JP2017171746A - Water-soluble conductive copolymer, method for producing the same, and aqueous solution thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel water-soluble copolymer having high conductivity, an aqueous solution thereof, and a use therefor.SOLUTION: A copolymer has the ratio of formula M1/formula M2 (mole/mole) of 1-9999.SELECTED DRAWING: None

Description

  The present invention relates to a water-soluble conductive copolymer having a novel polythiophene structure, a production method thereof, and an aqueous solution thereof.

  Application of the water-soluble conductive polymer to a resist antistatic film forming material used for forming a circuit pattern of a semiconductor by electron beam lithography, a solid electrolyte of a capacitor, and the like has been studied.

  So far, polythiophene alkanesulfonic acid (for example, Patent Document 1), polyisothianaphthenesulfonic acid (for example, Patent Document 2), poly (4) substituted with a linear alkylenesulfonic acid group as a water-soluble conductive polymer. -(2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-ylmethoxy) -1-butanesulfonic acid) (PEDT-S), polythiophene substituted with branched alkylenesulfonic acid, etc. are reported (For example, refer to Patent Documents 3 and 4 and Non-Patent Documents 1 and 2).

Japanese Patent Publication No.8-13873 Japanese Patent No. 3182239 Japanese Patent No. 4974095 International Publication No. 2014/007299 Specification

Chemisty Materials, 21, 1815-1821 (2009) Advanced Materials, 23 (38), 4403-4408 (2011)

  In the use of the solid electrolytic capacitor described in the background art, conductive polythiophene obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in the presence of a water-soluble polymer dopant such as polystyrene sulfonic acid (= PSS). The application of PEDOT: PSS is being studied. However, although PEDOT: PSS exhibits high conductivity, it is a dispersion solution having a particle diameter of several tens to several hundreds of nanometers. Therefore, the PEDOT: PSS is smaller than the particle diameter of the dielectric alumina, tantalum oxide, and the like. As a result, there was a problem that sufficient performance could not be exhibited in terms of capacitance, equivalent series resistance and the like.

  On the other hand, PEDT-S, which is a self-doped polythiophene different from the above-mentioned externally doped PEDOT: PSS, and polythiophene substituted with a branched alkylene sulfonic acid have a particle size of 0.8 nm or less while being highly conductive. For example, when applied to a polymer substrate, polythiophene cannot be uniformly applied.

  The present invention has been made in view of the above-described background art, and an object thereof is to provide a novel thiophene copolymer excellent in coatability while exhibiting high conductivity and an aqueous solution thereof.

  As a result of intensive studies to solve the above problems, the present inventors have found that a repeating unit derived from a water-soluble thiophene compound having an alkylene spacer having a specific branched structure and a repeating unit derived from a specific comonomer. The present inventors have found that the copolymer to be contained is excellent in conductivity and coatability and have completed the present invention.

  That is, the present invention relates to a copolymer containing a repeating unit derived from a thiophene compound and a repeating unit derived from a comonomer, a production method thereof, and an aqueous solution thereof as described below.

  More specifically, the present invention relates to a repeating unit represented by the following formula (M1) (hereinafter referred to as “thiophene monomer unit”) and a repeating unit represented by the following formula (M2) (hereinafter referred to as “comonomer unit”). And a thiophene monomer unit and a comonomer unit may be self-doped, and a ratio of thiophene monomer unit / comonomer unit (mol / mol) is 1 to 9999. An object of the present invention is to provide a production method thereof and an aqueous solution thereof.

(In the formula, R may be the same or different for each repeating unit, and represents a chain, branched or cyclic alkyl group having 1 to 6 carbon atoms or a fluorine atom. M is different for each repeating unit. And represents a hydrogen ion, an alkali metal ion, or a conjugate acid of an amine compound, and q represents an integer of 1 to 4.)

  The copolymer having a polythiophene structure according to the present invention has higher conductivity and excellent coatability as compared with conventional water-soluble conductive polymers. Therefore, it can be used as a material for forming an antistatic film for a resist used when forming a semiconductor circuit pattern by electron beam lithography and as a solid electrolyte for a capacitor, and is extremely useful in the industry.

