylcellulose and sodium hyaluronate
Or the ratio of its physiologically acceptable salt is (10-50): (50-100), preferably 1:80, more preferably 1:60;
In sodium hyaluronate composition provided by the present invention, wherein the buffer solution maintains the pH of composition in 5 and 8.5
Between, between more preferably 6.8 and 8, between most preferably 7.0 and 8.Wherein, suitable buffer solution can be selected from phosphorus
Hydrochlorate buffer solution, for example, NaH2PO4-NaHPO4, acetate buffer solution, benzoate buffer solution, Citrate buffer
Solution, maleate buffer solution, Tartrate buffer solution.
In sodium hyaluronate composition provided by the present invention, the weight based on sodium hyaluronate or its physiologically acceptable salt is sweet
Reveal alcohol concentration can less than 3%, for example, concentration existing for mannitol can for 2.8%, 2.5%, 2%, 1.6%, 1.5%,
1.2%, 1.0%, 0.8%, 0.5%.
In addition to this, the present invention also provides a kind of method for preparing sodium hyaluronate composition, include the following steps:
(1) Cross-linked gel is prepared;
Poly- (the propylene glycol)-poly(ethylene glycol) of poly(ethylene glycol)-is added into the buffer solution of pH=7.0, is slowly stirred
It expands it sufficiently, sodium carboxymethylcellulose is added into system, heat cross-linking is carried out at 50 DEG C and forms cross-linked gel, it is spare;
(2) sodium hyaluronate gel is prepared
Sodium hyaluronate is added in the buffer solution of isotonic pH=7, mannitol is added, being slowly stirred keeps it sufficiently swollen
It is swollen;
(3) the obtained cross-linked gel of step (1) and the obtained sodium hyaluronate gel of step (2) are sufficiently mixed, ultrasound
Obtain sodium hyaluronate-sodium carboxymethylcellulose-(PEO-PPO-PEO) cross-linked gel;Wherein the ultrasonic power is 1000-
3000W, ultrasonic temperature are -50 DEG C of room temperature, and ultrasonic time is 30min-1 hours;
(4) nitrogen deoxygenation is poured into system, is fitted into syringe after sterilizing.
Specific embodiment
Embodiment 1
Sodium hyaluronate: sodium carboxymethylcellulose: (PEO-PPO-PEO)=100:10:10 (w/w)
(1) NaH for claiming 10 parts of PEO-PPO-PEO to be dissolved in pH=7.02PO4-NaHPO4In buffer solution, being slowly stirred makes
It is sufficiently expanded, and the 10 parts of sodium carboxymethylcelluloses weighed up are added into system, and it is solidifying that heat cross-linking formation crosslinking is carried out at 50 DEG C
Glue, it is spare;
(2) weighed 100 parts of sodium hyaluronates are added to the buffer solution (NaH of isotonic pH=72PO4-NaHPO4) in,
Addition concentration is 2% mannitol, and be slowly stirred expands it sufficiently at room temperature;
(3) the obtained cross-linked gel of step (1) and the obtained sodium hyaluronate gel of step (2) are sufficiently mixed, in room
It is solidifying that temperature lower ultrasonic (ultrasonic power 1000W) obtains sodium hyaluronate-sodium carboxymethylcellulose-(PEO-PPO-PEO) crosslinking for 30 minutes
Glue;
(4) after pouring nitrogen deoxygenation into system 1 hour, sterilizing is fitted into syringe.
Embodiment 2
Sodium hyaluronate: sodium carboxymethylcellulose: (PEO-PPO-PEO)=200:10:10 (w/w)
(1) NaH for claiming 10 parts of PEO-PPO-PEO to be dissolved in pH=7.02PO4-NaHPO4In buffer solution, being slowly stirred makes
It is sufficiently expanded, and the 10 parts of sodium carboxymethylcelluloses weighed up are added into system, and it is solidifying that heat cross-linking formation crosslinking is carried out at 50 DEG C
Glue, it is spare;
(2) buffer solution (NaH for 200 parts of sodium hyaluronates will have been weighed being added to isotonic pH=72PO4-NaHPO4) in, add
Entering concentration is 2.5% mannitol, and be slowly stirred expands it sufficiently at room temperature;
(3) the obtained cross-linked gel of step (1) and the obtained sodium hyaluronate gel of step (2) are sufficiently mixed, in room
It is solidifying that temperature lower ultrasonic (ultrasonic power 1000W) obtains sodium hyaluronate-sodium carboxymethylcellulose-(PEO-PPO-PEO) crosslinking for 30 minutes
Glue;
(4) after pouring nitrogen deoxygenation into system 1 hour, sterilizing is fitted into syringe.
