KR102265188B1 - Dopant for conductive polymer and method for producing conductive polymer and conductive polymer using the same - Google Patents

Abstract

This invention provides the dopant for conductive polymers which makes it possible to obtain the conductive polymer excellent in the dispersibility with respect to the organic solvent.
According to the present invention, there is provided a dopant for a conductive polymer having a weight average molecular weight of 500 or more, a compound having a silicon skeleton and at least one substituent, wherein the substituent is any one of a sulfonic acid group, a phosphoric acid group, or a salt thereof.

Description

Dopant for conductive polymer and method for producing conductive polymer and conductive polymer using the same

The present invention relates to a dopant for a conductive polymer, a method for producing a conductive polymer using the dopant, and a conductive polymer.

As a conventional conductive polymer, PEDOT-PSS in which polyethylenedioxythiophene (PEDOT) is doped with polystyrene sulfonic acid (PSS) is exemplified, and is used industrially (eg, Patent Document 1). However, since this PEDOT-PSS is characterized by dispersion stability in water by a sulfonic acid group not used as a dope of PSS, it is stable to problems such as having metal corrosiveness due to high acidity and to organic solvents. There were problems such as not being dispersed into Moreover, when various materials are mixed and mix|blended as a coating material, there existed a subject, such as a binder and various additives being limited to water system.

In response to these problems, polyaniline, which is essentially insoluble in solvents, is pulverized to a nano-size level and pulverized, and paratoluenesulfonic acid with high affinity to polyaniline and solvents (Patent Document 2), dodecylbenzenesulfonic acid (Patent Document 3) Using a sulfonic acid anion emulsifier such as a dispersant as a dispersant to co-disperse in a solvent, a study on the provision of a micro-dispersion solution at the nano level, and di(2-ethylhexyl)sulfosuccinic acid using branched alkyl having high steric hindrance Examination (Patent Document 4) is being conducted. Moreover, examination regarding the conductive polymer which doped the sulfonic-acid group containing poly(meth)acrylic acid ester for the purpose of the solubility with respect to a solvent is also performed (patent document 5).

Japanese Laid-Open Patent Publication No. 7-90060 Japanese Patent Publication No. 2007 - 518859 Japanese Laid-Open Patent Publication No. 2014-075415 Japanese Registered Patent No. 4137583 Japanese Registered Patent No. 5435436

However, in the examination in Patent Documents 2 and 3, the dopant having a small molecular size and there is a limitation in affinity with various organic solvents, the stack inhibitory effect between the π-conjugated moieties is small, and the solvent dispersibility is sufficiently imparted. There are tasks that cannot be done.

In examination in patent document 4, dispersibility was not yet enough, and it was difficult to make it disperse|distribute to the solvent of wide polarity.

In addition, in the examination in Patent Document 5, although a certain amount of solvent dispersibility can be obtained, π-conjugated portions are non-uniformly generated on the polymer dopant, so the π-conjugated portion, which is an insoluble site, is an aggregation state within and between molecules. It becomes a structure which it is easy to take, and the particle diameter of a conductive polymer becomes large in many cases, and there exists a subject that it is difficult to ensure a dispersion stable state.

This invention was made in view of such a situation, It is providing the dopant for conductive polymers from which the conductive polymer excellent in the dispersibility with respect to an organic solvent can be obtained.

According to the present invention, there is provided a dopant for a conductive polymer having a weight average molecular weight of 500 or more, a compound having a silicon skeleton and at least one substituent, wherein the substituent is any one of a sulfonic acid group, a phosphoric acid group, or a salt thereof.

As a result of intensive studies conducted by the inventors of the present invention to improve the solvent dispersibility of the conductive polymer, the dopant for the conductive polymer has a weight average molecular weight of 500 or more, has a silicon skeleton, and has at least one sulfonic acid or phosphoric acid or salt thereof. In the case of a compound, it discovered that it was excellent in the solvent dispersibility of a conductive polymer, and it reached the completion of this invention.

Hereinafter, various embodiments of the present invention will be exemplified. Embodiments shown below can be combined with each other.

Preferably, it is a dopant for conductive polymers in which the said substituent is couple|bonded with the single terminal or both terminals in a silicon skeleton.

Preferably, it is a dopant for conductive polymers whose said silicon skeleton is a compound which has a structural unit represented by following General formula (1).

