TWI718819B - Conductive fiber and method for fabricating the same - Google Patents

Abstract

A conductive fiber and a method for fabricating the conductive fiber are provided. The method for fabricating the conductive fiber includes following steps. A first solution is provided, where the first solution includes a spinnability polymer dissolved in a first solvent, wherein the weight ratio of the spinnability polymer to the first solvent is from 5:95 to 20:80. A second solution is provided, where the second solution includes a conductive material dispersed in a second solvent, wherein the weight ratio of the conductive material to the second solvent is from 5:95 to 20:80, wherein the shape of the conductive material is dendrite or snowflake like Next, a wet spinning process employing the first solution and the second solution is performed to obtain the conductive fiber.

Description

Conductive fiber and its manufacturing method

This disclosure relates to a conductive fiber and a manufacturing method of the conductive fiber.

In the textile fiber industry, conductive fiber is an important key material for manufacturing smart textiles and wearable devices. Traditional conductive fibers are mainly metal fibers, which have strength and rigidity, but do not have elasticity and stretchability, so they have poor wearing comfort.

Although traditional fibers used in clothing have better wearing comfort, they do not have conjugation properties because of their chemical structure and do not have conductive properties. In order to make traditional fibers have conductive properties, carbon black and polymer materials are generally mixed and extruded to form a masterbatch before spinning. However, this method needs to add more carbon black (above 50%), so that the fiber strength is reduced by too much carbon black addition. In addition, due to the poor compatibility of carbon black with polymers, phase separation is prone to occur, and conductivity is not easy to improve. Another way to make traditional fibers have conductive properties is to mix conductive agents with polymers to impart conductivity to the fibers, but the fiber processability and conductivity are relatively poor. In addition, when the traditional conductive agent is mixed with the polymer, a relatively large amount of the conductive agent needs to be added to have excellent conductive properties, which will increase the manufacturing cost.

Therefore, the industry needs a new type of conductive material to obtain conductivity Fiber and its manufacturing method to solve the problems encountered by the prior art.

According to an embodiment of the present disclosure, the present disclosure provides a method for manufacturing a conductive fiber, which includes the following steps. A first solution is provided, wherein the first solution includes a spinnable polymer dissolved in a first solvent, and the weight ratio of the spinnable polymer to the first solution is 5:95 to 20:80. A second solution is provided, wherein the second solution includes a conductive material dispersed in a second solvent, wherein the weight ratio of the conductive material to the second solution is 5:95 to 20:80; wherein the conductive material type Department of dendrite (dendrite) or snowflake-like (snowflake like). Then, the first solution and the second solution are subjected to a wet spinning process to obtain the conductive fiber.

According to another embodiment of the present disclosure, the present disclosure provides a conductive fiber. The conductive fiber includes a conductive material and a spinnable polymer, wherein the conductive material type includes dendrite or snowflake like, and the weight ratio of the spinnable polymer to the conductive material is 7:3 To 3:7, based on the total weight of the spinnable polymer and the conductive material.

1‧‧‧Central backbone

3, 9‧‧‧ lateral branches

5‧‧‧Accessories

7‧‧‧Branch

8‧‧‧Multi-fork branch point

10‧‧‧Conductive fiber

11‧‧‧Hollow part

12‧‧‧Spinnable polymer

13‧‧‧Shell

14‧‧‧Conductive material

15‧‧‧Elastic polymer

16‧‧‧Core

17‧‧‧Sheath

100‧‧‧Dendrite conductive material

200‧‧‧Snow-like conductive material

Figures 1-2 show the dendrite of the conductive material in the embodiment of the disclosure;

FIG. 3 is a schematic diagram of a snowflake-like shape of the conductive material according to the embodiment of the present disclosure;

Figure 4 is a schematic cross-sectional structure diagram of a solid conductive fiber according to an embodiment of the present disclosure;

FIG. 5 is a schematic cross-sectional structure diagram of the hollow conductive fiber according to the embodiment of the disclosure; as well as

Figure 6 is a schematic cross-sectional structure diagram of a conductive fiber with a core-sheath structure according to other embodiments of the present disclosure; and;

FIG. 7 is a schematic cross-sectional structure diagram of a conductive fiber with a core-sheath structure according to another embodiment of the present disclosure.

