JP7294651B2 - Manufacturing method of conductive polymer conductor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a conductive polymer conductor using a conductive polymer and a method for producing the same.

In recent years, a conductive polymer fiber is known in which a conductive polymer such as PEDOT-PSS {poly(3.4-ethylenedioxythiophene)-poly(styrenesulfonic acid)} is adhered to a substrate made of silk. (See, for example, Patent Document 1). Since this conductive polymer fiber has conductivity, hydrophilicity, tensile strength, and water resistance, it can be used particularly as a material for bioelectrodes.

JP 2015-77414 A

However, conventional conductive polymer fibers have a problem that the conductive polymer on the surface is peeled off after repeated washing, resulting in a decrease in conductivity.

The present invention has been made based on such problems, and an object of the present invention is to provide a conductive polymer conductor capable of improving washing durability, and a method for producing the same.

The conductive polymer conductor of the present invention comprises a base material to which a conductive polymer is attached, and the base material includes at least one of silk, cotton, and synthetic fibers, and is electrically conductive. The polymer is poly3,4-ethylenedioxythiophene added with iron salt of p-toluenesulfonic acid as an oxidizing agent and dopant, and iron salt of p-toluenesulfonic acid and poly3,4-ethylenedioxythiophene Using a reaction solution containing a monomer of p-toluenesulfonic acid, ethanol and water, the ratio of the iron salt of p-toluenesulfonic acid and the monomer of poly3,4-ethylenedioxythiophene in the reaction solution (p-toluenesulfonic acid (iron salt of poly(3,4-ethylenedioxythiophene): poly(3,4-ethylenedioxythiophene monomer)) are polymerized at a molar ratio within the range of 1:0.2 to 1:0.6.

In the method for producing a conductive polymer conductor of the present invention, an iron salt of p-toluenesulfonic acid is added as an oxidizing agent and dopant to a base material containing at least one of silk, cotton, and synthetic fibers. A method for manufacturing a conductive polymer conductor to which a conductive polymer made of poly 3,4-ethylenedioxythiophene is attached, comprising ethanol, iron salt of p-toluenesulfonic acid, and poly 3,4 - a monomer of ethylenedioxythiophene, and the ratio of the iron salt of p-toluenesulfonic acid and the monomer of poly 3,4-ethylenedioxythiophene (iron salt of p-toluenesulfonic acid: poly 3 , 4-ethylenedioxythiophene monomer) in a molar ratio of 1:0.2 to 1:0.6, and mixing water into the mixed solution. The method includes a step of preparing a reaction solution, and a step of applying the reaction solution to a base material to polymerize the poly-3,4-ethylenedioxythiophene monomer.

According to the conductive polymer conductor of the present invention, the conductive polymer contains an iron salt of p-toluenesulfonic acid, a monomer of poly3,4-ethylenedioxythiophene, ethanol and water, and p - The iron salt of toluenesulfonic acid and the poly 3,4-ethylenedioxythiophene monomer are polymerized using a reaction solution in which the ratio is within a predetermined range, so that the resistance to washing is improved. be able to.

In particular, if the ratio of water in the reaction solution is 1% by volume or more and 30% by volume or less, a higher effect can be obtained.

According to the method for producing a conductive polymer conductor of the present invention, ethanol, an iron salt of p-toluenesulfonic acid, and a monomer of poly-3,4-ethylenedioxythiophene are included, After preparing a mixed solution in which the ratio of the iron salt of the acid and the monomer of poly3,4-ethylenedioxythiophene is within a predetermined range, water is mixed with this mixed solution to form a reaction solution, which is applied to a substrate. Since the polymer is polymerized by using the above method, the conductive polymer conductor of the present invention can be easily obtained, and the resistance to washing can be improved.

In particular, if the ratio of water in the reaction solution is 1% by volume or more and 30% by volume or less, a higher effect can be obtained.