[Formula 1]

[Wherein, n represents an integer of 2 to 200, and each R independently represents an alkyl group having 3 or less carbon atoms or an unsubstituted or substituted phenyl group.]

Preferably, the dopant for a conductive polymer having a weight average molecular weight of 500 to 20000.

ADVANTAGE OF THE INVENTION According to this invention, the conductive polymer containing the said dopant for conductive polymers and (pi) conjugated polymer is provided.

Preferably, the ?-conjugated polymer is a conductive polymer formed by polymerizing at least one monomer selected from the group consisting of thiophene, aniline, pyrrole, and derivatives thereof.

ADVANTAGE OF THE INVENTION According to this invention, the dispersion liquid of the conductive polymer which disperse|distributed the said conductive polymer in the organic solvent is provided.

According to the present invention, there is provided a step of preparing the dopant for a conductive polymer, a step of preparing a mixture containing the dopant for a conductive polymer and a monomer of a π-conjugated polymer, and a step of performing polymerization in the mixture A method for producing a conductive polymer is provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. Various characteristics exemplified in the embodiments shown below can be combined with each other. In addition, the invention is established independently for each characteristic.

<1. Dopant A for Conductive Polymers>

The dopant for conductive polymers of the present invention is a compound having a weight average molecular weight of 500 or more, having a silicon skeleton, and having at least one substituent which is a sulfonic acid group, a phosphoric acid group, or a salt thereof (hereinafter referred to as dopant A for conductive polymers). That is, by setting it as the said structure, the solubility with respect to an organic solvent can be acquired. In addition, although the dopant A for conductive polymers has a hydrophilic group site and a hydrophobic group site in the compound, solubility in a wide range of solvents can be obtained regardless of a polar solvent or a non-polar solvent by using the above structure.

<1.1 Weight Average Molecular Weight>

The weight average molecular weight of the dopant A for conductive polymers of this invention is 500 or more, Preferably it is 1000 or more, More preferably, it is 2000 or more. In this case, the solvent solubility of dopant A itself becomes favorable, and the dispersibility with respect to the organic solvent of the conductive polymer produced using this dopant A improves. The weight average molecular weight of the dopant A is preferably 20000 or less, more preferably 15000 or less, and still more preferably 10000 or less. In this case, the solubility with respect to the polymerization field (water solubility) at the time of the synthesis|combination of a conductive polymer, and the solvent dispersibility of a conductive polymer can be acquired. Specifically, the weight average molecular weight of the dopant A is, for example, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000, 10000, 12000, 14000. , 16000, 18000, 20000, and may be within a range between any two numerical values exemplified herein.

The weight average molecular weight of the dopant for conductive polymers can be measured using GPC (gel permeation chromatography), for example.

<1.2 Silicon skeleton>

Although it will not specifically limit if the dopant A for conductive polymers has a silicon skeleton in a principal chain, For example, the compound etc. which have a structural unit represented by following General formula (1) are mentioned.

[Formula 1]

[Wherein, n represents an integer of 2 to 200, and each R independently represents an alkyl group having 3 or less carbon atoms or an unsubstituted or substituted phenyl group.]

Here, the alkyl group is preferably a methyl group, and more preferably each R is a methyl group, which is preferable from the viewpoint of suppressing aggregation of the conductive polymer and securing more excellent solvent dispersibility. The value of n is 2-200, Preferably it is 2-120, More preferably, it is 2-60.

<1.3 Substituents>

The dopant A for conductive polymers will not be specifically limited if it has at least 1 or more of a sulfonic acid group, a phosphoric acid group, or those salts as a substituent. That is, when the dopant for conductive polymers has the said substituent, water solubility can be acquired, superposition|polymerization of a conductive polymer can advance in water, and it becomes possible to dope simultaneously. Here, more preferably, the substituent is a sulfonic acid group.

Examples of the sulfonate or phosphate include sulfonic acid metal salts such as sodium sulfonate and potassium sulfonate, sulfonic acid ammonium salt, sulfonate pyridinium salt, and the like, or phosphate metal salts and ammonium phosphate such as sodium phosphate and potassium phosphate.

The dopant A for conductive polymers, Preferably the number of substituents is 1 or 2 pieces. More preferably, the substituent is bonded to one or both ends of the silicon skeleton. That is, if it is such a compound, aggregation of the conductive polymer obtained at the time of doping as a dopant for conductive polymers can be suppressed, it can suppress that the particle diameter of a conductive polymer becomes large, and high dispersibility can be acquired with respect to an organic solvent. In order to obtain more excellent solvent dispersibility, it is preferable that the above substituents are bonded to one end of the silicone skeleton.

