CN113790831A - Ultrafast-response breathable flexible pressure sensor and preparation method thereof - Google Patents

Ultrafast-response breathable flexible pressure sensor and preparation method thereof Download PDF

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CN113790831A
CN113790831A CN202111096476.6A CN202111096476A CN113790831A CN 113790831 A CN113790831 A CN 113790831A CN 202111096476 A CN202111096476 A CN 202111096476A CN 113790831 A CN113790831 A CN 113790831A
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pvp
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李元岳
任萌娜
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Qingdao University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
    • G01L1/142—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
    • G01L9/12—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in capacitance, i.e. electric circuits therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Power Engineering (AREA)
  • Measuring Pulse, Heart Rate, Blood Pressure Or Blood Flow (AREA)
  • Measuring Fluid Pressure (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Abstract

The invention belongs to the technical field of sensors, and relates to an ultrafast-response breathable flexible pressure sensor and a preparation method thereof, wherein a first PVP nanofiber thin film layer and a second PVP nanofiber thin film layer are oppositely arranged; the first electrode layer is attached to the inner side of the first PVP nanofiber thin film layer; the second electrode layer is attached to the inner side of the second PVP nanofiber thin film layer, and a PVP nanofiber film dielectric layer is arranged between the first electrode layer and the second electrode layer; the substrate and the dielectric layer of the breathable flexible pressure sensor are both PVP nanofiber membranes with micro-nano structures obtained by electrostatic spinning, the preparation process is simplified, the cost is low, large-area production can be realized, the sensitivity of the sensor is high, and the response time is short; the PVP nanofiber membrane is used in the breathable flexible pressure sensor, so that the whole device has good breathability and excellent flexibility, and the long-time wearing of a human body is facilitated to monitor the breathing condition of the human body and weak vital sign signals of the human body in real time.