1 is a diagram showing a schematic configuration of a conductive polymer conductor according to an embodiment of the present invention; FIG. 2 is a diagram showing the configuration of a manufacturing apparatus for manufacturing the conductive polymer conductor shown in FIG. 1. FIG. FIG. 2 is a characteristic diagram showing the results of X-ray diffraction of conductive polymer conductors and substrates according to Example 1-1 and Comparative Example 1-1. 1 is a characteristic diagram superimposing the results of X-ray diffraction of Example 1-1, Comparative Example 1-1, and a base material. FIG. FIG. 2 is a characteristic diagram showing changes in resistance values depending on the number of washings of conductive polymer conductors according to Examples 1-1 to 1-3 and Comparative Example 1-1. FIG. 4 is a characteristic diagram showing changes in resistance values depending on the number of washings of conductive polymer conductors according to Examples 2-1 to 2-3 and Comparative Example 2-1; FIG. 10 is a characteristic diagram showing changes in resistance values depending on the number of washings of conductive polymer conductors according to Examples 3-1 to 3-3.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 shows a schematic configuration of a conductive polymer conductor 10 according to one embodiment of the present invention. This conductive polymer conductor 10 is obtained by attaching a conductive polymer 12 to a substrate 11, and can be used as, for example, a conductive polymer electrode.

Any material can be used to form the base material 11, but fibers are preferable, and those containing at least one of natural fibers such as silk and cotton, and chemical fibers such as synthetic fibers are preferable. . It is because it is excellent in productivity and stretchability. In particular, it is preferable to include a synthetic fiber having a modified cross section (that is, a modified cross section yarn) because the conductive polymer 12 adheres also between the fibers and the washing resistance can be improved.

The shape of the substrate 11 is preferably, for example, thread-like, cloth-like, or sheet-like, and in the case of cloth-like or sheet-like, it may be any of woven fabric, knitted fabric, or non-woven fabric. A non-woven fabric is a sheet-like material in which fibers are entangled without being woven, and fibers are bonded or entangled by heat, mechanical or chemical action. When the base material 11 is filamentous, the filamentous conductive polymer conductor 10 having the conductive polymer 12 attached to the base material 11 may be used as it is. may be used.

As the conductive polymer 12, poly 3,4-ethylenedioxythiophene (hereinafter referred to as PEDOT) added with iron salt of p-toluenesulfonic acid (hereinafter referred to as pTS) is preferable. That is, the conductive polymer 12 contains pTS and PEDOT. pTS functions as an oxidizing agent when polymerizing the PEDOT monomer, that is, 3,4-ethylenedioxythiophene (hereinafter referred to as EDOT), and also functions as a dopant for making PEDOT exhibit conductivity. It is.

PEDOT is preferably polymerized using a reaction solution containing pTS, a PEDOT monomer (that is, EDOT), ethanol, and water. This is because the crystallinity of PEDOT is lowered, the adhesion to the substrate 11 is improved, and the resistance to washing can be improved. The crystallinity of PEDOT can be determined, for example, by measuring the intensity of the crystallinity peak, which appears in the vicinity of 2θ=5° to 7° in X-ray diffraction. The proportion of water in the reaction solution (water/reaction solution) is preferably in the range of 1% by volume or more and 30% by volume or less. This is because higher effects can be obtained.

In addition, PEDOT is polymerized with the molar ratio of pTS and PEDOT monomer (pTS:PEDOT monomer) in the reaction solution within the range of 1:0.2 to 1:0.6. It is preferable that the This is because the electrical conductivity and washing resistance can be further improved. Moreover, by polymerizing at such a ratio, the ratio of PEDOT with which pTS is coordinated among the PEDOT of the conductive polymer 12 can be 10% or more and 50% or less. The ratio of pTS-coordinated PEDOT to PEDOT is determined by comparing, for example, the PEDOT peak obtained by XPS (X-ray Photoelectron Spectroscopy) and the ratio of pTS-coordinated PEDOT. It can be determined from the area ratio to the peak.

The conductive polymer 12 may be formed over the entire surface of the substrate 11 or may be formed partially. For example, when the base material 11 is filamentous, it may be formed on the entire surface of the base material 11 as shown in FIG. It may be formed on one side as shown in FIG. 1B, or may be formed on both sides (not shown). Also, although the conductive polymer 12 adheres to the surface of the base material 11 , it may permeate the surface of the base material 11 .

Moreover, as shown in FIG. 1C, the conductive polymer conductor 10 preferably has a coating film 13 crosslinked by a water-based crosslinking agent on the surface of the conductive polymer 12 . This is because the washing resistance can be further improved. The water-based cross-linking agent is a water-soluble cross-linking agent, and examples thereof include isocyanate-based cross-linking agents containing isocyanate.