  Hereinafter, the present invention will be described in detail.

  The copolymer of the present application comprises a thiophene monomer unit represented by the following general formula (M1) and a comonomer unit represented by the following general formula (M2). The thiophene monomer unit and the comonomer unit are self-doped for each repeating unit. The ratio of thiophene monomer unit / comonomer unit (mol / mol) is 1 to 9999.

(In the formula, R may be the same or different for each repeating unit, and represents a chain, branched or cyclic alkyl group having 1 to 6 carbon atoms or a fluorine atom. M is different for each repeating unit. And represents a hydrogen ion, an alkali metal ion, or a conjugate acid of an amine compound, and q represents an integer of 1 to 4.)
In the above formula (M1), R represents a chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a fluorine atom. Although it does not specifically limit as a C1-C6 linear, branched or cyclic alkyl group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group , Sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, cyclohexyl group, or n-octyl group, etc. Is mentioned.

  In the above formula (M1), M represents a hydrogen ion or a conjugate acid of an amine compound.

  Although it does not specifically limit as said alkali metal ion, For example, the alkali metal ion chosen from the group which consists of Li ion, Na ion, and K ion is mentioned.

The conjugate acid of the amine compound represents a cationic compound in which a proton is added to the amine compound. The amine compound is not particularly limited, and examples thereof include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine and the like (the general formula N (R ¹ ) Amine compound having sp ₃ hybrid orbital of (R ² ) (R ³ ) (amine compound represented by (R ³ )), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridinepyridine (hereinafter referred to as pyridines) , Imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, amine having sp ₂ hybrid orbital such as 1-methylimidazole (above, imidazoles) Compound etc. It is below.

Note that R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 40 carbon atoms which may have a substituent. Among these, it is more preferable that R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and has a substituent. More preferably an alkyl group having 1 to 6 carbon atoms in total, each independently being a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. preferable.

  Here, the alkyl group having 1 to 40 carbon atoms which may have a substituent and the alkyl group having 1 to 20 carbon atoms which may have a substituent are not particularly limited. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2 -Hydroxypropyl group, 2,3-dihydroxypropyl group, methoxymethyl group, ethoxymethyl group, hydroxyethoxyethyl group, hydroxyethoxyethoxyethyl group, benzyl group, phenethyl group, aminoethyl group and the like.

  The linear, branched or cyclic alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Group, t-butyl group, n-hexyl group, cyclohexyl group and the like.

  Although it does not specifically limit as a C1-C6 alkyl group which may have a substituent, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl Group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, methoxymethyl group, ethoxymethyl group, hydroxyethoxy Examples thereof include an ethyl group, a hydroxyethoxyethoxyethyl group, and an aminoethyl group.

Of these, the substituents R ^{1 to} R ³ are more preferably a hydrogen atom or a methyl group. Examples of the substituent when R ^{1 to} R ³ are alkyl groups having a substituent include, for example, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 1 to 20 carbon atoms, a hydroxy group, an amino group, Examples thereof include an alkyl ether group, an aryl ether group, a thiol group, an alkyl sulfide group, or a carboxyl group, and more preferably a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, 2, 3 -An alkyl group having a hydroxy group such as a dihydroxypropyl group.

  Moreover, as said imidazole, a C3-C20 imidazole compound is preferable, Although it does not specifically limit, For example, imidazole, N-methylimidazole, 1, 2- dimethylimidazole etc. are mentioned.

  The pyridines are preferably pyridine compounds having 3 to 20 carbon atoms, and are not particularly limited. Examples thereof include pyridine, picoline, and lutidine. Of these, imidazole is more preferable.

  That is, M is a hydrogen ion, an alkali metal ion, or ammonia, trimethylamine, triethylamine, monoethanolamine, N-methylethanolamine, 3-amino-1,2-, from the viewpoint of water solubility and coatability of the copolymer. It is preferably a conjugate acid of an amine selected from the group consisting of propanediol, N-methyl-3-amino-1,2-propanediol, diethanolamine, triethanolamine, pyridine, methylpyridine, imidazole, and methylimidazole, Hydrogen ion, Li ion, Na ion, K ion, or a conjugate acid of an amine selected from the group consisting of ammonia, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, and imidazole. It is more preferable.