<1.4 Synthesis of dopant A for conductive polymers>

The synthetic route of the dopant A for conductive polymers is not particularly limited, and any compound capable of introducing a sulfonic acid group or a salt thereof or a phosphoric acid group or a salt thereof to a compound in which a part of the dopant for conductive polymer is modified with an organic group. For example, a sulfonic acid group in which a part of the silicone compound is modified with an epoxy group, a carbinol group, a diol group, a methacryl group, a carboxyl group, a polyether group, an amino group, a mercapto group, a phenol group, a silanol group, an acryl group, etc. Alternatively, phosphoric acid groups or salts thereof are introduced.

The dopant A for conductive polymers can be synthesize|combined as follows, for example. That is, a compound having a weight average molecular weight of 500 or more and having a silicone skeleton (eg, single-terminal epoxyorganosiloxane (X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd.)) and 2-mercaptoethane Sodium sulfonate, isopropyl alcohol, and triethylamine are mixed and reacted for a predetermined time (for example, 15 hours) under heating and reflux, water is added to the reaction product, and isopropyl alcohol is removed by distillation under reduced pressure, The dopant A for conductive polymers can be obtained with the emulsion of a sulfonic acid compound. Here, the bonding position of the organic substituent is not limited to one terminal, but may be bonded to both terminals.

<2. Conductive Polymer>

The conductive polymer of this invention contains the dopant A for conductive polymers, and (pi) conjugated polymer|macromolecule. This conductive polymer has solvent dispersibility. Here, about the dopant for conductive polymers, if it is within the range of the structure of the dopant A of this invention, it is possible to change suitably.

Moreover, it is also possible to use together the dopant generally used in the field|area of a conductive polymer other than the said dopant A for polymers.

The dopant generally used in the field of a conductive polymer is generally an electron-accepting substance, For example, a halogen, a Lewis acid, a protonic acid, a transition metal halide, etc. can be used. When using together the general dopant mentioned above other than the said dopant A for conductive polymers as dopant B for conductive polymers, dopant A and dopant B can be used together in arbitrary ratios, It is possible to select suitably according to the objective.

The π-conjugated polymer refers to a polymer obtained by polymerization of a monomer of a π-conjugated polymer, and specifically, polythiophene, polyaniline, polypyrrole, poly3,4-ethylenedioxythiophene, poly3-methoxythiophene, Poly3,4-dimethoxythiophene, poly3-hexylthiophene, poly3-methylpyrrole, poly3-methylthiophene, polyo-toluidine, polyo-anisidine, polyo-ethylaniline, polysec- Butylaniline, etc. are mentioned.

In addition, the number average molecular weight of the π-conjugated polymer is usually 1000 to 300000. If it is in this range, it is preferable at the point which can utilize without limiting a use as a conductive polymer. This number average molecular weight is a value measured by GPC using a solvent in which the π-conjugated polymer skeleton is soluble after the doping component is removed, and the π-conjugated polymer at the time of the doping desorption process (alkali treatment, electrolysis, etc.) The decomposition of , etc. are also included reference values.

The conductive polymer of the present invention has a conductivity equal to or higher than that of a conductive polymer obtained by doping a π-conjugated polymer such as polythiophene, polyaniline, or polypyrrole (10 ⁻⁶ [S/cm] or more), and the conductivity is It is possible to apply to the required part, and the use is not particularly limited. The electrical conductivity of a conductive polymer should just show the electrical conductivity ^{within the range of 10 -6} to 10 ^-1 [S/cm] specifically, for example, and you may show the electrical conductivity higher than the electrical conductivity of this range. In addition, the conductivity of the conductive polymer is a range between any two selected from the numerical values represented by ^{10 -6} , 10 ^-5 , 10 ^-4 , 10 ^-3 , 10 ^-2 , and 10 ^{-1 [S/cm].} may be mine Among them, it is preferable to show a conductivity of ^{10 -3} [S/cm] or more from the viewpoint of practically expressing stable performance.