This conductive polymer conductor 10 can be produced, for example, as follows. FIG. 2 shows the configuration of a manufacturing apparatus 20 for manufacturing the conductive polymer conductor 10. As shown in FIG. This manufacturing apparatus 20, for example, manufactures a reaction solution containing pTS and PEDOT monomers, ethanol, and water, and heats the coating portion 21 that coats the substrate 11 and the substrate 11 coated with the reaction solution. and a moving means 23 for moving the substrate 11 from the coating section 21 to the heating section 22 .

The application unit 21 includes, for example, a first tank 21A containing a first liquid containing pTS and ethanol, a second tank 21B containing a second liquid containing a PEDOT monomer and ethanol, and water. The first tank 21A, the second tank 21B, and the third tank 21C are connected to the third tank 21C, and the first liquid, the second liquid, and water are mixed to prepare a reaction solution, and It has a mixing/applying section 21</b>D for applying to the material 11 . The heating unit 22 has, for example, a hot air device 22A, and applies hot air to the base material 11 to heat it. The moving means 23 has a plurality of pairs of rollers 23A that sandwich the substrate 11, and the substrate 11 is supported and moved by these rollers 23A.

The conductive polymer conductor 10 is preferably manufactured using this manufacturing apparatus 20, for example, as follows. First, the first liquid containing pTS and ethanol stored in the first tank 21A and the second liquid containing the PEDOT monomer and ethanol stored in the second tank 21B are put into the mixing/applying section 21D, A mixed solution is produced by mixing (step S101; mixed solution producing step). At that time, the ratio of pTS and PEDOT monomer (pTS: PEDOT monomer) is adjusted so that the molar ratio is in the range of 1:0.2 to 1:0.6. It is preferable to adjust the mixing ratio of the second liquid and the second liquid.

Next, the water stored in the third tank 21C is put into the mixing/applying section 21D and mixed to prepare a reaction solution (step S102; reaction solution preparation step). At that time, it is preferable to adjust the mixing ratio so that the ratio of water in the reaction solution (water/reaction solution) is in the range of 1% by volume or more and 30% by volume or less. The reason why water is subsequently added to the mixed solution to prepare the reaction solution is that the reaction solution deteriorates quickly when water is added.

Subsequently, after the reaction solution is prepared, the reaction solution is applied to the substrate 11 as soon as possible, and the PEDOT monomer is polymerized to adhere the conductive polymer 12 to the substrate 11 (step S103; polymerization step). ). At that time, it is preferable to heat in the heating unit 22 as necessary, and after heating, it is preferable to react at room temperature, for example. The heating temperature is preferably 20° C. to 60° C., for example. The heating time is preferably 5 to 60 minutes, for example. The reaction time is preferably 10 minutes to 24 hours.

After that, for example, it is washed with water and dried (step S104; washing/drying step). The mixed solution preparation step (step S101) to the water washing/drying step (step S104) are preferably repeated a plurality of times, more preferably two or more times. This is because the electrical conductivity and washing resistance can be further improved. Furthermore, after forming the conductive polymer 12, it is preferable to form the coating film 13 on the surface of the conductive polymer 12 by cross-linking the water-based cross-linking agent (step S105; coating film forming step). This is because the washing resistance can be improved. The coating film 13 can be formed, for example, by applying a water-based cross-linking agent to the surface of the conductive polymer 12 and then performing heat treatment. As for the heat treatment, for example, it is preferable to perform a firing treatment of firing after performing a dry treatment of drying.

As described above, according to the conductive polymer conductor 10 of the present embodiment, the conductive polymer 12 contains pTS and PEDOT monomers, ethanol, and water, and the pTS and PEDOT monomers Since it is composed of a material polymerized using a reaction solution having a ratio within a predetermined range, resistance to washing can be improved.

In particular, if the ratio of water in the reaction solution is 1% by volume or more and 30% by volume or less, a higher effect can be obtained.

According to the production method of the present embodiment, after preparing a mixed solution containing ethanol, pTS and PEDOT monomers and having a ratio of pTS and PEDOT monomers in a predetermined range (step S101; mixed solution preparation step), this mixed solution is mixed with water to form a reaction solution (step S102; reaction solution preparation step), and is applied to the substrate 11 and polymerized (step S103; polymerization step). It is possible to easily obtain the conductive polymer conductor 10 in the form of a morphology, and to improve washing resistance.

In particular, if the ratio of water in the reaction solution is 1% by volume or more and 30% by volume or less, a higher effect can be obtained.