Description

Ultrafast-response breathable flexible pressure sensor and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of sensors, and relates to an ultrafast-response breathable flexible pressure sensor and a preparation method thereof.
Background art:
the sensor is a device or apparatus which can sense the measured quantity and convert it into usable output signal according to a certain rule, and is an important means for obtaining information of measurement, measurement and control and intelligent automation system. A pressure sensor is usually composed of a pressure sensitive element and a signal processing unit. According to the signal conversion mechanism, the flexible pressure sensor is mainly classified into a piezoelectric type, a piezoresistive type and a capacitive type. The wearable system based on the flexible pressure sensors can continuously, non-invasively, real-timely and comfortably monitor vital sign signals of the body weight of a person, and provides important clinical information for disease diagnosis, prevention and rehabilitation health care. Particularly, the capacitive flexible pressure sensor has the advantages of high sensitivity, short response time, wide detection range, small hysteresis and the like, and is widely applied to a plurality of emerging wearable flexible electronic devices, such as human motion monitoring equipment, medical health equipment and the like in recent years.
At present, a commonly used technology for improving the sensitivity of a sensor is to introduce a microstructure, which can significantly improve the signal intensity and the sensing performance of the sensor, but the acquisition mode of the microstructure, such as a silicon reverse membrane method, a photolithography method, a reactive ion beam etching method and the like, is complex in preparation process, time-consuming and labor-consuming, is not beneficial to large-scale production, and thus limits the wide application of the microstructure. Polydimethylsiloxane (PDMS) film and polyethylene terephthalate (PET) are commonly used as substrates for flexible pressure sensors, but the substrates are air-tight, and inflammation symptoms can occur when the substrates are attached to the skin for a long time, and the sensitivity and response time of the sensors can be affected when the films are thick, for example, patent CN 111552381 a designs an electrode plated with gold on the PDMS substrate, and a capacitive pressure sensor using AgNWs/TPU (silver nanowire/thermoplastic polyurethane elastomer rubber) nanofiber film as a dielectric layer can improve the sensitivity of a low pressure state to a certain extent, but the response time is slow and the air permeability is poor; patent CN 110926663 a designs a flexible capacitive pressure sensor with a conductive nanofiber membrane obtained by chemical silver plating of a palladium source and a PAN (polyacrylonitrile) spun nanofiber membrane as an electrode and a nylon mesh as a dielectric layer, which has the advantages of simple preparation process and good air permeability, but the response time is not greatly improved.
The invention content is as follows:
the invention aims to overcome the defects of low response time, poor air permeability, complicated preparation steps and the like of a flexible pressure sensor in the prior art, and provides an air-permeable flexible pressure sensor with ultra-fast response time and a preparation method thereof.
In order to achieve the purpose, the ultra-fast response breathable flexible pressure sensor comprises a first PVP nanofiber thin film layer, a second PVP nanofiber thin film layer, a first electrode layer, a second electrode layer and a PVP nanofiber film medium layer; the first PVP nanofiber thin film layer and the second PVP nanofiber thin film layer are oppositely arranged; the first electrode layer is attached to the inner side of the first PVP nanofiber thin film layer; the second electrode layer is attached to the inner side of the second PVP nanofiber thin film layer, and a PVP nanofiber film dielectric layer is arranged between the first electrode layer and the second electrode layer.
Further, the first PVP nanofiber thin film layer, the second PVP nanofiber thin film layer and the PVP nanofiber thin film layer are all made of polyvinylpyrrolidone (PVP), and the nanofiber film with the micro-nano structure is obtained through electrostatic spinning.
Further, the first electrode layer and the second electrode layer are made of silver nanoparticles or one of silver nanowires, gold, copper foil and aluminum foil, and the silver nanowires are preferably selected.
The invention relates to a specific process for preparing an ultrafast-response breathable flexible pressure sensor, which comprises the following steps:
(1) firstly, adding 1g of polyvinylpyrrolidone (PVP) powder into 5g of N, N-Dimethylformamide (DMF) organic solvent, magnetically stirring for 12 hours at room temperature to prepare spinning solution, then adding the spinning solution into an injector, and carrying out electrostatic spinning to obtain a PVP nano-fiber membrane, wherein electrostatic spinning parameters are as follows: the spinning voltage is 14kV, the liquid inlet speed is 10mL/h, the receiving distance is 15cm, and the spinning time is 1 h; then, placing the prepared PVP nano fiber membrane in a heating table, drying for 10min at the temperature of 150 ℃, and then irradiating for 40min under a UV lamp to obtain a first PVP nano fiber membrane layer; preparing a second PVP nanofiber thin film layer by the same method;
(2) respectively spraying a first electrode layer and a second electrode layer on the first PVP nanofiber thin film layer and the second PVP nanofiber thin film layer;
(3) preparing a PVP nano fiber membrane medium layer by adopting the method in the step (1);