The following is a detailed description of the conductive fiber and the manufacturing method of the conductive fiber described in this disclosure. It should be understood that the following description provides many different embodiments or examples for implementing different aspects of the present disclosure. The specific elements and arrangements described below are only a brief description of the present disclosure. Of course, these are only examples and not the limitation of this disclosure. In addition, repeated reference numbers or labels may be used in different embodiments. These repetitions are only used to describe the disclosure simply and clearly, and do not represent any relevance between the different embodiments and/or structures discussed. Moreover, in the drawings, the shape, number, or thickness of the embodiments can be expanded, and are simplified or marked for convenience. Furthermore, the parts of each element in the drawing will be described separately. It is worth noting that the elements not shown or described in the figure are in the form known to those with ordinary knowledge in the technical field. In addition, the specific The embodiments are only for revealing specific ways of using the present disclosure, and they are not used to limit the present disclosure.

The present disclosure provides a conductive fiber and a manufacturing method of conductive fiber. By providing a novel conductive material to uniformly disperse it in a spinnable polymer structure, a network structure is formed by branching of the conductive material with a special shape, which can achieve low addition It also has the effect of high volume and low resistance; or it can be further combined with the addition of elastic polymers for wet spinning process. In this way, conductive fibers with conductive solid, hollow or core-sheath structures can be prepared. In addition, the conductive fiber described in this disclosure In addition to electrical conductivity, it can further improve the comfort and low impedance of wearing.

The present disclosure provides a manufacturing method of conductive fiber, which includes the following steps. A first solution is provided, wherein the first solution includes a spinnable polymer dissolved in a first solvent, and the weight ratio of the spinnable polymer to the first solution is 5:95 to 20:80 (for example, 7 : 93, 10:90, 12:88, 15:85, or 17:83). A second solution is provided, wherein the second solution includes a conductive material dispersed in a second solvent, and the weight ratio of the conductive material to the second solution is 5:95 to 20:80 (for example, 7:93, 10 : 90, 12: 88, 15: 85, or 17: 83); wherein the conductive material is dendrite or snowflake like. Then, the first solution and the second solution are subjected to a wet spinning process to obtain the conductive fiber.

According to an embodiment of the present disclosure, the conductive material may be a metal material.

According to an embodiment of the present disclosure, the conductive material is a dendrite conductive material or a snowflake-like conductive material.

Please refer to FIG. 1, the dendritic conductive material 100 in the present disclosure refers to the conductive material having a central stem 1 and a plurality of side branches 3. Wherein, the minimum included angle θ between the side branch and the central trunk can be 30 degrees to 90 degrees. Still referring to Figure 1, the length (L) of the dendritic conductive material is defined as the maximum distance of the central backbone, and the diameter (D) of the dendritic conductive material is defined as the conductive The maximum width of the material in the direction perpendicular to the central trunk. According to an embodiment of the present disclosure, the dendritic conductive material may have a length to diameter ratio (L/D) ranging from about 5 to 15, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. According to some embodiments of the present disclosure, the length (L) of the dendrite conductive material may be 1 μm to 20 μm, and the diameter (D) may be 0.3 μm to 5 μm. According to the embodiment of the present disclosure, please refer to FIG. 2. The dendritic conductive material 100 of the present disclosure has a central stem 1, and its side branch 3 may also have a plurality of sub-side branches. )5. According to an embodiment of the present disclosure, the sub-side branch 5 may also be branched (not shown).

Please refer to FIG. 3, the snowflake-shaped conductive material 200 in the present disclosure refers to a conductive material having at least one multifurcated branch point 8. Among them, the multi-branched branch point 8 refers to a tetrafurcated branch point, a pentafurcated branch point, or a six-furced branch point. Still referring to FIG. 3, the branches 7 on the snowflake-shaped conductive material 200 of the present disclosure may also have a plurality of side branches 9.

According to the embodiment of the present disclosure, the conductive material can be a metal or an alloy of the metal, wherein the metal can be gold, silver, copper, aluminum, nickel, or an alloy thereof. For example, the conductive material can be gold, silver, copper, aluminum, nickel, gold-containing alloys, silver-containing alloys, copper-containing alloys, aluminum-containing alloys, nickel-containing alloys, or a combination of the foregoing.

