CN109278219A - A kind of microneedles template and the preparation method and application thereof - Google Patents
A kind of microneedles template and the preparation method and application thereof Download PDFInfo
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- CN109278219A CN109278219A CN201811351425.1A CN201811351425A CN109278219A CN 109278219 A CN109278219 A CN 109278219A CN 201811351425 A CN201811351425 A CN 201811351425A CN 109278219 A CN109278219 A CN 109278219A
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- CN
- China
- Prior art keywords
- micropore
- microneedles
- epoxy resin
- template
- micropin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
- A61M2037/0023—Drug applicators using microneedles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
- A61M2037/0053—Methods for producing microneedles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
- A61M2037/0061—Methods for using microneedles
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Heart & Thoracic Surgery (AREA)
- Hematology (AREA)
- Dermatology (AREA)
- Medical Informatics (AREA)
- Anesthesiology (AREA)
- Biomedical Technology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Media Introduction/Drainage Providing Device (AREA)
Abstract
The present invention relates to a kind of microneedles templates and the preparation method and application thereof, belong to dosage form equipment technical field.The microneedles template is made of epoxy resin film, is equipped with vertically arranged microwell array in epoxy resin film surface；Micropore is in inverted cone body, and tip is vertically on the inside of film；Micropin needle body forms in micropore in micropin preparation process.Compared with prior art, the micropore homogeneity of microneedles template of the present invention is good, and template is tough and tensile durable, can be used for the preparation of medicine, beauty treatment fields bio-soluble micropin, and prepares micropin and can be used for percutaneous dosing or transdermal processing.The making material of microneedles template is single, simple process, and solidification is convenient, with curing agent match can self-defoaming, easy mold release preparation efficiency is high, and easily realizes production automation.Template performance shrinkage is low, and chemical property is stablized, and cost is more much lower than the prior art on the market.
Description
Technical field
The present invention relates to a kind of microneedles templates and the preparation method and application thereof, belong to dosage form equipment technical field.
Background technique
Cutaneous penetration is a kind of novel administration mode, it can to avoid caused by oral administration liver first-pass effect and
Degradation of the stomach and intestine to drug avoids drug administration by injection bring pain etc., therefore has obtained quick development.But due to skin angle
The transmission rates of the barrier action of matter layer, most of preparation capable of permeating skin are low, and effective treatment concentration is far not achieved.It is asked to solve this
Topic, people use a variety of physics, chemical method to promote the percutaneous absorbtion of drug.Wherein, micropin is as a kind of novel warp
Skin medicine-feeding technology increasingly causes to pay close attention to.
Micropin production method mainly has chemical etching method, photoetching process, laser cutting method and template method of forming etc. at present.Micropin
Template takes on a key player in the preparation process of micropin.Current microneedles template mainly includes silicon wafer template, poly- diformazan
Radical siloxane (PDMS) template and the microneedles template made using the inorganic material such as gypsum, boccaro or composite material as blank.Its
Middle silicon micropin mold is prepared with microelectronics system facture and chemical etching method processing, the former operating process is complicated, the latter
It is difficult to prepare the sharp keen micropin in tip；The preparation of PDMS micropin mold need to first use chemical etching method, photoetching process, laser cutting method
Deng, solid micropin is prepared with silicon materials or metal material, then with form micropin mold preparation PDMS reversion mold, the technology need
First there is molding solid micropin mold cooperation that could prepare, influences the acutance of pin hole tip and preparation efficiency is low, complex process, at
This is higher；The hard materials such as gypsum, boccaro, which prepare micropin mold, to carry out bundle hole by pore tool, it is difficult to ensure that pin hole is uniform
Property and the acutance and being unsuitable for of tip prepare and soluble carry medicine micropin.
Summary of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of microneedles templates and the preparation method and application thereof.
The technical solution adopted by the present invention are as follows:
A kind of microneedles template is the epoxy resin film that micropore is arranged vertically on a side surface；The micropore is in the circle that stands upside down
Cone or conoid, tip is vertically on the inside of epoxy resin film.
The micropore of the microneedles template is to be formed by metal micro-needle in epoxy resin film surface rolling, the array of micropore
The parameter of distribution parameter and epoxy resin film is determined by shape, size and the array of metal micro-needle.The array distribution parameter of micropore
Including hole depth, basal diameter, spacing and quantity；The dimensional parameters of epoxy resin film include epoxy resin film thickness and epoxy resin
The side area of micropore is disposed on film.