(Examples 1-1 to 1-3)
First, a first liquid containing pTS and ethanol and a second liquid containing a PEDOT monomer and ethanol were prepared, respectively, and the first and second liquids were mixed to prepare a mixed solution ( step S101; mixed solution preparation step). The molar ratio of pTS to PEDOT monomer (pTS:PEDOT monomer) was 1:0.2 to 1:0.6. Then, this mixed solution was mixed with water to prepare a reaction solution (step S102; reaction solution preparation step). The proportion of water in the reaction solution (water/reaction solution) was 20% by volume.

Subsequently, the reaction solution was immediately applied to the substrate 11, heated, and then held in a room at 25° C. and 60% humidity for 2 hours to polymerize EDOT and adhere the conductive polymer 12 (step S103). ; polymerization step). A cloth made of polyester was used for the base material 11 . The heating temperature was 40 ° C., and the heating time was changed in Examples 1-1 to 1-3, with Example 1-1 being 6 minutes, Example 1-2 being 9 minutes, and Example 1-3 being 12 minutes. bottom. After that, it was washed with water and dried (step S104; washing/drying step). Furthermore, the mixed solution preparation step (step S101) to the water washing/drying step (step S104) were sequentially performed once more.

(Comparative Example 1-1)
As Comparative Example 1-1 for Examples 1-1 to 1-3, the same mixed solution as in Examples 1-1 to 1-3 was applied to the same substrate as it was without adding water. EDOT was polymerized in the same manner as in 1 to 1-3 to attach a conductive polymer. The conditions during polymerization were the same as in Examples 1-1 to 1-3, except that the heating time was 12 minutes. Further, after polymerizing, washing and drying are performed in the same manner as in Examples 1-1 to 1-3, and further, in the same manner as in Examples 1-1 to 1-3, the mixed solution is applied, polymerized, washed and dried. was repeated one more time.

(Results of Examples 1-1 to 1-3 and Comparative Example 1-1)
Each conductive polymer conductor 10 thus obtained was subjected to X-ray diffraction to examine the crystallinity of the conductive polymer 12 . FIG. 3A shows the results of Example 1-1, and FIG. 3B shows the results of Comparative Example 1-1. Moreover, the result of the X-ray diffraction of a base material is shown in FIG.3(C) for reference. Further, FIG. 4 shows the results of Example 1-1, Comparative Example 1-1, and the base material. As shown in FIGS. 3 and 4, looking at the crystalline peak of PEDOT near 2θ=6 degrees, Example 1-1 has a smaller peak strength than Comparative Example 1-1, and the crystal It was found that the degree of quenching was low. 3 and 4 show the results of Example 1-1, similar results were obtained for Examples 1-2 and 1-3.

In addition, each conductive polymer conductor 10 obtained was washed 1 to 10 times, and the sheet resistance was measured before washing (i.e., 0 times of washing) and after each washing, and the change in resistance due to washing was measured. Examined. The washing method was JIS L 103 method. For the sheet resistance, the surface resistance was measured between three points separated by 8 mm using Loresta-AX MCP-T370 manufactured by Mitsubishi Chemical Analytic Tech. The results obtained are shown in FIG.

As shown in FIG. 5, according to the present example, the sheet resistance after repeated washing could be reduced as compared with Comparative Example 1-1. That is, it was found that the crystallinity of PEDOT can be lowered and the resistance to washing can be improved by polymerizing EDOT using a reaction solution in which water is added to the mixed solution.

(Examples 2-1 to 2-3)
In the reaction solution preparation step (step S102), the ratio of water in the reaction solution (water/reaction solution) is changed, and the mixed solution preparation step (step S101) to the water washing/drying step (step S104) are repeated three times in order. A conductive polymer conductor 10 was produced in the same manner as in Example 1-3 except for the above. The ratio of water in the reaction solution (water/reaction solution) was 10% by volume in Example 2-1, 20% by volume in Example 2-2, and 30% by volume in Example 2-3.

(Comparative Example 2-1)
As Comparative Example 2-1 for Examples 2-1 to 2-3, the same mixed solution as in Examples 2-1 to 2-3 was applied to the same substrate as it was without adding water. Other than that, conductive polymer conductors were produced in the same manner as in Examples 2-1 to 2-3.