Embodiment 3
Sodium hyaluronate: sodium carboxymethylcellulose: (PEO-PPO-PEO)=100:20:10 (w/w)
(1) NaH for claiming 10 parts of PEO-PPO-PEO to be dissolved in pH=7.02PO4-NaHPO4In buffer solution, being slowly stirred makes
It is sufficiently expanded, and the 20 parts of sodium carboxymethylcelluloses weighed up are added into system, and it is solidifying that heat cross-linking formation crosslinking is carried out at 50 DEG C
Glue, it is spare;
(2) buffer solution (NaH for 200 parts of sodium hyaluronates will have been weighed being added to isotonic pH=72PO4-NaHPO4) in, add
Entering concentration is 2.5% mannitol, and be slowly stirred expands it sufficiently at room temperature;
(3) the obtained cross-linked gel of step (1) and the obtained sodium hyaluronate gel of step (2) are sufficiently mixed, in room
It is solidifying that temperature lower ultrasonic (ultrasonic power 1000W) obtains sodium hyaluronate-sodium carboxymethylcellulose-(PEO-PPO-PEO) crosslinking for 30 minutes
Glue;
(4) after pouring nitrogen deoxygenation into system 1 hour, sterilizing is fitted into syringe.
Embodiment 4 (blank control group)
Sodium hyaluronate: (PEO-PPO-PEO)=100:10 (w/w)
(1) NaH for claiming 10 parts of PEO-PPO-PEO to be dissolved in pH=7.02PO4-NaHPO4In buffer solution, being slowly stirred makes
It is sufficiently expanded, and heat cross-linking is carried out at 50 DEG C and forms cross-linked gel, spare;
(2) weighed 100 parts of sodium hyaluronates are added to the buffer solution (NaH of isotonic pH=72PO4-NaHPO4) in,
Addition concentration is 2% mannitol, and be slowly stirred expands it sufficiently at room temperature;
(3) the obtained cross-linked gel of step (1) and the obtained sodium hyaluronate gel of step (2) are sufficiently mixed, in room
It is solidifying that temperature lower ultrasonic (ultrasonic power 1000W) obtains sodium hyaluronate-sodium carboxymethylcellulose-(PEO-PPO-PEO) crosslinking for 30 minutes
Glue;
(4) after pouring nitrogen deoxygenation into system 1 hour, sterilizing is fitted into syringe.
Embodiment 5
Rheology testing
Using the elasticity of rotary vertebral plate rheometer (TA Instruments, model AR2000ex) detection adhesive gel
Modulus (G ') and viscous modulus (G ") variation with temperature.According to embodiment 1-3 preparation method be made injectable gel and
Blank control group is injected 1mL gel on the plane aluminium sheet that diameter is 40mm using duplex injection device, sample gap length
It is set as 1mm, is tested at different ambient temperatures, the frequency of related rheometer parameter are as follows: 1rads-1, testing result is such as
Shown in table 1-4.
The embodiment 1-4 preparation produced is removed this at different temperatures, uses rheometer (Discovery Hybrid rheology
Instrument -3- (DHR) measures the viscosity of each preparation, and test condition is as follows:
Shear rate: 10-5-1000 (l/s) measures temperature T=243K to T=313K.
The modulus of the preparation of 1 embodiment 1 of table at different temperatures and specific viscosity are tested
Temperature | Elastic modulus G ' (Pa) | Viscous modulus G " (Pa) | Specific viscosity (Ps) |
T=243K | 92.3±0.6 | 24.1±0.4 | 869.4 |
T=253K | 90.4±0.3 | 22.8±0.6 | 872.3 |
T=273K | 89.2±0.8 | 22.4±0.3 | 886.5 |
T=295K | 88.3±0.2 | 20.4±0.2 | 892.4 |
T=313K | 74.2±0.5 | 19.8±0.2 | 900.6 |
The modulus of the preparation of 2 embodiment 2 of table at different temperatures and specific viscosity are tested
The modulus of the preparation of 3 embodiment 3 of table at different temperatures and specific viscosity are tested
Temperature | Elastic modulus G ' (Pa) | Viscous modulus G " (Pa) | Specific viscosity (Ps) |
T=243K | 88.2±0.4 | 22.1±0.2 | 863.2 |
T=253K | 86.3±0.2 | 20.4±0.1 | 872.1 |
T=273K | 82.3±0.4 | 19.2±0.3 | 884.6 |
T=295K | 76.2±0.4 | 18.6±0.2 | 904.2 |
T=313K | 68.2±0.5 | 16.4±0.1 | 943.2 |
The modulus of the preparation of 4 blank control group of table at different temperatures and specific viscosity are tested
Temperature | Elastic modulus G ' (Pa) | Viscous modulus G " (Pa) | Specific viscosity (Ps) |
T=243K | 518.2±0.4 | 22.1±0.2 | 83.2 |
T=253K | 506.3±0.2 | 20.4±0.1 | 102.1 |
T=273K | 406.3±0.4 | 19.2±0.3 | 124.6 |
T=295K | 232.2±0.4 | 18.6±0.2 | 426.2 |
T=313K | 88.2±0.5 | 16.4±0.1 | 882.6 |
From the point of view of from table 1 to the result of table 4, for being added to preparation of the sodium carboxymethylcellulose as crosslinking agent in gel
(embodiment 1-3), when the temperature decreases, rheological property are almost unchanged, for being not added with sodium carboxymethylcellulose as crosslinking
The preparation (blank control group) of agent, when temperature is reduced to T=273K by T=313K, elastic modulus G ' gradually increases, is sticky
Modulus G " is gradually decreased, and specific viscosity gradually decreases, and rheological property is gradually deteriorated with the reduction of temperature.