  The copolymer of the present application has a ratio of thiophene monomer unit / comonomer unit (mol / mol) of 1 to 9999. If the ratio of thiophene monomer unit / comonomer unit (mole / mole) is less than 1, the copolymer tends to be poor in water solubility, and the effects of the invention unique to the present application cannot be fully exhibited, and should be avoided. . Further, when the ratio of thiophene monomer unit / comonomer unit (mole / mole) is larger than 9999, the applicability tends to be inferior, and the effect of the invention unique to the present application cannot be sufficiently exhibited.

  In addition, from the viewpoint of water solubility and coatability of the copolymer, the ratio of thiophene monomer unit / comonomer unit (mol / mol) is more preferably 1 to 999, and more preferably 2 to 99.

  In the copolymer of the present application, q represents an integer of 1 to 4. In addition, from the viewpoint of water solubility and coatability of the copolymer, q is preferably 2 to 4, and more preferably 3.

  The copolymer of the present application is a copolymer of a thiophene compound represented by the following formula (1) and a thiophene compound represented by the following formula (2). More specifically, the copolymer of the present application is a self-doped conductive copolymer in which a side chain sulfo group or sulfonate group of the thiophene compound represented by the above formula (1) acts as a p-type dopant, For example, it can be expressed as the following general formula (3).

(In the formula, R, M and q have the same meanings as in the above formulas (M1) and (M2). M and n represent the abundance ratio of repeating units and are real numbers satisfying 3 ≦ m / n ≦ 9999.)
In the above formula (3), the above formula (C) is derived from the thiophene compound represented by the following formula (2), and the above formula (D) is represented by the above formula by the side chain sulfo group or sulfonate group. (C) represents an oxidized state. Moreover, the said formula (A) originates in the thiophene compound represented by following formula (1), and the said formula (B) represents the oxidation state of the said formula (A).

  That is, in the above formula (3), the repeating unit represented by the above (A) or (B) (so-called thiophene monomer unit) and the repeating unit represented by (C) or (D) (so-called comonomer unit). ), And is not necessarily limited to a copolymer containing the units continuously, and as long as it has the desired conductivity, it is not present in the π-conjugated main chain as in the random copolymer. It may be a copolymer containing repeating units continuously.

  The copolymer of the present application is produced by polymerizing a thiophene compound represented by the following general formula (1) and a thiophene compound represented by the above formula (2) in the presence of an oxidizing agent in water or an alcohol solvent. can do.

[In the formula (1), R and q have the same meanings as R and q in the general formulas (M1) and (M2). ]
In the copolymer of the present invention, the ratio of the thiophene compounds represented by the above formulas (1) and (2) is not particularly limited, but the ratio of the thiophene monomer unit / the comonomer unit (mol / mol) is 1. It is preferable that the ratio of the thiophene compound represented by the formula (1) / the thiophene compound represented by the formula (2) (mol / mol) is basically 1 to 9999. . From the viewpoint of water solubility and coatability of the copolymer, the amount of the thiophene compound represented by the above formula (2) is based on the total amount of the thiophene compounds represented by the above formulas (1) and (2). And more preferably 0.01 mol% or more and 50 mol% or less.

  The weight average molecular weight of the copolymer of the present invention is not particularly limited, but it is usually preferably in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid, and preferably 1,000 for water-soluble conductive polymer applications. It is in the range of ~ 200,000. From the viewpoint of removing unreacted monomers, low-molecular impurities and inorganic salts from the polymer, the range of 1.5000 to 100,000 is more preferable.

  The copolymer of the present invention is obtained by polymerizing the thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2) in water or an alcohol solvent in the presence of an oxidizing agent. Can be manufactured.

  The thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2) are not particularly limited, but [the amount of the thiophene compound represented by the above formula (1) / the above formula ( The total amount of thiophene compounds represented by 2)] is preferably polymerized at a ratio of 1 to 9999 (molar ratio) from the viewpoint of coatability and water solubility of the copolymer.