In addition, you may use the conductive polymer of this invention in combination with polymer|macromolecules other than the conductive polymer of this invention. It does not specifically limit here as polymer|macromolecule, A well-known thing can be applied, For example, various resin, such as an acrylic resin, a methacryl resin, a polyurethane resin, a polyester resin, an epoxy resin, is mentioned.

<3. Dispersion of Conductive Polymer>

The conductive polymer of the present invention is stable in ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone, ester solvents such as ethyl acetate and butyl acetate, aromatic solvents such as toluene, ether solvents such as tetrahydrofuran, etc. can be distributed as Here, it is preferable to disperse|distribute to methyl ethyl ketone and ethyl acetate from the point which can disperse|distribute the conductive polymer of this invention more stably and can use it as a general-purpose solvent of various solvent type resin.

The dispersion liquid of a conductive polymer can be prepared as follows, for example. The conductive polymer of the present invention is put into a container into which the above-described solvent is put, while shearing using a disperser to prepare a dispersion. Here, the conductive polymer may be fed in at once, or a part thereof may be divided and thrown in multiple times. It is preferable to inject at once because the dispersion time can be shortened. Moreover, even if it prepares a dispersion liquid by inject|throwing-in simultaneously a solvent and a conductive polymer, there is no problem at all. As a disperser, a homomixer, a high pressure homogenizer, an ultrasonic homogenizer, etc. can be used.

In the dispersion of the conductive polymer obtained as described above, an auxiliary agent for promoting advanced conversion, a dispersing agent for enhancing dispersion stability, and others, a leveling agent, a plasticizer, a wetting agent, a thickener, an antioxidant, an ultraviolet absorber, a filler, a rust preventive agent, You may use various general-purpose additives, such as a pigment.

<4. Method for Producing Conductive Polymer>

The method for producing a conductive polymer of the present invention includes the steps of preparing the dopant A for the conductive polymer, the step of preparing a mixture containing the dopant A for the conductive polymer and the monomer of the π-conjugated polymer, and polymerization in the mixture process is provided. That is, the conductive polymer of this invention can be obtained by doping the said dopant A for conductive polymers at the time of superposition|polymerization of the monomer of (pi) conjugated polymer. As a result, aggregation of the conductive polymer can be suppressed, and stable dispersibility in organic solvents (eg, ethyl acetate, methyl ethyl ketone, toluene, etc., regardless of polarity or non-polarity) can be obtained.

The conductive polymer of this invention can be synthesize|combined as follows, for example. That is, the monomer of the π-conjugated polymer (eg, thiophene), the dopant A for a conductive polymer, concentrated hydrochloric acid, and iron sulfate are mixed and controlled to maintain a predetermined temperature (eg, 30 ° C.) After stirring for a predetermined time, an oxidizing agent such as ammonium persulfate is added dropwise over a predetermined period of time (eg, 1 hour), followed by oxidation polymerization for several hours (eg, 5 hours) to obtain a polymer. Then, solid-liquid separation is performed for a reaction liquid by a predetermined method, and the wet body of a conductive polymer is obtained. Thereafter, the conductive polymer can be freeze-dried under conditions of a predetermined temperature and for a predetermined time to obtain a conductive polymer.

The manufacturing method of the conductive polymer of this invention WHEREIN: It can prepare by the method mentioned above about the dopant A for conductive polymers.

Next, a mixture for polymerizing the conductive polymer can be obtained by including the monomer of the π-conjugated polymer in the dopant A for the conductive polymer. Moreover, you may use together dopants other than the dopant A for polymers.

The monomer of the π-conjugated polymer refers to a monomer that can obtain a polymer in which the polymer obtained by polymerization has a structure in which π electrons can be conjugated or a structure in which single bonds and multiple bonds are alternately connected, for example, Examples thereof include monomers such as thiophene, aniline, pyrrole and derivatives thereof. In addition, the monomer is at least one of an alkyl substituent having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group) and an alkoxy substituent (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group) It is preferable from a viewpoint of solvent solubility to have one substituent.

In addition, as the polymerization initiator of the monomer of the π-conjugated polymer, for example, ammonium persulfate, a peroxide such as aqueous hydrogen peroxide or benzoyl peroxide, benzoquinone such as chloranil, and a chemical oxidizing agent such as ferric chloride can be used. .

The conductive polymer of the present invention can be obtained by polymerizing the mixture of the above-mentioned dopant A for conductive polymers and monomers of the π-conjugated polymer, including additives such as a predetermined oxidizing agent.