With a thickness of 1000 μm -5000 μm, the side area that micropore is disposed on epoxy resin film is the epoxy resin film
4cm2-10000cm2；The hole depth of the micropore is 200 μm -3000 μm, and the basal diameter of micropore is 100 μm -1000 μm；It is described
The spacing of micropore is 600 μm -10000 μm, and the quantity of the micropore is 1-200 needle.
Preferably, the epoxy resin film is disposed with the side of micropore with a thickness of 3000 μm -5000 μm on epoxy resin film
Area is 4cm2-6cm2；The hole depth of the micropore is 200 μm -500 μm, and the basal diameter of micropore is 200 μm -500 μm；It is described micro-
The spacing in hole is 1700 μm -2000 μm, and the quantity of the micropore is 140 needles.
The present invention can adjust the shape, size and array of micropin according to the actual situation, design the micro- of Different structural parameters
Needle mould plate.
A kind of preparation method of microneedles template, including the following steps:
1) epoxide-resin glue and curing agent glue are mixed to form drop glue according to mass ratio 2-4:1, stirring is interior without drawing to drop glue
Silk and it is fully transparent, formed epoxy resin film, solidify 1-3h under the conditions of 40-70 DEG C, epoxy resin film made to enter maturation stage；
2) metal micro-needle is placed in the epoxy resin film surface for the maturation stage that step 1) is prepared, is uniformly pressed,
3-5h is placed under room temperature, obtains the uniform microneedles template of thickness, encapsulation at room temperature is placed in and saves.
The microneedles template is applied to solution-casting method and prepares micropin product.
For preparing bio-soluble macromolecule micropin, including the following steps: 1) by macromolecule soluble material with it is small
2h or more is stood after peptide mixing, obtains mixed liquor；2) at room temperature, a dropping step 1 on the micropore of microneedles template) be prepared
Mixed liquor guarantees that micropore is completely covered in mixed liquor, is vacuum-treated 10-30min, and micropin needle body forms in micropore；3) by micropore
The microneedles template that mixed liquid is completely covered is placed in ventilation natural air drying, demoulds drying, it is micro- to obtain bio-soluble macromolecule
Needle, cryo-conservation after sealing.
The macromolecule soluble material be carboxymethyl cellulose, hyaluronic acid, chitosan, maltose, sodium alginate,
The mixing of one or more of polyvinyl alcohol, fibroin, chondroitin sulfate.
The beneficial effects of the present invention are: the micropore homogeneity on microneedles template of the invention is good, and microneedles template is tough and tensile
Durable, no physiological side effects are harmless, can be used for the preparation of medicine, beauty treatment fields bio-soluble micropin, and prepare
Micropin can be used for percutaneous dosing or transdermal processing.The making material of microneedles template is single, simple process, and solidification is convenient, and solid
Agent match can self-defoaming, easy mold release preparation efficiency is high, and easily realizes production automation.Template performance shrinkage is low, changes
It learns property to stablize, cost is more much lower than the prior art on the market.
Detailed description of the invention
Fig. 1 is microneedles template schematic diagram；
Fig. 2 is molding micropin schematic diagram；
Fig. 3 is microneedles template and micropin preparation flow figure；
Fig. 4 (a) is the top view of microneedles template Zeiss microphoto in embodiment 2；
Fig. 4 (b) is the sectional drawing of microneedles template Zeiss microphoto in embodiment 2；
Fig. 5 is hyaluronic acid micropin fluorescence micrograph.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Microneedles template prepared by the present invention is as shown in Figure 1, molding micropin is as shown in Figure 2.Microneedles template and micropin preparation stream
Journey is as shown in Figure 3.
Embodiment 1
Highly 300 μm, 300 μm of bottom diameter, 1700 μm of spacing, the microneedles template production of 10 × 14 arrays, steps are as follows:
1) low molecular weight bisphenol A type epoxy resin glue (A) is mixed with amine curing agent glue (B) according to mass ratio 2.5:1,
It is fully transparent without wire drawing inside stirring to drop glue, solidify 90min under the conditions of 50 DEG C, makes it into maturation stage.
2) prepared metal micro-needle is placed on the epoxy resin film of maturation stage, uniformly presses, places 5h under room temperature,
Obtain the uniform microneedles template of thickness.
3) measurement gained microneedles template thickness is put in encapsulation at room temperature and is saved, and marks microneedles template dimensional parameters.
The parameter of above-mentioned microneedles template be height 300 ± 10 μm, 300 ± 10 μm of bottom diameter, 1700 μm of spacing, array micropin number 10 × 14.