  Specific examples of the thiophene compound represented by the above formula (1) include 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Sodium methyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-ethyl-1-propanesulfonic acid Sodium, sodium 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-propyl-1-propanesulfonate, 3-[(2, Sodium 3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4- b]-[1,4] Dioxy N-2-yl) methoxy] -1-pentyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] Sodium 1-hexyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopropyl-1-propane Sodium sulfonate, sodium 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isobutyl-1-propanesulfonate, 3-[( 2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopentyl-1-propanesulfonate sodium, 3-[(2,3-dihydrothie [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-b]- [1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate potassium, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2 -Yl) methoxy] -1-methyl-1-propanesulfonic acid, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl -1-ammonium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate triethylammonium Etc. .

  The thiophene compound exemplified in the above formula (1) is obtained from a sultone compound branched with thieno [3,4-b] -1,4-dioxin-2-methanol according to a known method (for example, cited document 4). Easy to synthesize.

  The solvent used in the polymerization reaction is water or an alcohol solvent. Examples of water include pure water, and may be distilled water or ion exchange water. Examples of the alcohol solvent include alcohols such as methanol, ethanol, propanol, and butanol. These alcohol solvents may be used alone or in combination with water. Of these solvents, water or methanol is preferable, and water is more preferable. In addition, the solvent may be replaced with an inert gas such as degassed or nitrogen.

  The amount of solvent used in the polymerization reaction is, for example, an amount in which the thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2) are dissolved, and is not particularly limited. The range of 0.1 to 100 times by weight is preferable with respect to the total charged amount of the thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2), and the range of 1 to 20 times by weight Is more preferable.

  The oxidizing agent used in the polymerization reaction is one that promotes oxidative polymerization by oxidative dehydrogenation reaction, and is not particularly limited. For example, persulfuric acid, iron salt (III), hydrogen peroxide, hydrogen peroxide, Manganates, dichromates, cerium (IV) sulfate, oxygen and the like can be mentioned, and these may be used alone or in admixture of two or more.

  Specific examples of the persulfuric acid include persulfuric acid, ammonium persulfate, sodium persulfate, and potassium persulfate.

Specific examples of the iron salt (III) include FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , iron perchlorate, iron (III) para-toluenesulfonate, and the like. These may use anhydrides or hydrates.

  Specific examples of permanganate include sodium permanganate, potassium permanganate, and magnesium permanganate.

  Specific examples of the dichromate include ammonium dichromate and potassium dichromate.

Among these oxidizing agents, FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , or a combined system of persulfate and iron salt (III) is particularly preferable.

  The amount of the oxidizing agent used for the main polymerization reaction is not particularly limited, but is preferably 0.5 to 50 times the molar amount relative to the total number of moles charged of the thiophene compound and the comonomer. More preferably, it is 1-20 times mole. More preferably, it is 1-10 times mole.

  The pressure of the polymerization reaction may be normal pressure, reduced pressure, or increased pressure.

  The reaction atmosphere of the polymerization reaction may be in the air or in an inert gas such as nitrogen or argon. More preferably, it is in an inert gas.

  The reaction temperature of the main polymerization reaction is, for example, a temperature at which the thiophene compounds represented by the above formulas (1) and (2) can be subjected to oxidative polymerization, and is not particularly limited, but is preferably in the range of −10 to 150 ° C. The range of 5-100 degreeC is still more preferable.

  The reaction time of the main polymerization reaction is, for example, a time during which oxidative polymerization of the thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2) proceeds sufficiently, and is particularly limited. However, the range of 0.5 to 200 hours is preferable, and the range of 0.5 to 80 hours is more preferable.

  The reaction method of the present polymerization reaction is not particularly limited. For example, the thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2) are dissolved in water in advance. The oxidant may be added dropwise to the oxidant at once or, conversely, the thiophene compound represented by the above formula (1) and the thiophene compound represented by the above formula (2) in a solid or aqueous solution of the oxidant. May be dripped at once or slowly. Moreover, when using 2 or more types of oxidizing agents, you may add each oxidizing agent sequentially.