According to the embodiment of the present disclosure, the weight ratio of the spinnable polymer to the conductive material is 7:3 to 3:7 (for example, 3.5:6.5, 4:6, 5:5, 6:4).

According to an embodiment of the present disclosure, the solid content of the first solution may be about 5 wt% to 20 wt%; and the solid content of the second solution may be about 5 wt% to 20 wt%.

According to the embodiment of the present disclosure, the spinnable polymer can be polyvinyl alcohol, sodium alginate, carboxy methyl cellulose, polyurethane, polyester (polyvinyl alcohol), sodium alginate, carboxy methyl cellulose, polyurethane, and polyester. polyester), polystyrene-butadiene-styrene resin (SBS), polyacrylonitrile-butadiene rubber (NBR), or a combination of the above. In addition, according to some embodiments of the present disclosure, the weight average molecular weight of the spinnable polymer may be 10,000 g/mol to 500,000 g/mol), for example, 50,000 g/mol to 300,000 g/mol. According to an embodiment of the present disclosure, the first solvent and the second solvent may be the same or different. For example, the first solvent and the second solvent can be deionized water, dimethyl formamide, dimethyl acetamide, and dimethylsulfone. , Tetrahydrofuran (tetrahydrofuran), dichloromethane (dichloromethane), methyl ethyl ketone (methylethyl ketone), or chloroform (chloroform). According to the embodiment of the present disclosure, the first solvent and the second solvent are mutually soluble.

According to an embodiment of the present disclosure, the weight ratio of the first solution to the second solution is 1:2 to 3:1.

According to an embodiment of the present disclosure, the present disclosure provides a conductive fiber. The conductive fiber includes a conductive material and a spinnable polymer, and the weight ratio of the spinnable polymer to the conductive material is 7:3 to 3:7, (for example, 3.5:6.5, 4:6, 5:5, or 6:4). If the weight ratio of the spinnable polymer is too low, it is easy to cause the conductive material in the resulting conductive fiber to be exposed from the fiber (that is, it cannot be fiberized); and if the weight ratio of the conductive material is too low, it is easy to cause the resulting conductive fiber The conductivity drops very much To non-conductive. According to the embodiment of the present disclosure, the fiber fineness of the conductive fiber of the present disclosure can be 0.3mm to 2mm (for example, 0.3mm to 1.0mm, 0.4mm to 0.9mm, or 0.5mm to 0.8mm), and the resistance value can be 9Ω/cm To 300Ω/cm.

According to an embodiment of the present disclosure, please refer to FIG. 4, which is a schematic cross-sectional structure diagram of the conductive fiber 10 of the present disclosure. As shown in FIG. 4, the conductive fiber 10 can be a solid conductive fiber, and the conductive fiber 10 is composed of a spinnable polymer 12 and a conductive material 14. According to the embodiment of the disclosure, the conductive fiber 10 is composed of a spinnable polymer 12 and a conductive material 14. According to the embodiment of the present disclosure, the weight ratio of the spinnable polymer to the conductive material is 7:3 to 3:7 (for example, 3.5:6.5, 4:6, 5:5, or 6:4).

According to an embodiment of the present disclosure, the manufacturing method of the solid conductive fiber described in FIG. 4 may include the following steps. First, the above-mentioned first solution and the above-mentioned second solution are provided. Then, the first solution and the second solution are mixed to obtain a third solution, wherein the weight ratio of the first solution to the second solution is about 1:2 to 3:1. It should be noted that the first solvent and the second solvent are mutually soluble, and the spinnable polymer needs to be soluble in the second solvent. Next, wet spinning is performed using the third solution as a spinning solution to obtain the solid conductive fiber.

