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CN102926135A - Biodegradable composite superfine fiber non-woven fabric and preparation method thereof - Google Patents

Biodegradable composite superfine fiber non-woven fabric and preparation method thereof Download PDF

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Publication number
CN102926135A
CN102926135A CN 201110238669 CN201110238669A CN102926135A CN 102926135 A CN102926135 A CN 102926135A CN 201110238669 CN201110238669 CN 201110238669 CN 201110238669 A CN201110238669 A CN 201110238669A CN 102926135 A CN102926135 A CN 102926135A
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pla
caprolactone
epsilon
poly
nonwoven fabric
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朱思君
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Toray Fibers and Textiles Research Laboratories China Co Ltd
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Toray Fibers and Textiles Research Laboratories China Co Ltd
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  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention discloses a polylactic acid/poly epsilon-caprolactone biodegradable composite superfine fiber non-woven fabric and a preparation method thereof. The non-woven fabric is composed of polylactic acid superfine fibers and poly epsilon-caprolactone superfine fibers, wherein the mass ratio of the polylactic acid superfine fibers to the poly epsilon-caprolactone superfine fibers is (1:9)-(9:1); and in the biodegradable composite superfine fiber non-woven, the polylactic acid superfine fibers to the poly epsilon-caprolactone superfine fibers are arranged in a mutually entangled and mutually woven mode. The non-woven fabric disclosed by the invention can be used for avoiding the problem of performance degradation in use caused by phase separation, and can be widely used in different fields of wound dressing, drug carriers, tissue engineering and the like.

Description

A kind of biodegradation composite ultrafine fiber nonwoven fabric and preparation method thereof
Technical field
The present invention relates to a kind of biodegradation composite ultrafine fiber nonwoven fabric and preparation method thereof, concrete, be a kind of PLA by the electrostatic spinning preparation/poly-epsilon-caprolactone biodegradation composite ultrafine fiber nonwoven fabric and preparation method thereof.
Background technology
In recent years, the Biodegradable high-molecular that has good biocompatibility and a Bioabsorbable is widely used in field of tissue engineering technology.Electrostatic spinning is that polymer solution or melt spray stretching and the spinning process of acquisition nano-scale fiber under electrostatic interaction.In recent years, and even electrostatic spinning has caused the extensive concern of countries in the world as a kind of novel processing method for preparing the superfine fibre nanofiber.With the fiber that electrostatic spinning technique makes, diameter can reach nanoscale, than the little several orders of magnitude of the fibre diameter that makes with conventional method.This superfine fibre has that specific area is large, porosity is high, draw ratio is large, fiber fine degree and a homogeneity advantages of higher.Use electrostatic spinning technique Biodegradable high-molecular can be prepared into the super-fine fiber material with high-specific surface area and porosity, and make it show better biocompatibility, degradability, regeneration induction and mechanical performance.Report with Biodegradable high-molecular electrospinning researchs such as PLA (PLA), poly-epsilon-caprolactone (PCL), PTMCs (PTMC) is a lot of at present, and concrete application comprises Wound dressing, pharmaceutical carrier and tissue engineering material etc.But under many circumstances, single its performance of a kind of material often is difficult to satisfy the requirement of using.At this moment, common solution is to adopt the method for blending and modifying.Yet, in use, because the difference of intermingling material compatibility is separated between intermingling material, may cause performance degradation.
PLA (PLA) is a kind of polymer with good biocompatibility and biodegradation character, is a class biomaterial of FDA authentication, not only have higher mechanical strength and modulus, and degradation speed is very fast.PCL also is a class biomaterial of FDA authentication, is a kind of semi-crystalline polymer with good biocompatibility, because the existence of its higher degree of crystallinity and nonpolar methylene, so that the PCL hydrophily is relatively poor and biodegradation is slow.The strand of PCL is comparatively soft, so toughness is higher but strength and modulus is little.Because the mechanical performance of both complementations and the greatest differences of biodegradation rate can be by regulating its degradation rate with PLA and PCL blend.Yet adopt the intermingling material of this method preparation in use, because PLA and PCL are separated, will cause performance degradation.