(Results of Examples 2-1 to 2-3 and Comparative Example 2-1)
For each of the conductive polymer conductors 10 thus obtained, changes in resistance due to washing were examined in the same manner as in Examples 1-1 to 1-3. The results obtained are shown in FIG. As shown in FIG. 6, according to the present example, the sheet resistance after repeated washing could be reduced as compared with Comparative Example 2-1. That is, it was found that washing resistance can be improved by polymerizing EDOT using a reaction solution obtained by adding water to a mixed solution.

(Examples 3-1 to 3-3)
A conductive polymer conductor 10 was produced in the same manner as in Example 1-3, except that the number of repetitions of the mixed solution preparation step (step S101) to the water washing/drying step (step S104) was changed. The number of repetitions was 3 in Example 3-1, 2 in Example 3-2, and 1 in Example 3-3.

For each of the conductive polymer conductors 10 thus obtained, changes in resistance due to washing were examined in the same manner as in Examples 1-1 to 1-3. The results obtained are shown in FIG. As shown in FIG. 7, Examples 3-1 and 3-2 were significantly improved in washing resistance as compared with Example 3-3. That is, it was found that it is preferable to repeat the mixed solution preparation step (step S101) to the water washing/drying step (step S104) two or more times.

Although the present invention has been described above with reference to the embodiments, the present invention is not limited to the above embodiments and can be variously modified. For example, in the above embodiments, each component was specifically described, but not all components may be included, or other components may be included.

In recent years, the aging of Japan has progressed, and in order to monitor health conditions and extend healthy life expectancy, casual sensing is used to detect biological information such as electrocardiograms (information that is the basis of electrocardiograms; the same applies hereinafter) and myoelectricity. As a result, wearable devices are being developed that can prevent diseases and injuries and detect diseases at an early stage. However, when measuring the electrocardiogram, it was difficult to wear it for a long time because it was necessary to attach a gel or sticky sticker to the device or to press it strongly with a belt. Disposable seals are also used as substitutes, but problems such as uncomfortable feeling and rough skin may occur when worn.
In addition, conventionally, those coated mainly with Ag metal have been generally used, but there is concern about adverse effects on the living body. Furthermore, there is also the problem that the electrodes are oxidized by moisture and sweat, causing deterioration in performance. In other words, there is a demand for an electrode that does not adversely affect the living body even when used continuously for a long period of time.
According to the present invention, for example, a mixed solution containing a conductive polymer monomer, an oxidizing agent, and ethanol as a solvent is applied to the surface of commercially available underwear, polymerized by a chemical reaction, and conductive Functions can be given to underwear. The electrodes can be measured without being strongly pressed against the living body, underwear can be manufactured at a lower cost than conventional products, and biological information can be detected. If the price of wear becomes cheaper, it can be widely applied to healthcare and nursing support robots, work support robots, fitness, work clothes, and the like.

DESCRIPTION OF SYMBOLS 10... Conductive polymer conductor, 11... Base material, 12... Conductive polymer, 13... Coating film, 20... Manufacturing apparatus, 21... Application part, 21A... First tank, 21B... Second tank, 21C 3rd tank 21D Mixing/coating section 22 Heating section 22A Warm air device 23 Moving means 23A Roller

Claims (2)

A method for producing a conductive polymer conductor in which a conductive polymer is attached to a base material,
the substrate comprises at least one of silk, cotton, and synthetic fibers;
The conductive polymer is poly3,4-ethylenedioxythiophene added with iron salt of p-toluenesulfonic acid as an oxidizing agent and dopant, and the iron salt of p-toluenesulfonic acid and poly3,4-ethylene Using a reaction solution containing a dioxythiophene monomer, ethanol, and water, the ratio (p - iron salt of toluenesulfonic acid:poly3,4 - ethylenedioxythiophene monomer) in a molar ratio within the range of 1:0.2 to 1:0.6; Polymerize the ratio within the range of 10% by volume or more and 30% by volume or less
A method for producing a conductive polymer conductor, characterized by: Ethanol, iron salt of p-toluenesulfonic acid, and a monomer of poly3,4-ethylenedioxythiophene; The ratio with the monomer (iron salt of p-toluenesulfonic acid: poly 3,4-ethylenedioxythiophene monomer) is within the range of 1:0.2 to 1:0.6 in terms of molar ratio. creating a mixed solution;
A step of mixing water with the mixed solution to prepare the reaction solution;
2. The method for producing a conductive polymer conductor according to claim 1, further comprising the step of applying the reaction solution to the base material to polymerize the poly-3,4-ethylenedioxythiophene monomer. .

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