Here, the molar mixing ratio of the monomer of the π-conjugated polymer and the dopant A for the conductive polymer is preferably within the range of the monomer of the π-conjugated polymer/dopant A for the conductive polymer = 100/1 to 100/70, and more Preferably, it is in the range of π-conjugated polymer monomer/dopant for conductive polymer A = 100/5 to 100/50. That is, the π-conjugated polymer monomer / dopant for conductive polymer A = within the range of 100/5 ~ 100/50, the stacking of the π-conjugated polymer skeletons due to the steric hindrance of the dopant is suppressed and stable dispersion in solvent This is possible, and when the solvent is volatilized by heat drying, it is preferable for the reason that high conductivity can be expressed by stacking π-conjugated polymer skeletons together.

The conductive polymer of the present invention may be appropriately blended with a monomer of a non-(pi) conjugated polymer, a polymer derived therefrom, a conductive agent, and the like at the time of polymerization.

In the present invention, the non-π-conjugated polymer means a polymer other than the polymer in which single bonds and multiple bonds are alternately connected, like the π-conjugated polymer.

Examples of the non-?-conjugated polymer include thermoplastic resins such as acrylic polymers, methacrylic polymers, urethane polymers, and rubber polymers, thermosetting resins such as phenolic polymers, and thermoplastic elastomers. These may be used individually or in combination of 2 or more types.

Example

Next, an Example is demonstrated below with a comparative example.

<Synthesis of silicone compound>

Synthesis Example 1: Synthesis of silicone compound 1

30 g of single-ended epoxy organosiloxane (X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd.), 1.98 g of 2-mercaptoethanesulfonate sodium, 23 g of isopropyl alcohol, and 0.3 g of triethylamine were mixed and heated under reflux for 15 hours. reacted. Water was added to the reaction product, and isopropyl alcohol was removed by distillation under reduced pressure to obtain an emulsion of silicone compound 1 (12.6% of nonvolatile components). As a result of measuring the weight average molecular weight of compound 1 by GPC, it was 3500.

Synthesis Example 2: Synthesis of silicone compound 2

One-end epoxy organosiloxane (X-22-173DX manufactured by Shin-Etsu Chemical Co., Ltd.) and sodium 2-mercaptoethanesulfonate were reacted in the same manner as in Synthesis Example 1 to obtain an emulsion of silicone compound 2. As a result of measuring the weight average molecular weight of compound 2 by GPC, it was 5400.

Synthesis Example 3: Synthesis of silicone compound 3

Mix 15 g of single-ended methacryloyl organosiloxane (X-22-2426 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 2.08 g of 2-mercaptoethanesulfonate sodium, and 48 g of isopropyl alcohol, under nitrogen atmosphere, under heating and reflux for 30 minutes. stirred. After that, 1.55 g of benzoyl peroxide was added and reacted for 15 hours. An emulsion of silicone compound 3 was obtained by adding water to the reaction product and removing isopropyl alcohol by distillation under reduced pressure. As a result of measuring the weight average molecular weight of compound 3 by GPC, it was 16300.

Synthesis Example 4: Synthesis of silicone compound 4

Mix 15 g of single-ended methacryloyl organosiloxane (X-22-2404 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 5.93 g of 2-mercaptoethanesulfonate sodium, and 66 g of isopropyl alcohol, under nitrogen atmosphere, under heating and reflux for 30 minutes. stirred. Then, 4.12 g of benzoyl peroxide was added and the reaction was carried out for 7 hours. An emulsion of silicone compound 4 was obtained by adding water to the reaction product and removing isopropyl alcohol by distillation under reduced pressure. As a result of measuring the weight average molecular weight of compound 4 by GPC, it was 750.

Synthesis Example 5: Synthesis of silicone compound 5

30 g of carboxyorganosiloxane (X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd.) at both ends and 20 g of thionyl chloride were reacted for 5 hours at room temperature in a nitrogen atmosphere, and then unreacted thionyl chloride was removed by distillation under reduced pressure. By doing so, the functional group was converted into carboxylic acid chloride. An emulsion of silicone compound 5 was obtained by making 3.68 g of sodium isethionate react with the obtained carboxylic acid chloride body at 60 degreeC for 5 hours. As a result of measuring the weight average molecular weight of compound 5 by GPC, it was 5600.