Consider above-mentioned reason, the present invention is PLA and PCL electrospinning simultaneously, utilizes the moving effect of whip of jet in the electrospinning process and entangled to each other, makes the PLA superfine fibre mutually compound with the PCL superfine fibre, acquisition PLA/PCL composite ultrafine fiber nonwoven fabric.By regulating the ratio of PLA and PCL, can effectively control the performance of the PLA/PCL composite ultrafine fiber nonwoven fabric that obtains.And since the present invention adopt PLA and PCL separately mode entangled to each other after the electrospinning fibroblast, that weave prepare the composite ultrafine fiber nonwoven fabric, the easy and simple to handle and problem that is separated of having avoided direct blend to cause.
Summary of the invention
The object of the present invention is to provide a kind of PLA by the electrostatic spinning preparation/poly-epsilon-caprolactone biodegradation composite ultrafine fiber nonwoven fabric and preparation method thereof, be used for satisfying the demand in the fields such as Wound dressing, pharmaceutical carrier and organizational project.
The invention provides a kind of biodegradation composite ultrafine fiber nonwoven fabric, be comprised of PLA superfine fibre and poly-epsilon-caprolactone superfine fibre, wherein, the mass ratio of PLA and poly-epsilon-caprolactone is 1: 9~9: 1; In the described this biodegradation composite ultrafine fiber nonwoven fabric, PLA superfine fibre and poly-epsilon-caprolactone superfine fibre are form entangled to each other, mutual braiding.
The average diameter of PLA superfine fibre and poly-epsilon-caprolactone superfine fibre is 100nm~2000nm in the above-mentioned this biodegradation composite ultrafine fiber nonwoven fabric.
This biodegradation composite ultrafine fiber nonwoven fabric provided by the invention is comprised of PLA and two kinds of Biodegradable materials of PCL, because PLA and PCL be in the good complementarity of the aspects such as mechanical property, degradation rate, they compoundly can effectively be obtained degradation rate and the marginal new bio degradable material of mechanical property.
The preparation method of a kind of biodegradation composite ultrafine fiber nonwoven fabric provided by the invention, adopt multi-nozzle electrospinning, PLA and poly-epsilon-caprolactone are being prepared into the Biodegradable composite superfine fiber nonwoven fabric with form entangled to each other, braiding in the fibroblast separately by electrostatic spinning; Wherein, the mass ratio of PLA and poly-epsilon-caprolactone is 1: 9~9: 1.
Among the above-mentioned preparation method, may further comprise the steps:
A, PLA and poly-epsilon-caprolactone be dissolved in respectively PLA spinning solution and the poly-epsilon-caprolactone spinning solution that forms stable homogeneous in the same solvent, wherein, the PLA mass concentration is 4%~12%, the poly-epsilon-caprolactone mass concentration is 6%~12%, solvent is a kind of and N in carrene or the chloroform, double solvents behind a kind of composite in dinethylformamide or DMA and the dimethyl sulfoxide (DMSO); Wherein, a kind of and DMA in carrene or the chloroform and a kind of mass ratio in the dimethyl sulfoxide (DMSO) are 1: 1~5: 1;
B, PLA spinning solution and the poly-epsilon-caprolactone spinning solution that makes among the step a is respectively charged in the different syringe of electrospinning device, spinning solution in the syringe extremely links to each other with one of high voltage source by the syringe metal needle, syringe is promoted by accurate sampling pump, with the spouting velocity of the spinning solution in the control syringe;
The ratio of c, the syringe by regulating PLA spinning solution and the concentration of poly-epsilon-caprolactone spinning solution and pack into PLA spinning solution and poly-epsilon-caprolactone spinning solution, being used for the PLA of electrospinning and the mass ratio of poly-epsilon-caprolactone is 1: 9~9: 1;
D, use metal deflector roll or flat board are as gathering-device, and another utmost point of high voltage source links to each other with gathering-device, and receiving range is 5~25cm;
The voltage to 5 of e, rising high voltage source~40KV, each spinning solution form jet from each syringe ejection respectively under the high voltage electric field effect; Form the composite ultrafine fiber nonwoven fabric that PLA superfine fibre and poly-epsilon-caprolactone superfine fibre form.