Embodiment 2
Highly 500 μm, 500 μm of bottom diameter, 1800 μm of spacing, 10 × 14 gusts of microneedles template production.Steps are as follows:
1) low molecular weight bisphenol A type epoxy resin glue (A) is mixed with amine curing agent glue (B) according to mass ratio 3:1, is stirred
Mix to drop glue inside it is fully transparent without wire drawing, solidify 1h under the conditions of 70 DEG C, make it into maturation stage.
2) prepared metal micro-needle is placed on the epoxy resin film of maturation stage, uniformly presses, places 3h under room temperature,
Obtain the uniform microneedles template of thickness.
3) measurement gained microneedles template thickness is put in encapsulation at room temperature and is saved, and marks microneedles template dimensional parameters.
The parameter of above-mentioned microneedles template be height 500 ± 10 μm, 500 ± 10 μm of bottom diameter, 1800 μm of spacing, array micropin number 10 × 14.
The epoxy resin microneedles template Zeiss microphoto of 500 μm of height, 500 μm of bottom diameter, 1800 μm of spacing in embodiment 2
Top view and sectional drawing such as Fig. 4 (a) and Fig. 4 (b) shown in
The metal micro-needle of the microneedles template prepared in above-mentioned two embodiment is customization, 300 μm and 500 μm of height, bottom diameter
300 μm and 500 μm, 1700 μm and 1800 μm of spacing, 10 × 14 arrays.
Compliance test result:
The preparation of macromolecule soluble transparent matter acid micropin
The preparation of polymer hyaluronic acid solubility micropin, steps are as follows:
1) selecting molecular weight is the hyaluronic acid of 10kDa and 100kDa, is separately added into suitable ultrapure water, it is prepared
At 5% hyaluronic acid solution, 2h or more is stood after mixing evenly, 4 DEG C of refrigerations is placed it in, stands overnight, fill its water suction
Divide and is expanded to gel, it is spare.
2) at room temperature, molecular weight is added dropwise respectively for the hyaluronic acid solution that 10kDa and 100kDa concentration is 5%
1ml (according to drugloading rate, microneedles template area and required microneedle patch thickness, can adjust the number that solution is added dropwise) is in cleaning
On the micropore of microneedles template, guarantees that micropore is completely covered in mixed liquor, be vacuum-treated 30min.
3) microneedles template is placed in ventilation natural air drying, demoulds drying, cryo-conservation is spare after sealing.
Highly 500 μm, 500 μm of bottom diameter, 1800 μm of spacing molecular weight be 10kDa hyaluronic acid micropin fluorescence microscopy shine
Piece is as shown in Figure 5.
Claims (8)
1. a kind of microneedles template, which is characterized in that the microneedles template is the asphalt mixtures modified by epoxy resin for being arranged vertically micropore on a side surface
Adipose membrane；The micropore is in inverted cone body, and tip is vertically on the inside of epoxy resin film.
2. a kind of microneedles template according to claim 1, which is characterized in that the hole depth of the micropore is 200 μm of -3000 μ
M, the basal diameter of micropore are 100 μm -1000 μm；The spacing of the micropore is 600 μm -10000 μm.
3. a kind of microneedles template according to claim 1 or 2, which is characterized in that the epoxy resin film is with a thickness of 1000 μ
M-5000 μm, the side area that micropore is disposed on epoxy resin film is 4cm2-10000cm2。
4. the preparation method of claims 1 or 2 or 3 microneedles templates, characterized in that it comprises the following steps:
1) epoxide-resin glue and curing agent glue are mixed to form drop glue according to mass ratio 2-4:1, in stirring to drop glue without wire drawing and
It is fully transparent, epoxy resin film is formed, solidifies 1-3h under the conditions of 40-70 DEG C, epoxy resin film is made to enter maturation stage；
2) metal micro-needle is placed in the epoxy resin film surface for the maturation stage that step 1) is prepared, is uniformly pressed, Yu Chang
Temperature is lower to place 3-5h, obtains the uniform microneedles template of thickness, is placed in encapsulation at room temperature and saves.
5. a kind of preparation method of microneedles template according to claim 4, which is characterized in that the microneedles template it is micro-
The array distribution parameter in hole and the dimensional parameters of epoxy resin film are determined by the shape, size and array of metal micro-needle.
6. claims 1 or 2 or 3 microneedles templates, which are applied to solution-casting method, prepares micropin product.