Synthesis Example 6: Synthesis of silicone compound 6

30 g of both terminal thiolorganosiloxane (X-22-167B manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3.70 g of 2-(methacryloyloxy)ethyl phosphate, and 66 g of isopropyl alcohol were mixed and heated under reflux under nitrogen atmosphere for 30 minutes stirred. Then, 4.27 g of benzoyl peroxide was added and the reaction was carried out for 7 hours. Water was added to the reaction product, isopropyl alcohol was removed by distillation under reduced pressure, and further, an emulsion of silicone compound 6 was obtained by neutralizing using sodium hydrogen carbonate. As a result of measuring the weight average molecular weight of compound 6 by GPC, it was 4100.

Synthesis Example 7: Synthesis of silicone compound 7

15 g of triisopropylsilyl acrylate, 16.2 g of 3-sulfopropyl methacrylate potassium, and 66 g of isopropyl alcohol were mixed, and the mixture was stirred under heating and refluxing under nitrogen atmosphere for 30 minutes. After that, 16.2 g of benzoyl peroxide was added and reacted for 7 hours. An emulsion of silicone compound 7 was obtained by adding water to the reaction product and removing isopropyl alcohol by distillation under reduced pressure. As a result of measuring the weight average molecular weight of compound 7 by GPC, it was 340.

The silicone compounds 1 to 7 obtained in Synthesis Examples 1 to 7 and other compounds A to C used as comparison objects and their structures (molecular weight, main chain structure, substituent, etc.) are listed below as Table 1 below.

Compound A: Polycyclic phenyl ether polyethylene oxide-terminated sulfonic acid emulsifier (Newcol 723-SF molecular weight 1100 manufactured by Nippon Nyukazai)

Compound B: sodium dodecylbenzenesulfonate (molecular weight 348)

Compound C: carboxyorganosiloxane at both ends (X-22-162C manufactured by Shin-Etsu Chemical, molecular weight 4600)

The weight average molecular weight of the dopant for conductive polymers measured on the following conditions using GPC (HLC-8120GPC: made by Tosoh).

In addition, at the time of measurement, after ion exchange was performed and it was dissolved in tetrahydrofuran, it calculated|required by standard polyethylene oxide conversion under the following conditions.

<Measurement conditions>

GPC column configuration: the following 5 columns

(i) TSK-GEL HXL-H (guard column, manufactured by Tosoh)

(ii) TSK-GEL 7000HXL (made by Toso)

(iii) TSK-GEL GMHXL (made by Toso)

(iv) TSK-GEL GMHXL (made by Toso)

(V) TSK-GEL G2500HXL (made by Toso)

Sample concentration: diluted with tetrahydrofuran to 1.0 mg/cm ³

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 cm ³ /min.

Column temperature: 40℃

<Synthesis of conductive polymer>

Conductive polymers were synthesized using the silicone compounds shown in Table 1 and other compounds A to C as dopants.

Synthesis Example 8: Synthesis of conductive polymer

142.5 g of the emulsion of the acid-modified silicone compound 1 obtained in Synthesis Example 1, 1.6 g of concentrated hydrochloric acid, 3.2 g of ethylenedioxythiophene (EDOT) as a monomer of the π-conjugated polymer, and 0.09 g of iron sulfate were mixed, respectively, and heated at 30 ° C. for 30 minutes. stirred. Thereafter, an aqueous solution in which 5.9 g of ammonium persulfate was dissolved in 50 g of ion-exchanged water was added dropwise to the mixture over 1 hour. Then, it was made to react for 5 hours, maintaining the state at 30 degreeC. The wet article of the conductive polymer 1 was obtained by solid-liquid separation of the obtained reaction liquid. This wet article was freeze-dried at 0°C for 24 hours to obtain a dry powder of conductive polymer 1.

Synthesis Examples 9 to 19: Synthesis of conductive polymer

Using the dopant and π-conjugated polymer monomers shown in Table 2, conductive polymers 2 to 12 were synthesized in the same manner as in Synthesis Example 8, and dry powders of each conductive polymer were obtained. could not be obtained). Here, in any synthesis example, the molar ratio of the monomer/dopant of the π-conjugated polymer is 100/23 and is the same. They are shown in Table 2 below.

Examples 1 to 8, Comparative Examples 1 to 4

Solvent dispersibility and electroconductivity were evaluated as follows using each conductive polymer 1-11 synthesize|combined by said procedure. The results are shown below as Table 3.