Above-mentioned receiving range is the beeline between the terminal line of a plurality of syringe needles and gathering-device.
Described solvent is preferably the double solvents of carrene and DMF; More preferably the mass ratio of carrene and DMF is 2: 1~4: 1.
The present invention has used a kind of simple and easy to do method to prepare PLA/PCL composite ultrafine fiber nonwoven fabric.Prepared PLA/PCL composite ultrafine fiber nonwoven fabric has the controllability of good biocompatibility and biodegradation rate, can effectively control the structure of prepared superfine fibre nonwoven cloth by regulating the electrospinning technological parameter.By the concentration of adjusting PLA spinning solution and poly-epsilon-caprolactone spinning solution and the ratio of the syringe of pack into PLA spinning solution and poly-epsilon-caprolactone spinning solution, can be easy with the mass ratio of PLA and poly-epsilon-caprolactone in the prepared composite ultrafine fiber nonwoven fabric an adjusting in 1: 9~9: 1, thereby control the degradation rate of prepared superfine fibre nonwoven cloth.PLA/PCL composite ultrafine fiber nonwoven fabric provided by the present invention can satisfy the different real needs of different field such as Wound dressing, pharmaceutical carrier and organizational project by the in advance design of above-mentioned parameter in the preparation process.
Before this, adopt different materials while electrospinning with the method for preparing composite fibre nonwoven cloth report to be arranged once also.Yet, with several different spinning solutions adopt identical parameter simultaneously electrospinnings often cause prepared composite fibre nonwoven cloth the problems such as the inhomogeneous and bad point of distribution of material is too much to occur.In order to address this problem, we have used PLA and the common double solvents of poly-epsilon-caprolactone to prepare respectively PLA spinning solution and poly-epsilon-caprolactone spinning solution and all can form without form defective and the composite ultrafine fiber nonwoven fabric that is evenly distributed to guarantee under identical electrospinning parameter PLA spinning solution and poly-epsilon-caprolactone spinning solution.
In addition, with existing with PLA and poly-epsilon-caprolactone in cosolvent blend then the technology of electrospinning compare, PLA/PCL composite ultrafine fiber nonwoven fabric provided by the present invention in the performance of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of effective control, the problem of the in use performance degradation that having avoided is separated causes.
Description of drawings
Fig. 1 is employed many shower nozzles electro-spinning equipment schematic diagram.
Fig. 2 is the stereoscan photograph (150 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of embodiment 1.
Fig. 3 is the stereoscan photograph (5000 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of embodiment 1.
Fig. 4 is the stereoscan photograph (150 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of Comparative Examples 1.
Fig. 5 is the stereoscan photograph (150 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of embodiment 2.
Fig. 6 is the stereoscan photograph (150 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of Comparative Examples 2.
Fig. 7 is the stereoscan photograph (150 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of embodiment 3.
Fig. 8 is the stereoscan photograph (150 *) of the prepared PLA/PCL composite ultrafine fiber nonwoven fabric of embodiment 4.
The specific embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
Employed poly-epsilon-caprolactone is that a kind of number-average molecular weight is 80,000 among the embodiment, and fusing point is 60 ℃ biodegradated polymer materal, available from Sigma-Aldrich; PLA is that a kind of number-average molecular weight is 100,000, and fusing point is 160 ℃ biodegradated polymer materal, available from Chemical Reagent Co., Ltd., Sinopharm Group; All the other medicines are available from Chemical Reagent Co., Ltd., Sinopharm Group.
The superfine fibre average diameter is by ESEM (JSM-6700F, JEOL, Japan) observation among the embodiment, and concrete method is that 100 data of observation are got its mean value.
In experimentation, used an as shown in Figure 1 electrospinning device of three shower nozzles (three syringes).