  The purification method of the copolymer of the present invention obtained by the main polymerization reaction is not particularly limited, and examples thereof include solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, and ion exchange resin treatment. Can be mentioned. Each may be performed alone or in combination.

  A typical isolation and purification method for the copolymer of the present invention is, for example, as follows.

  First, the aqueous solution after the polymerization reaction is added to a poor solvent such as acetone to precipitate the copolymer, and then the copolymer obtained by filtration under reduced pressure is washed with the poor solvent until the filtrate is colorless and transparent. When this copolymer contains an Fe salt that is insoluble in water, it must be added once to an aqueous sodium hydroxide solution, dissolved in water, and converted to a Na salt type copolymer in which M is Na ion. Is preferred.

  Next, this is added to a poor solvent such as alcohol to precipitate the copolymer, the alkali is removed, and the solid obtained by filtration under reduced pressure is washed with a poor solvent such as alcohol. Next, it is washed with a poor solvent such as acetone to obtain a Na salt type copolymer.

  When the obtained Na salt type copolymer is subsequently converted to an H type copolymer in which M is a hydrogen ion, it is treated with a cation exchange resin. Examples of the treatment method include a method in which an aqueous solution of the obtained Na salt type copolymer is passed through a column filled with a cation exchange resin, a body feed method in which the cation exchange resin is added to the aqueous solution, and the like. It is done.

As another method, the aqueous solution after polymerization is ultrafiltered to remove excess inorganic salts and unreacted monomers, and the resulting Na-type polymer is then subjected to cation exchange treatment to form an H-type copolymer. Can be obtained. Further, anion exchange treatment may be performed for the purpose of removing a small amount of anions.
The aqueous solution thus obtained was roughly concentrated, added to a poor solvent such as acetone and precipitated, and the solid obtained by filtration under reduced pressure was thoroughly washed with the poor solvent and dried under reduced pressure to obtain an H-type copolymer. can get.

Furthermore, when forming a salt with various ammonium salts, for example, adding various amine compounds or ammonium salt stock solutions or aqueous solutions thereof, or those diluted with an appropriate solvent to an aqueous solution of an H salt copolymer. It can be easily converted into an ammonium salt type copolymer in which M is NH ₄ ⁺ . For example, in the case of treatment with aqueous ammonia, the reaction solution is roughly concentrated, the aqueous solution is added to a poor solvent such as acetone to precipitate the copolymer, and then the solid obtained by vacuum filtration is added to the poor solvent. An ammonium salt copolymer is obtained by washing and drying under reduced pressure.

  In each step of the post-polymerization treatment, centrifugal sedimentation and homogenization treatment may be performed as necessary. Thereby, improvement of filtration efficiency can be aimed at. Further, when persulfate is used as the polymerization oxidant, ultrafiltration, dialysis, and cation / anion exchange resin mixing treatment are performed to remove inorganic salts.

  By using a water-soluble conductive polymer aqueous solution containing the copolymer of the present invention, molding processing for various uses becomes possible.

  Although the preparation method of water-soluble conductive polymer aqueous solution is not specifically limited, It is achieved by mixing and dissolving with water at room temperature or under heating (preferably 100 ° C. or less). At that time, a general mixing and dissolving operation using a stirrer chip or a stirring blade can be used. As other methods, ultrasonic irradiation, homogenization treatment (for example, use of a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, etc.) May be performed. In the case of homogenizing treatment, it is preferable to carry out the treatment while cooling in order to prevent thermal degradation of the polymer.

  The concentration of the copolymer of the present invention in the water-soluble conductive polymer aqueous solution is not particularly limited, but is usually 50% by weight or less, preferably 20% by weight or less, more preferably 10% by weight from the viewpoint of viscosity. It is as follows.