7. application according to claim 6, which is characterized in that when preparing bio-soluble macromolecule micropin, including it is following
Step:
1) 2h or more is stood after mixing macromolecule soluble material with small peptide, obtains mixed liquor；
2) at room temperature, a dropping step 1 on the micropore of microneedles template) mixed liquor that is prepared, guarantee that mixed liquor is completely covered
Micropore, is vacuum-treated 10-30min, and micropin needle body forms in micropore；
3) micropore is mixed the microneedles template that liquid is completely covered and is placed in ventilation natural air drying, demould drying, obtaining biology can
Soluble macromolecular micropin, cryo-conservation after sealing.
8. application according to claim 7, which is characterized in that the macromolecule soluble material is carboxymethyl cellulose
One or both of element, hyaluronic acid, chitosan, maltose, sodium alginate, polyvinyl alcohol, fibroin, chondroitin sulfate
The above mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811351425.1A CN109278219A (en) | 2018-11-14 | 2018-11-14 | A kind of microneedles template and the preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811351425.1A CN109278219A (en) | 2018-11-14 | 2018-11-14 | A kind of microneedles template and the preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110153651A (en) * | 2019-05-13 | 2019-08-23 | 大连理工大学 | Big L/D ratio planar metal microneedle array, preparation method and its clamping are pierced into auxiliary device |
| CN114147892A (en) * | 2021-10-28 | 2022-03-08 | 吉林大学 | Preparation method of bionic high-length-diameter ratio cilium |
| CN114558992A (en) * | 2022-02-23 | 2022-05-31 | 浙江大学 | Method for manufacturing micro-perforated metal plate |
| CN115501474A (en) * | 2022-09-16 | 2022-12-23 | 深圳高性能医疗器械国家研究院有限公司 | Preparation method of soluble microneedle adhesive film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008006178A (en) * | 2006-06-30 | 2008-01-17 | Fujifilm Corp | Manufacturing method and device for microneedle sheet |
| JP2010030201A (en) * | 2008-07-30 | 2010-02-12 | Toppan Printing Co Ltd | Manufacturing of needle-like body, needle-like body, and duplicate plate of needle-like body |
| CN101670611A (en) * | 2009-10-15 | 2010-03-17 | 上海交通大学 | Preparation method for preparing plaster mold of transdermal micro needle array |
| CN104844814A (en) * | 2015-05-29 | 2015-08-19 | 北京化工大学 | Microneedle template and preparation method thereof |
| JP2017071109A (en) * | 2015-10-06 | 2017-04-13 | 富士フイルム株式会社 | Die for resin molding, and method of making a resin molding using the same |
-
2018
- 2018-11-14 CN CN201811351425.1A patent/CN109278219A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008006178A (en) * | 2006-06-30 | 2008-01-17 | Fujifilm Corp | Manufacturing method and device for microneedle sheet |
| JP2010030201A (en) * | 2008-07-30 | 2010-02-12 | Toppan Printing Co Ltd | Manufacturing of needle-like body, needle-like body, and duplicate plate of needle-like body |
| CN101670611A (en) * | 2009-10-15 | 2010-03-17 | 上海交通大学 | Preparation method for preparing plaster mold of transdermal micro needle array |
| CN104844814A (en) * | 2015-05-29 | 2015-08-19 | 北京化工大学 | Microneedle template and preparation method thereof |
| JP2017071109A (en) * | 2015-10-06 | 2017-04-13 | 富士フイルム株式会社 | Die for resin molding, and method of making a resin molding using the same |
Non-Patent Citations (1)
| Title |
|---|
| 鞠涛: "《构思与创意的三维智造》", 30 September 2014, 中国环境出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110153651A (en) * | 2019-05-13 | 2019-08-23 | 大连理工大学 | Big L/D ratio planar metal microneedle array, preparation method and its clamping are pierced into auxiliary device |
| CN114147892A (en) * | 2021-10-28 | 2022-03-08 | 吉林大学 | Preparation method of bionic high-length-diameter ratio cilium |
| CN114558992A (en) * | 2022-02-23 | 2022-05-31 | 浙江大学 | Method for manufacturing micro-perforated metal plate |
| CN114558992B (en) * | 2022-02-23 | 2023-03-14 | 浙江大学 | Method for manufacturing micro-perforated metal plate |
| CN115501474A (en) * | 2022-09-16 | 2022-12-23 | 深圳高性能医疗器械国家研究院有限公司 | Preparation method of soluble microneedle adhesive film |
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