The preparation example of embodiment 1, PLA/PCL composite ultrafine fiber nonwoven fabric
The preparation of a, spinning solution
According to carrene/proportional arrangement double solvents of 2: 1 of DMF double solvents mass ratio; A certain amount of PLA is added in this double solvents, make the PLA solution of 8% (wt%); A certain amount of PCL is added in this double solvents, make the PCL solution of 10% (wt%);
B, electrostatic spinning
Two kinds of solution that step a is obtained are injected in three syringes of electrostatic spinning apparatus, wherein respectively add the PLA solution of 5 grams, 8% (wt%) in the syringe of both sides, add the PCL solution of 5 grams, 10% (wt%) in the middle syringe.The feeding rate of adjusting spinning solution is 100ul/min, receiving range (beeline between the terminal line of three syringe needles and gathering-device) is 15cm, open high voltage source, voltage is 15kV, open sampling pump, spray thread and be ejected on the collector, obtaining the PLA/PCL mass ratio at collector is 8: 5 PLA/PCL composite ultrafine fiber nonwoven fabric.Average fibre diameter in the gained PLA/PCL composite ultrafine fiber nonwoven fabric is about 620nm.
As shown in Figures 2 and 3, the photo under ESEM shows, the fibre morphology no significant defect in the PLA/PCL composite ultrafine fiber nonwoven fabric of gained, (thicker PCL fiber and thinner PLA fiber) distribution uniform.
The preparation example of Comparative Examples 1, defective PLA/PCL composite ultrafine fiber nonwoven fabric
The preparation of a, spinning solution
A certain amount of PLA is added in the DMF, make the PLA solution of 8% (wt%); A certain amount of PCL is added in the trifluoroethanol solvent, make the PCL solution of 10% (wt%);
B, electrostatic spinning
Two kinds of solution that step a is obtained are injected in three syringes of electrostatic spinning apparatus, wherein respectively add the PLA solution of 5 grams, 8% (wt%) in the syringe of both sides, add the PCL solution of 5 grams, 10% (wt%) in the middle syringe.The feeding rate of adjusting spinning solution is 100ul/min, and receiving range is 15cm, opens high voltage source, voltage is 15kV, open sampling pump, spray thread and be ejected on the collector, obtaining the PLA/PCL mass ratio at collector is 8: 5 PLA/PCL composite ultrafine fiber nonwoven fabric.
Although adopt PLA/N, dinethylformamide and PCL/ trifluoroethanol the system separately example of electrospinning success early have report, but as shown in Figure 4, photo under ESEM shows, when the two simultaneously during electrospinning because the spinning solution nature difference is larger, cause in the PLA/PCL composite ultrafine fiber nonwoven fabric of gained appearance obvious beading structure (defective).
The preparation example of embodiment 2, PLA/PCL composite ultrafine fiber nonwoven fabric
The preparation of a, spinning solution
According to carrene/proportional arrangement double solvents of 2: 1 of DMF double solvents mass ratio; A certain amount of PLA is added in this double solvents, make the PLA solution of 6% (wt%); A certain amount of PCL is added in this double solvents, make the PCL solution of 6% (wt%);
B, electrostatic spinning
Two kinds of solution that step a is obtained are injected in three syringes of electrostatic spinning apparatus, wherein respectively add the PCL solution of 5 grams, 6% (wt%) in the syringe of both sides, add the PLA solution of 5 grams, 6% (wt%) in the middle syringe.The feeding rate of adjusting spinning solution is 150ul/min, and receiving range is 15cm, opens high voltage source, voltage is 15kV, open sampling pump, spray thread and be ejected on the collector, obtaining the PLA/PCL mass ratio at collector is 1: 2 PLA/PCL composite ultrafine fiber nonwoven fabric.Average fibre diameter in the gained PLA/PCL composite ultrafine fiber nonwoven fabric is about 380nm.
As shown in Figure 5, the photo demonstration under ESEM, the fibre morphology no significant defect in the PLA/PCL composite ultrafine fiber nonwoven fabric of gained is evenly distributed.