According to an embodiment of the present disclosure, please refer to FIG. 5, which is a schematic cross-sectional structure diagram of the conductive fiber 10 of the present disclosure. As shown in FIG. 5, the conductive fiber 10 can be a hollow conductive fiber, wherein the hollow conductive fiber includes a hollow portion 11 and a shell portion 13, and the shell portion 13 is composed of a spinnable polymer 12 and a conductive material 14. According to the embodiment of the disclosure, the shell portion 13 is composed of a spinnable polymer 12 and a conductive material 14. According to the embodiment of the disclosure, the hollow portion 11 and the shell portion 13 of the hollow conductive fiber The volume ratio can be about 3:1 to 1:3. According to the embodiment of the present disclosure, the weight ratio of the spinnable polymer to the conductive material is about 1:2 to 3:1, such as 1:1, 1.5:1, 2:1, or 2.5:1.

According to an embodiment of the present disclosure, the method for manufacturing the hollow conductive fiber described in FIG. 5 may include the following steps. First, the above-mentioned first solution and the above-mentioned second solution are provided. Then, the first solution and the second solution are mixed to obtain a third solution, wherein the weight ratio of the first solution to the second solution is about 1:2 to 3:1. It should be noted that the first solvent and the second solvent are mutually soluble, and the spinnable polymer needs to be soluble in the second solvent. Next, a spinning coagulation bath (for example, an aqueous sodium sulfate solution with a concentration of 1% to 15%, based on the total weight of the sodium sulfate aqueous solution) is used as the inner spinning solution and the third solution obtained is used as an outer spinning solution , And wet spinning through a dual-spinning spinning device to obtain the hollow conductive fiber.

According to an embodiment of the present disclosure, please refer to FIG. 6, which is a schematic cross-sectional structure diagram of the conductive fiber 10 of the present disclosure. As shown in Figure 6, the conductive fiber 10 can be a conductive fiber with a core-sheath structure, wherein the core-sheath structure is composed of a core 16 and a sheath 17, wherein the core 16 includes the spinnable height The molecule 12 and the conductive material 14, and the sheath 17 includes an elastic polymer 15. According to an embodiment of the present disclosure, the volume ratio of the core portion 16 and the sheath portion 17 of the conductive elastic fiber having a core-sheath structure may be about 3:1 to 1:3.

According to an embodiment of the present disclosure, the manufacturing method of the conductive fiber having a core-sheath structure described in FIG. 6 may include the following steps. First, the above-mentioned first solution and the above-mentioned second solution are provided. Then, the first solution and the second solution are mixed to obtain a third solution, wherein the first solvent and the second solvent are mutually soluble, and The spinnable polymer is soluble in the second solvent. Then, a fourth solution is provided, wherein the fourth solution includes an elastic polymer dissolved in a third solvent; finally, the third solution is used as an inner spinning solution, and the fourth solution is used as an outer spinning solution. Orifice spinning solution and wet spinning through a double-orifice spinning device to obtain the conductive fiber with core-sheath structure. According to other embodiments of the present disclosure, the fourth solution includes the above-mentioned elastic polymer dissolved in the third solvent, wherein the weight ratio of the elastic polymer to the third solution is about 5:95 to 20:80 (for example, 7: 93, 10:90, 12:88, 15:85, or 17:83). According to an embodiment of the present disclosure, the solid content of the first solution may be about 5wt% to 20wt%; the solid content of the second solution may be about 5wt% to 20wt%; and the solid content of the second solution may be about 5wt% % To 20wt%.

According to other embodiments of the present disclosure, please refer to FIG. 7. The conductive fiber 10 can be a conductive fiber with a core-sheath structure, wherein the core-sheath structure is composed of a core 16 and a sheath 17, wherein the core 16 includes the elastic polymer 15, and the sheath 17 includes the spinnable polymer 12 and the conductive material 14.

In order to make the above and other objectives, features, and advantages of this disclosure more obvious and understandable, a few embodiments are given below, which are described in detail as follows:

Preparation of dendritic silver powder

0.1-0.6 wt% of silver nitrate (Silver nitrate, purchased from Sigma-Aldrich) and 1-5 wt% of nitric acid (Nitric acid, purchased from Sigma-Aldrich) are dissolved in deionized water to obtain a solution. After adding 0.02-0.2wt% polyvinylpyrrolidone (purchased from Sigma-Aldrich) to the above solution and stirring, the above solution is placed in an electrochemical deposition equipment, the current density is set to 4ASD, and ITO (oxidized Indium tin) glass is the working electrode, Ag-AgCl As the reference electrode, platinum (Pt) was used as the counter electrode, and the deposition time was 5-15 minutes to obtain dendritic silver powder (the diameter was about 0.5-2 μm, and the length was about 5-20 μm).