<Evaluation of solvent dispersibility>

Each of the conductive polymers 1 to 11 is mixed in a ratio such that the non-volatile components are 1.5% with respect to ethyl acetate, methyl ethyl ketone and toluene, and treated with a probe-type ultrasonic homogenizer to obtain an organic solvent dispersion of each conductive polymer 1 to 11 prepared In each organic solvent dispersion liquid, the method of visually confirming the sediment 1 hour after the ultrasonic treatment was evaluated. Here, when filtration with qualitative filter paper (No. 2) after 1 hour from the dispersion treatment, ○ indicates that no aggregates are observed, △ indicates that aggregates are observed, and × indicates that aggregates are generated immediately after ultrasonic treatment to form a heterogeneous liquid. did with

<Evaluation of Conductivity>

The ethyl acetate dispersion of each of the conductive polymers 1 to 11 prepared in the evaluation of solvent dispersibility was added dropwise to a dry film thickness of 2 µm on a washed glass substrate, and then dried by heating at 90 ° C. for 5 minutes to prepare a conductivity measurement sample. . The electrical conductivity (S/cm) was measured about the produced sample using the resistivity meter (Mitsubishi Chemical ANALYTECH make, Loresta GP).

As shown in Examples 1-8, it turned out that conductive polymers 1-8 have shown the dispersibility and electroconductivity with respect to the organic solvent more than a wide range from a polar solvent to a non-polar solvent. Among them, in Examples 1 and 2, excellent dispersibility was exhibited in ethyl acetate and methyl ethyl ketone, which are preferred types of solvents, and high electrical conductivity was exhibited. In addition, Example 3 with a large weight average molecular weight of the dopant A showed a lower conductivity while exhibiting better solvent dispersibility, and Example 4 with a small weight average molecular weight showed a lower solvent dispersibility and higher electrical conductivity. . About Examples 5 and 6, since it has a functional group at both ends, although the solvent dispersibility was inferior compared with Examples 1 and 2, compared with the comparative example, the solvent dispersibility and electrical conductivity were shown sufficiently high. For Examples 7 and 8, it was shown that even if the monomer of the π-conjugated polymer was changed, it had high solvent dispersibility.

On the other hand, in Comparative Example 1, the weight average molecular weight of the dopant A is smaller than 500, and in Comparative Example 2, since it does not have a silicon skeleton, the dispersibility in the solvent is very poor, and therefore the film quality is also poor, and the conductivity is low or the conductivity is low. measurement was not possible. About Comparative Example 3, the molecular weight was smaller than 500, and since it did not have a silicone skeleton, there was no solvent dispersibility, Therefore, it was not able to form into a film and to evaluate electrical conductivity. In the comparative example 4, since there was no water solubility in the dopant A, since superposition|polymerization of a conductive polymer did not advance suitably, evaluation was not able to be performed.

Claims (8)

A compound having a weight average molecular weight of 500 or more, having a silicone skeleton, and having at least one substituent, wherein the substituent is any one of a sulfonic acid group, a phosphoric acid group, or a salt thereof;
The dopant for conductive polymers whose said silicon skeleton is a compound which has a structural unit represented by following General formula (1).
[Formula 1]

[Wherein, n represents an integer of 2 to 200, and each R independently represents an alkyl group having 3 or less carbon atoms or an unsubstituted or substituted phenyl group.] The method of claim 1,
The dopant for conductive polymers in which the said substituent is couple|bonded with the single terminal or both terminals in silicon skeleton. delete 3. The method according to claim 1 or 2,
A dopant for a conductive polymer having the weight average molecular weight of 500 to 20000. The conductive polymer containing the said dopant for conductive polymers of Claim 1, and (pi) conjugated system polymer|macromolecule. 6. The method of claim 5,
A conductive polymer formed by polymerizing at least one monomer selected from the group consisting of thiophene, aniline, pyrrole, and derivatives thereof, wherein the π-conjugated polymer is polymerized. The dispersion liquid of the conductive polymer which disperse|distributed the conductive polymer of Claim 5 or 6 in the organic solvent. The step of preparing the dopant for a conductive polymer according to claim 1 or 2, the step of preparing a mixture containing the dopant for the conductive polymer and a monomer of the π-conjugated polymer, and polymerization in the mixture The manufacturing method of a conductive polymer provided with a process.