The preparation example of Comparative Examples 2, defective PLA/PCL composite ultrafine fiber nonwoven fabric
The preparation of a, spinning solution
According to carrene/proportional arrangement double solvents of 2: 1 of DMF double solvents mass ratio; A certain amount of PCL is added in this double solvents, make the PCL solution of 4% (wt%); A certain amount of PLA is added in this double solvents, make the PLA solution of 6% (wt%);
B, electrostatic spinning
Two kinds of solution that step a is obtained are injected in three syringes of electrostatic spinning apparatus, wherein respectively add the PCL solution of 5 grams, 4% (wt%) in the syringe of both sides, add the PLA solution of 5 grams, 6% (wt%) in the middle syringe.The feeding rate of adjusting spinning solution is 100ul/min, and receiving range is 15cm, opens high voltage source, and voltage is 15kV, opens sampling pump, sprays thread and is ejected on the collector, and obtaining the PLA/PCL mass ratio at collector is 3: 4 PLA/PCL sample.
As shown in Figure 6, photo under ESEM shows, obvious pearl aggregate has appearred in the PLA/PCL composite ultrafine fiber nonwoven fabric of gained, and this can spin scope and cause owing to employed PCL spinning solution PCL content is lower than it.
The preparation example of embodiment 3, PLA/PCL composite ultrafine fiber nonwoven fabric
The preparation of a, spinning solution
According to carrene/proportional arrangement double solvents of 2: 1 of DMF double solvents mass ratio; A certain amount of PLA is added in this double solvents, make the PLA solution of 10% (wt%); A certain amount of PCL is added in this double solvents, make the PCL solution of 12% (wt%);
B, electrostatic spinning
Two kinds of solution that step a is obtained are injected in three syringes of electrostatic spinning apparatus, wherein respectively add the PCL solution of 5 grams, 12% (wt%) in the syringe of both sides, add the PLA solution of 5 grams, 10% (wt%) in the middle syringe.The feeding rate of adjusting spinning solution is 200ul/min, and receiving range is 15cm, opens high voltage source, voltage is 25kV, open sampling pump, spray thread and be ejected on the collector, obtaining the PLA/PCL mass ratio at collector is 5: 12 PLA/PCL composite ultrafine fiber nonwoven fabric.Average fibre diameter in the gained PLA/PCL composite ultrafine fiber nonwoven fabric is about 1990nm.
As shown in Figure 7, the photo demonstration under ESEM, the fibre morphology no significant defect in the PLA/PCL composite ultrafine fiber nonwoven fabric of gained is evenly distributed.
The preparation example of embodiment 4, PLA/PCL composite ultrafine fiber nonwoven fabric
The preparation of a, spinning solution
According to carrene/proportional arrangement double solvents of 4: 1 of DMF double solvents mass ratio; A certain amount of PLA is added in this double solvents, make the PLA solution of 6% (wt%); A certain amount of PCL is added in this double solvents, make the PCL solution of 8% (wt%);
B, electrostatic spinning
Two kinds of solution that step a is obtained are injected in three syringes of electrostatic spinning apparatus, wherein respectively add the PCL solution of 5 grams, 8% (wt%) in the syringe of both sides, add the PLA solution of 5 grams, 6% (wt%) in the middle syringe.The feeding rate of adjusting spinning solution is 100ul/min, and receiving range is 25cm, opens high voltage source, voltage is 30kV, open sampling pump, spray thread and be ejected on the collector, obtaining the PLA/PCL mass ratio at collector is 3: 8 PLA/PCL composite ultrafine fiber nonwoven fabric.Average fibre diameter in the gained PLA/PCL composite ultrafine fiber nonwoven fabric is about 380nm.As shown in Figure 8, the photo demonstration under ESEM, the fibre morphology no significant defect in the PLA/PCL composite ultrafine fiber nonwoven fabric of gained is evenly distributed.

Claims (6)

1. biodegradation composite ultrafine fiber nonwoven fabric, it is characterized in that: be comprised of PLA superfine fibre and poly-epsilon-caprolactone superfine fibre, wherein, the mass ratio of PLA and poly-epsilon-caprolactone is 1: 9~9: 1; In the described biodegradation composite ultrafine fiber nonwoven fabric, PLA superfine fibre and poly-epsilon-caprolactone superfine fibre are form entangled to each other, mutual braiding.