Preparation of conductive fiber

Example 1:

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of the water-based polyurethane as a benchmark) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder (as a conductive material) is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Next, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 5:5). Next, stirring is carried out at 50° C. for 120 minutes (stirring speed is 100 rpm) so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution. Next, wet spinning is performed using a spinning device, and the third solution is used as a spinning solution to obtain solid conductive fibers (1). The spinning conditions are as follows: the spinning nozzle diameter is 1.0mm; the spinning temperature is 50°C; the liquid output speed is 3cc/min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (1) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (1) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Example 2:

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of water-based polyurethane based Standard) (The ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder (as a conductive material) is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 5:5). Next, stirring is carried out at 50° C. for 120 minutes (stirring speed is 100 rpm) so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution. Polyurethane (as an elastic polymer) (manufactured by Formosa Asahi spandex, product number Roica) was dissolved in N,N-dimethyl acetamide to obtain a fourth solution (solid content of 15 wt%). Next, use a double-spindle spinning device to perform wet spinning, use the third solution as the inner spinning dope and the fourth solution as an outer spinning dope, and spin through a double-spindle The device performs wet spinning. A conductive fiber (2) having a core-sheath structure is obtained (in which the aqueous polyurethane/polyvinyl alcohol/dendritic silver powder constitutes the core part, and the polyurethane constitutes the sheath part). The spinning conditions are as follows: inner spinning orifice diameter is 1.0mm; outer spinning orifice diameter is 0.6mm; spinning temperature is 50℃; inner spinning orifice liquid outlet speed is 3.6cc/min; outer spinning orifice liquid outlet speed is 2.4cc/ min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (2) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (2) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Example 3:

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of the water-based polyurethane as a benchmark) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder (as The conductive material is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 5:5). Next, stir at 50°C for 120 minutes (stirring speed is 100 rpm), so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution, and the obtained third solution is used as the spinning solution . Next, wet spinning was performed using a double-spindle spinning device, the resulting mixed solution was used as the outer spinning dope, and a 5% sodium sulfate aqueous solution was used as the inner spinning dope to obtain hollow conductive fibers (3 ). The spinning conditions are as follows: inner spinning orifice diameter is 1.0mm; outer spinning orifice diameter is 1.9mm; spinning temperature is 50℃; inner spinning orifice liquid outlet speed is 0.6cc/min; outer spinning orifice liquid outlet speed is 2.1cc/ min; the spinning speed is 15m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (3) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (3) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Example 4:

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of the water-based polyurethane as a benchmark) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder (as a conductive material) is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 4:6). Next, stirring is carried out at 50° C. for 120 minutes (stirring speed is 100 rpm) so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution. Polyurethane (as an elastic polymer) (by Formosa Asahi Spandex, product number Roica) was dissolved in N,N-dimethyl acetamide (N,N-dimethyl acetamide) to obtain a fourth solution (the weight ratio of polyurethane to dimethyl acetamide is 15:85). Next, use a double-spindle spinning device to perform wet spinning, use the third solution as the inner spinning dope and the fourth solution as an outer spinning dope, and spin through a double-spindle The device performs wet spinning. A conductive fiber (4) having a core-sheath structure is obtained (in which the aqueous polyurethane/polyvinyl alcohol/dendritic silver powder constitutes the core part, and the polyurethane constitutes the sheath part). The spinning conditions are as follows: inner spinning orifice diameter is 1.0mm; outer spinning orifice diameter is 0.6mm; spinning temperature is 50℃; inner spinning orifice liquid outlet speed is 3.6cc/min; outer spinning orifice liquid outlet speed is 2.4cc/ min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (4) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (4) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Example 5:

Polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) is dissolved in deionized water to obtain a first solution (the weight ratio of polyvinyl alcohol to water is 12:88). In addition, the dendritic silver powder (as a conductive material) is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 5:5). Next, stir at 50°C for 120 minutes (stirring speed is 100 rpm), so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution, and the obtained third solution is used as the spinning solution . Next, wet spinning is performed using a spinning device to obtain solid conductive fibers (5). The spinning conditions are as follows: the diameter of the spinning nozzle is 1.0mm; the spinning temperature is 50℃; the liquid output speed is 3.0cc/min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (5) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (5) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Example 6:

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of the water-based polyurethane as a benchmark) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder (as a conductive material) is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 3.5:6.5). Next, stir at 50°C for 120 minutes (stirring speed is 100 rpm), so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution, and the obtained third solution is used as the spinning solution . Next, wet spinning is performed using a spinning device to obtain solid conductive fibers (6). The spinning conditions are as follows: the spinning nozzle diameter is 1.0mm; the spinning temperature is 50°C; the liquid output speed is 3.0cc/min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and, the coagulation bath temperature It is 25°C. Next, measure the fiber fineness of the conductive fiber (6) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (6) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Comparative example 1

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and (product number Paramillion AF36) in deionized water to obtain a first solution (solid content is 12wt%, based on the total weight of water, polyvinyl alcohol, and water-based polyurethane) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, flake silver powder (as a conductive material) (manufactured by AgPro technology, product number SYP981) (diameter 50:9μm) is dispersed in deionized water to obtain a second solution (conductive material and water weight The ratio is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 5:5). Next, stir at 50°C for 120 minutes (stirring speed is 100 rpm), so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution, and the obtained third solution is used as the spinning solution . Next, wet spinning is performed using a spinning device to obtain solid conductive fibers (7). The spinning conditions are as follows: the spinning nozzle diameter is 1.0mm; the spinning temperature is 50°C; the liquid output speed is 3cc/min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (7) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (7) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Comparative example 2

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of the water-based polyurethane as a benchmark) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, silver nanowires (as a conductive material) (with a diameter of 60 nm and a length of 22 μm) were dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water was 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 5:5). Next, stir at 50°C for 120 minutes (stirring speed is 100 rpm) to make the dendritic silver powder in the resulting mixed solution sufficient Disperse in the above-mentioned first solution to obtain a third solution, and use the obtained third solution as a spinning solution. Next, wet spinning is performed using a spinning device to obtain solid conductive fibers (8). The spinning conditions are as follows: the spinning nozzle diameter is 1.0mm; the spinning temperature is 50°C; the liquid output speed is 3cc/min; the spinning speed is 1m/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, measure the fiber fineness of the conductive fiber (8) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (8) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Comparative example 3

Dissolve polyvinyl alcohol (polyvinyl alcohol, product number BF-24) and water-based polyurethane (as an elastic polymer) (product number Paramillion AF36) in deionized water (the ratio of polyvinyl alcohol to water-based polyurethane is 9/1) , Obtain a first solution (the solid content is 12 wt%, based on the total weight of water, polyvinyl alcohol, and water-based polyurethane) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 8:2). Next, stir at 50°C for 120 minutes (stirring speed is 100 rpm), so that the dendritic silver powder in the resulting mixed solution can be fully dispersed in the first solution to obtain a third solution, and the obtained third solution is used as the spinning solution . Next, wet spinning is performed using a spinning device to obtain solid conductive fibers (9). The spinning conditions are as follows: the spinning nozzle diameter is 1.0mm; the spinning temperature is 50°C; the liquid output speed is 3cc/min; the spinning speed is lm/min; the coagulation bath is a 5% sodium sulfate aqueous solution; and the coagulation bath temperature is 25°C. Next, the fiber fineness of the conductive fiber (9) was measured with an electron microscope (JEOLJSM6480), and the resistance of the conductive fiber (9) was measured with a micro-resistance meter (Hioki RM3544). The results are shown in Table 1.