(4) and packaging the first PVP flexible nanofiber thin film layer with the first electrode layer, the PVP nanofiber film dielectric layer and the second PVP flexible nanofiber thin film layer with the second electrode layer in a sandwich structure through ultrasonic bonds in a mode that the electrode layers are opposite to each other to obtain the breathable flexible pressure sensor.
Compared with the prior art, the invention has the following beneficial effects: firstly, this flexible pressure sensor of ventilative formula's base and dielectric layer are the PVP nanofiber membrane that utilizes electrostatic spinning to obtain to have the micro-nano structure, and the preparation flow of traditional micro-structure has greatly been simplified, when having realized low-cost, the large tracts of land production of flexible pressure sensing device, because the porous structure of nanofiber membrane for nanofiber membrane is the pressure deformation more easily, has further improved the sensitivity (0.3 kPa) of sensor-1) And response time (-50 ms); and secondly, the PVP nanofiber membrane is applied to each component of the breathable flexible pressure sensor, so that the whole device has good breathability and excellent flexibility, and the device is beneficial to long-time wearing of a human body to monitor the breathing condition of the human body and weak vital sign signals of the human body in real time.
Description of the drawings:
fig. 1 is a schematic structural principle diagram of the ultra-fast response air-permeable flexible pressure sensor of the present invention.
Fig. 2 is a schematic diagram of a manufacturing process of the ultra-fast response air-permeable flexible pressure sensor of the present invention.
Fig. 3 is a capacitance response graph of the gas permeable flexible pressure sensor prepared according to the embodiment of the present invention at different pressures, where S is sensitivity.
Fig. 4 is a response time plot of a vented flexible pressure sensor prepared according to an embodiment of the present invention.
Fig. 5 is a 8000 cycle test result chart of the air-permeable flexible pressure sensor prepared according to the embodiment of the present invention.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example (b):
the structure of the breathable flexible pressure sensor in this embodiment is shown in fig. 1, and includes a first PVP nanofiber thin film layer, a second PVP nanofiber thin film layer, a first electrode layer, a second electrode layer, and a PVP nanofiber film dielectric layer; the first PVP nanofiber thin film layer and the second PVP nanofiber thin film layer are oppositely arranged; the first electrode layer is attached to the inner side of the first PVP nanofiber thin film layer; the second electrode layer is attached to the inner side of the second PVP nanofiber thin film layer, and a PVP nanofiber film dielectric layer is arranged between the first electrode layer and the second electrode layer.
The specific process for preparing the breathable flexible pressure sensor in the embodiment is as follows:
(1) adding 1g of PVP powder into 5g of N, N-Dimethylformamide (DMF) organic solvent, magnetically stirring for 12 hours at room temperature to prepare spinning solution, adding the spinning solution into an injector, and carrying out electrostatic spinning to obtain a PVP nanofiber membrane, wherein the spinning parameters are as follows: the spinning voltage is 14kV, the liquid inlet speed is 10mL/h, the receiving distance is 15cm, and the spinning time is 1 h; placing the prepared PVP nanofiber membrane in a heating table, drying at 150 ℃ for 10min, irradiating under a UV lamp for 40min to obtain a first PVP nanofiber membrane layer, and preparing a second PVP nanofiber membrane layer by adopting the same method;
(2) spraying commercial AgNWs (XFJ81, XFINAN) on the first PVP nano fiber film layer and the second PVP nano fiber film layer by using a bar-shaped air compressor (IS-50, rock field) as a first electrode layer and a second electrode layer respectively; after the first electrode layer and the second electrode layer were prepared, copper wires were used as conductive wires, and Silver Paste (SPI) was attached to the electrodes for testing the performance of the sensor.
(3) Preparing a PVP nano fiber membrane medium layer by adopting the method in the step (1);
(4) and taking the first PVP nanofiber thin film layer coated with the first electrode layer and the second PVP nanofiber thin film layer coated with the second electrode layer as an upper electrode and a lower electrode, selecting a PVP nanofiber membrane medium layer as a dielectric layer in the middle layer, carrying out ultrasonic bonding, and combining the three layers to obtain the breathable flexible pressure sensor.
The working principle of the flexible capacitive pressure sensor prepared in the embodiment is as follows: when the first flexible PVP nanofiber thin film layer and the second flexible PVP nanofiber thin film layer which are used as substrates are under pressure, the PVP nanofiber film dielectric layer deforms, the distance between the first electrode layer and the second electrode layer which are attached to the inner sides of the first flexible PVP nanofiber thin film layer and the second flexible PVP nanofiber thin film layer respectively changes along with the deformation, accordingly, the change of the capacitance value of the sensor is caused, the capacitance tester is connected through the outer guide wire to detect the change of the capacitance value, the stress condition of the sensor can be further reflected, and therefore pressure sensing is achieved.
The results of the performance test of the prepared air-permeable flexible pressure sensor are shown in fig. 3-5, and it can be seen from the graphs that the air-permeable flexible pressure sensor prepared in the embodiment has short response time and can still achieve the effect of quick response after extremely small pressure and multiple cycles.