2. composite ultrafine fiber nonwoven fabric according to claim 1, it is characterized in that: the average diameter of described PLA superfine fibre and poly-epsilon-caprolactone superfine fibre is 100nm~2000nm.
3. method for preparing the composite ultrafine fiber of biodegradation described in the claim 1 nonwoven fabric, it is characterized in that: adopt multi-nozzle electrospinning, PLA and poly-epsilon-caprolactone are being prepared into the Biodegradable composite superfine fiber nonwoven fabric with form entangled to each other, braiding in the fibroblast separately by electrostatic spinning; Wherein, the mass ratio of PLA and poly-epsilon-caprolactone is 1: 9~9: 1.
4. preparation method according to claim 3, it is characterized in that: the method may further comprise the steps:
A, PLA and poly-epsilon-caprolactone are dissolved in respectively PLA spinning solution and the poly-epsilon-caprolactone spinning solution that forms respectively stable homogeneous in the same solvent, wherein, the mass concentration of PLA spinning solution is 4%~12%, the mass concentration of poly-epsilon-caprolactone spinning solution is 6%~12%, solvent is a kind of and N in carrene or the chloroform, double solvents behind a kind of composite in dinethylformamide or DMA and the dimethyl sulfoxide (DMSO); Wherein, a kind of and DMA in carrene or the chloroform and a kind of mass ratio in the dimethyl sulfoxide (DMSO) are 1: 1~5: 1;
B, PLA spinning solution and the poly-epsilon-caprolactone spinning solution that makes among the step a is respectively charged in the different syringe of electrospinning device, spinning solution in the syringe extremely links to each other with one of high voltage source by the injector tip metal needle, syringe is promoted by accurate sampling pump, with the spouting velocity of the spinning solution in the control syringe;
C, use metal deflector roll or flat board are as gathering-device, and another utmost point of high voltage source links to each other with gathering-device, and receiving range is 5~25cm;
The voltage to 5 of d, rising high voltage source~40KV, each spinning solution form jet from each syringe ejection respectively under the high voltage electric field effect; Form the composite ultrafine fiber nonwoven fabric that PLA superfine fibre and poly-epsilon-caprolactone superfine fibre form.
5. preparation method according to claim 4, it is characterized in that: solvent is carrene/DMF double solvents.
6. preparation method according to claim 5, it is characterized in that: carrene and DMF mass ratio are 2: 1~4: 1.
CN 201110238669 2011-08-09 2011-08-09 Biodegradable composite superfine fiber non-woven fabric and preparation method thereof Pending CN102926135A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104213331A (en) * 2014-09-12 2014-12-17 天津工业大学 Preparation method of electrostatic spinning polylactic acid nano-pore fiber membrane
CN112384650A (en) * 2018-07-09 2021-02-19 国立研究开发法人物质·材料研究机构 Nonwoven fabric, method for producing nonwoven fabric, and composition for electrospinning
CN113403750A (en) * 2021-06-28 2021-09-17 运鸿集团股份有限公司 Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask
GB2608471A (en) * 2021-06-28 2023-01-04 China Yunhong Holdings Co Ltd Method for preparing fully-degradable non-woven fabric by spun-bonding

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104213331A (en) * 2014-09-12 2014-12-17 天津工业大学 Preparation method of electrostatic spinning polylactic acid nano-pore fiber membrane
CN112384650A (en) * 2018-07-09 2021-02-19 国立研究开发法人物质·材料研究机构 Nonwoven fabric, method for producing nonwoven fabric, and composition for electrospinning
CN113403750A (en) * 2021-06-28 2021-09-17 运鸿集团股份有限公司 Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask
GB2608471A (en) * 2021-06-28 2023-01-04 China Yunhong Holdings Co Ltd Method for preparing fully-degradable non-woven fabric by spun-bonding
GB2608471B (en) * 2021-06-28 2024-03-27 China Yunhong Holdings Co Ltd Method for preparing fully-degradable non-woven fabric by spun-bonding

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Application publication date: 20130213