Comparative example 4

Dissolve polyvinyl alcohol (Polyvinyl alcohol, product number BF-24) and water-based polyurethane (product number Paramillion AF36) in deionized water to obtain a first solution (solid content of 12wt%, with water, polyvinyl alcohol , And the total weight of the water-based polyurethane as a benchmark) (the ratio of polyvinyl alcohol to water-based polyurethane is 9:1). In addition, the dendritic silver powder is dispersed in deionized water to obtain a second solution (the weight ratio of conductive material to water is 20:80). Then, the first solution is added to the second solution (the weight ratio of the first solution to the second solution is 2.5:7.5). After stirring for 120 minutes at 50° C. (stirring speed 100 rpm), the resulting mixed solution showed a partially agglomerated state, and the solution had dendritic silver powder precipitated out, showing a phase separation phenomenon, and spinning processing could not be performed. Next, measure the fiber fineness of the conductive fiber (10) with an electron microscope (JEOL JSM6480), and measure the resistance of the conductive fiber (10) with a micro-resistance meter (Hioki RM3544), The results are shown in Table 1.

Table 1

The manufacturing method of the conductive fiber disclosed in the present disclosure can be uniformly dispersed in the spinnable polymer by a conductive material with a special shape such as dendritic or snowflake shape, and a network structure is formed by the branches of the dendritic silver powder itself, as long as the dendritic When the branches of the silver powder are in contact with the conductive fibers, a conductive path can be formed, and the lowest resistance can be achieved. In addition, the present disclosure can achieve good conductive properties when the conductive material is added in a low amount. The present disclosure may be further combined with elastic polymers to prepare conductive fibers with conductive solid, hollow or core-sheath structure.

In summary, compared with traditional conductive materials (such as flake silver powder or nano-silver wire), dendritic silver powder constitutes a conductive path because the branch structure has more contact points, so the conductivity is better. In addition, the feature of more contact points can reduce the damage of contact points after washing, so the effect of washing resistance can be achieved. Furthermore, after the fiber is stretched, its conductive path points are easily damaged, leading to an increase in resistance. In contrast, dendritic silver powder has more contact points, so it can withstand damage and maintain better electrical conductivity. Therefore, the conductive fiber made of dendritic silver powder can take into account the advantages of wearing comfort and low impedance at the same time.

Although this disclosure has been disclosed in several embodiments as above, it is not intended to limit this disclosure. Anyone with ordinary knowledge in the art can make any changes and modifications without departing from the spirit and scope of this disclosure. Therefore, the protection scope of this disclosure shall be subject to those defined by the attached patent application scope.

10‧‧‧Conductive fiber

12‧‧‧Spinnable polymer

14‧‧‧Conductive material

Claims (20)