Claims (4)

1. An ultra-fast response breathable flexible pressure sensor is characterized by comprising a first PVP nanofiber thin film layer, a second PVP nanofiber thin film layer, a first electrode layer, a second electrode layer and a PVP nanofiber film medium layer; the first PVP nanofiber thin film layer and the second PVP nanofiber thin film layer are oppositely arranged; the first electrode layer is attached to the inner side of the first PVP nanofiber thin film layer; the second electrode layer is attached to the inner side of the second PVP nanofiber thin film layer, and a PVP nanofiber film dielectric layer is arranged between the first electrode layer and the second electrode layer.
2. The ultra-fast-response breathable flexible pressure sensor according to claim 1, wherein the first PVP nanofiber thin film layer, the second PVP nanofiber thin film layer and the PVP nanofiber film medium layer are all made of polyvinylpyrrolidone, and the nanofiber film with a micro-nano structure is obtained through electrostatic spinning.
3. The ultra-fast responding gas-permeable flexible pressure sensor according to claim 2, wherein the first and second electrode layers are made of silver nanoparticles or one of silver nanowires, gold, copper foil, and aluminum foil, preferably silver nanowires.
4. The preparation method of the ultrafast-response breathable flexible pressure sensor according to claim 3, which is characterized by comprising the following specific preparation processes:
(1) firstly, adding 1g of polyvinylpyrrolidone powder into 5g of N, N-dimethylformamide organic solvent, magnetically stirring for 12 hours at room temperature to prepare spinning solution, then adding the spinning solution into an injector, and carrying out electrostatic spinning to obtain a PVP nanofiber membrane, wherein electrostatic spinning parameters are as follows: the spinning voltage is 14kV, the liquid inlet speed is 10mL/h, the receiving distance is 15cm, and the spinning time is 1 h; then, placing the prepared PVP nano fiber membrane in a heating table, drying for 10min at the temperature of 150 ℃, and then irradiating for 40min under a UV lamp to obtain a first PVP nano fiber membrane layer; preparing a second PVP nanofiber thin film layer by the same method;
(2) respectively spraying a first electrode layer and a second electrode layer on the first PVP nanofiber thin film layer and the second PVP nanofiber thin film layer;
(3) preparing a PVP nano fiber membrane medium layer by adopting the method in the step (1);
(4) and packaging the first PVP flexible nanofiber thin film layer with the first electrode layer, the PVP nanofiber film dielectric layer and the second PVP flexible nanofiber thin film layer with the second electrode layer in a sandwich structure through ultrasonic bonds in a mode that the electrode layers are opposite to each other to obtain the breathable flexible pressure sensor.
CN202111096476.6A 2021-09-18 2021-09-18 Ultrafast-response breathable flexible pressure sensor and preparation method thereof Pending CN113790831A (en)

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Cited By (8)

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CN114176597A (en) * 2021-12-17 2022-03-15 广东思谷智能技术有限公司 All-electric spinning high-air-permeability high-hydrophobicity friction nano sensor and preparation method thereof
CN114279601A (en) * 2021-12-24 2022-04-05 南京大学 Flexible nano-film pressure sensor and preparation method thereof
CN114354172A (en) * 2022-01-10 2022-04-15 浙江吉利控股集团有限公司 Fault detection method and device for oil-gas separator and computer readable storage medium
CN114526849A (en) * 2022-02-23 2022-05-24 重庆文理学院 Preparation method of non-woven fabric-based flexible pressure sensor
CN115323621A (en) * 2022-07-05 2022-11-11 华南理工大学 High-sensitivity wide-detection-range flexible sensing composite film and preparation method and application thereof
CN115607142A (en) * 2022-10-13 2023-01-17 青岛大学 Full-fiber-based pressure monitoring system
CN115901028A (en) * 2022-09-02 2023-04-04 河北工业大学 Flexible touch sensor with adhesive property and air permeability and preparation method thereof
WO2024187891A1 (en) * 2023-03-15 2024-09-19 中国科学院深圳先进技术研究院 Flexible pressure sensor and preparation method therefor

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WO2015027769A1 (en) * 2013-08-29 2015-03-05 天津工业大学 Novel enhancing electrostatic spinning nanofiber membrane, producing method thereof, and device applied to method
WO2016058109A1 (en) * 2014-10-13 2016-04-21 太仓苏纶纺织化纤有限公司 Preparation method for collagen modified superfine acrylic fibres
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