The above is the preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned implementation
Invention is explained in detail for example, for those skilled in the art, still can be to foregoing embodiments
The technical solution of record is modified or equivalent replacement of some of the technical features.It is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of sodium hyaluronate composition, including following components: sodium hyaluronate or its physiologically acceptable salt, mannitol, poly- (second two
Alcohol)-poly- (propylene glycol)-poly(ethylene glycol) (PEO-PPO-PEO), sodium carboxymethylcellulose, buffer solution, water for injection.
2. sodium hyaluronate composition as described in claim 1, wherein the sodium hyaluronate or its physiologically acceptable salt has
Molecular weight is 500-2500kDa, preferably 800-2000kDa, more preferably 1000-1500kDa.
3. sodium hyaluronate composition as described in claim 1, wherein the PEO-PPO-PEO has the following structure:
Wherein x, z are the number within 2-100, the number within preferably 10-80;Y be 15-60 within number, preferably 20-50 with
Interior number.
4. sodium hyaluronate composition as described in claim 1, wherein when sodium hyaluronate forming salt, preferably its sodium salt.
5. sodium hyaluronate composition as described in claim 1, in which: with mass fraction ratio, sodium hyaluronate or its be physiologically subjected to
Salt and poly- (the propylene glycol)-poly(ethylene glycol) of poly(ethylene glycol)-ratio be (100-500): (10-50).
6. sodium hyaluronate composition as described in claim 1, with mass fraction ratio, wherein sodium carboxymethylcellulose and sodium hyaluronate or
The ratio of its physiologically acceptable salt is (10-50): (50-100), preferably 1:80, more preferably 1:60.
7. sodium hyaluronate composition as described in claim 1, wherein the buffer solution maintains the pH of composition in 5 and 8.5
Between, between more preferably 6.8 and 8, between most preferably 7.0 and 8, wherein suitable buffer solution can be selected from phosphorus
Hydrochlorate buffer solution, for example, NaH2PO4-NaHPO4, acetate buffer solution, benzoate buffer solution, Citrate buffer
Solution, maleate buffer solution, Tartrate buffer solution.
8. sodium hyaluronate composition as described in claim 1, wherein the weight based on sodium hyaluronate or its physiologically acceptable salt
Amount, the concentration of mannitol can less than 3%, for example, concentration existing for mannitol can for 2.8%, 2.5%, 2%, 1.6%,
1.5%, 1.2%, 1.0%, 0.8%, 0.5%.
9. the preparation method of sodium hyaluronate composition as described in claim 1, includes the following steps:
(1) Cross-linked gel is prepared;
Poly- (the propylene glycol)-poly(ethylene glycol) of poly(ethylene glycol)-is added into the buffer solution of pH=7.0, being slowly stirred makes it
Sufficiently expansion, sodium carboxymethylcellulose is added into system, and heat cross-linking is carried out at 50 DEG C and forms cross-linked gel, spare;
(2) sodium hyaluronate gel is prepared
Sodium hyaluronate is added in the buffer solution of isotonic pH=7, mannitol is added, being slowly stirred expands it sufficiently;
(3) the obtained cross-linked gel of step (1) and the obtained sodium hyaluronate gel of step (2) are sufficiently mixed, ultrasound obtains
Sodium hyaluronate-sodium carboxymethylcellulose-(PEO-PPO-PEO) cross-linked gel;Wherein the ultrasonic power is 1000-3000W, is surpassed
Sound temperature is -50 DEG C of room temperature, and ultrasonic time is 30min-1 hours;
(4) nitrogen deoxygenation is poured into system, is fitted into syringe after sterilizing.
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CN106074218A (en) * | 2016-06-22 | 2016-11-09 | 南京天朗制药有限公司 | Thermosensitive hydrogel injection smoothing wrinkle agent |
CN107811963A (en) * | 2016-09-13 | 2018-03-20 | 上海庚丰医药化工有限公司 | Soluble microneedle device and its application |
CN108744054A (en) * | 2018-06-15 | 2018-11-06 | 北京水元生生物科技有限公司 | A kind of injection-type beauty and shaping facial bulking agent compositions gel and preparation method thereof |
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2019
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US20120020932A1 (en) * | 2010-07-02 | 2012-01-26 | Zimmer Orthobiologics, Inc. | Thermosensitive hydrogel composition and method |
CN106074218A (en) * | 2016-06-22 | 2016-11-09 | 南京天朗制药有限公司 | Thermosensitive hydrogel injection smoothing wrinkle agent |
CN107811963A (en) * | 2016-09-13 | 2018-03-20 | 上海庚丰医药化工有限公司 | Soluble microneedle device and its application |
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Application publication date: 20190927 |