A manufacturing method of conductive fiber, comprising: providing a first solution, wherein the first solution includes a spinnable polymer dissolved in a first solvent, wherein the weight ratio of the spinnable polymer to the first solution is 5 : 95 to 20:80; Provide a second solution, wherein the second solution contains a conductive material dispersed in a second solvent, wherein the weight ratio of the conductive material to the second solution is 5:95 to 20:80 , Wherein the conductive material type is dendrite or snowflake-like, wherein the dendritic conductive material is composed of a central stem and a plurality of side branches, and the smallest included angle between the side branches and the central stem θ is 30 degrees to 90 degrees, wherein the snowflake-shaped conductive material has at least one multifurcated branch point, and the multifurcated branch point 8 refers to a four-forked branch point, a five-forked branch Point or six-point branch point; and subjecting the first solution and the second solution to a wet spinning process to obtain the conductive fiber. According to the method for manufacturing conductive fiber described in item 1 of the scope of patent application, the conductive material is gold, silver, copper, aluminum, nickel or a combination of the foregoing. As described in the first item of the scope of patent application, the conductive fiber manufacturing method, wherein the weight ratio of the spinnable polymer to the conductive material is 7:3 to 3:7. According to the manufacturing method of the conductive fiber described in claim 1, wherein the conductive material has an aspect ratio of 5-15. The manufacturing method of conductive fiber as described in item 1 of the scope of patent application, which Among the spinnable polymers are polyvinyl alcohol, sodium alginate, carboxy methyl cellulose, polyurethane, polyester, and polystyrene -Butadiene resin (styrene-butadiene-styrene resin, SBS), polyacrylonitrile-butadiene resin (Nitrile butadiene rubber, NBR), or a combination of the above. According to the method for manufacturing conductive fiber described in item 1 of the scope of patent application, the first solvent and the second solvent are each independently deionized water, dimethyl formamide, and dimethyl acetamide. Amine (dimethyl acetamide), dimethylsulfone (dimethylsulfone), tetrahydrofuran (tetrahydrofuran), dichloromethane (dichloromethane), methyl ethyl ketone (methylethyl ketone), or chloroform (chloroform). According to the manufacturing method of conductive fiber described in item 1 of the scope of patent application, the weight ratio of the first solution to the second solution is 1:2 to 3:1. According to the method for manufacturing conductive fiber as described in item 1 of the scope of patent application, the wet spinning process of the first solution and the second solution includes the following steps: mixing the first solution and the second solution to obtain A third solution, wherein the first solvent and the second solvent are mutually soluble, and the spinnable polymer is dissolved in the second solvent; and the third solution is used as a spinning solution for wet spinning. According to the method for manufacturing conductive fiber as described in item 1 of the scope of patent application, the wet spinning process of the first solution and the second solution includes the following steps: mixing the first solution and the second solution to obtain A third solution in which The first solvent and the second solvent are mutually soluble, and the spinnable polymer is dissolved in the second solvent; and a spinning coagulation bath is used as an inner spinning solution, and the obtained third solution is used as a Outer spinning mouth spinning solution, and wet spinning through a double spinning mouth spinning device. According to the method for manufacturing conductive fiber as described in item 1 of the scope of patent application, the wet spinning process of the first solution and the second solution includes the following steps: mixing the first solution and the second solution to obtain A third solution, wherein the first solvent and the second solvent are mutually soluble, and the spinnable polymer is soluble in the second solvent; providing a fourth solution, wherein the fourth solution includes an elastic polymer Dissolved in a third solvent; and the third solution is used as the inner spinning dope spinning solution, and the fourth solution is used as an outer spinning nozzle spinning solution, and the wet spinning is performed through a double-spindle spinning device . According to the manufacturing method of conductive fiber described in item 10 of the scope of patent application, the weight ratio of the elastic polymer to the third solvent is 5:95 to 20:80. The method for manufacturing conductive fiber as described in item 11 of the scope of patent application, wherein the elastic polymer is polyurethane, polystyrene-butadiene-styrene resin (SBS), polyacrylonitrile- Butadiene resin (nitrile butadiene rubber, NBR), or a combination of the above. A conductive fiber, comprising: a conductive material and a spinnable polymer, wherein the conductive material type includes tree branches Dendrite or snowflake-like, wherein the dendritic conductive material is composed of a central trunk and a plurality of side branches, and the minimum included angle θ between the side branches and the central trunk is 30 degrees to 90 degrees, where The snowflake-shaped conductive material has at least one multifurcated branch point, and the multifurcated branch point refers to a four-pronged branch point, a five-pronged branch point, or a six-pronged branch point, wherein The weight ratio of the spinnable polymer to the conductive material is 7:3 to 3:7, based on the total weight of the spinnable polymer and the conductive material. The conductive fiber described in item 13 of the scope of patent application, wherein the conductive material includes gold, silver, copper, aluminum, nickel or a combination of the above. The conductive fiber described in item 13 of the scope of patent application, wherein the conductive material has an aspect ratio of 5-15. The conductive fiber described in item 13 of the scope of patent application, wherein the spinnable polymer is polyvinyl alcohol, sodium alginate, carboxy methyl cellulose, polyurethane (polyurethane), polyester (polyester), polystyrene-butadiene-styrene resin (SBS), polyacrylonitrile-butadiene rubber (NBR), or a combination of the above. The conductive fiber described in item 13 of the scope of patent application, wherein the conductive fiber is a solid conductive fiber. The conductive fiber described in item 13 of the scope of patent application, wherein the conductive fiber is a hollow conductive fiber. The conductive fiber described in item 13 of the scope of patent application, wherein the conductive fiber The fiber further contains an elastic polymer. The conductive fiber described in claim 19, wherein the conductive fiber is a conductive fiber with a core-sheath structure, wherein the core-sheath structure is composed of a core and a sheath, and the core includes the spinnable The polymer and the conductive material, and the sheath includes the elastic polymer.

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