A conductive film can be produced using the copolymer of the present invention. For example, a conductive film can be easily obtained by applying the above water-soluble conductive polymer aqueous solution to a substrate and drying. Examples of the substrate include glass, plastic, polyester, polyacrylate, polycarbonate, resist substrate, and the like. Examples of the coating method include a casting method, a dipping method, a barcode method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, and an inkjet printing method. It not particularly limited as film ^thickness, but preferably in the range of 10 -2 ~10 ² μm. Although it does not specifically limit as surface resistance value of the coating film obtained, The thing of the range of 1-10 < ⁹ > ohm / square is preferable.

In the present invention, “water solubility sufficient for molding for various uses” means a particle diameter (D ₅₀ ) measured with a particle size distribution measuring device in a 10% by weight or less polymer aqueous solution prepared at room temperature or under heating. Is water-soluble so that it passes through a 0.02 μm filter.

  Moreover, in this invention, favorable electroconductivity means the electroconductivity whose electrical conductivity (electrical conductivity) in a film state is 50 S / cm or more.

Examples of the polythiophene and thiophene monomer of the present invention are shown below, but the present invention is not construed as being limited to these examples. The analytical instruments and measurement methods used in this example are listed below.
[GPC measurement]
Apparatus: GPC8020 manufactured by Tosoh Corporation
Column: TSKGel SuperAW5000 + SuperAW3000 + SuperAW2500 + guard column SuperAW-H
Detector: UV-8020
Eluent: 0.2M phosphate buffer (pH = 7) / CH ₃ CN = 9/1
Flow rate: 0.5mL / min
Detector: UV (220 nm)
Injection volume: 100 μL (about 500 ppm)
Temperature: 40 ° C
[HPLC measurement]
Column: TSK-GEL ODS-120T (250 mm × 4.6 mm ID)
Eluent: 50 mM phosphate buffer (pH = 2.8) / CH3CN = 1/11
Flow rate: 1.0 mL / min
Detector: UV (257 nm)
Temperature: 40 ° C
[Surface resistivity measurement]
Equipment: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation
[Film thickness measurement]
Equipment: DEKTAK XT manufactured by BRUKER
[Particle size measurement]
Apparatus: Nikkiso Co., Ltd. Microtrac Nanotrac UPA-UT151
[NMR measurement]
Equipment: Varian VXR-300S
[Viscosity measurement]
Complete Viscometer / BROOKFIELD VISCOMETER DV-1 P
lime
[Conductivity measurement]
A 0.5 mL aqueous solution containing a self-doped conductive polymer is applied to a 30 mm square alkali-free glass plate, dried at room temperature overnight, and then heated at 150 ° C. for 30 minutes on a hot plate to form a conductive polymer film. Got. It calculated based on the following formula | equation from the film thickness and the surface resistance value.

Electrical conductivity [S / cm] = 10 ⁴ / (surface resistivity [Ω / □] × film thickness [μm])
[Applicability & Antistatic evaluation]
The conductive polymer aqueous solution of the present invention was applied to a PET film (Lumirror T60 manufactured by Toray Industries Inc.) at a constant speed using a bar coater (Select Roller OSP-22 manufactured by OSG System Products Co., Ltd.), and then dried at 90 ° C. and 3 ° C. After partial drying to obtain a laminated film, the surface resistance value was measured. If the surface resistance value was stable, the coating property was good.
Synthesis Example 1 (2- (2- (2-((2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methoxy) ethoxy) ethoxy) ethanol (hereinafter abbreviated as TEG3OH) )] [Refer to formula (4) below])
To a 1 L separable flask was added (chloroethoxy) ethoxyethanol 25.0 g (148 mmol), 3,4-dihydropyran 24.9 g (296 mmol), Amberlite IR120B (acid type) 60 g, and chloroform 593 mL, and then nitrogen. The reaction was refluxed overnight under an air stream. Amberlite IR120B (acid type) was prepared by converting the corresponding Na type into an acid type with a 7% hydrochloric acid aqueous solution and then washing with acetone and chloroform. After cooling, the reaction solution was filtered and concentrated to synthesize 57.6 g of a pale yellow oily product (hereinafter referred to as “Compound A”). The compound A was used in the next reaction as it was without purification.

Next, a mixed solution of 445 mL of acetone and 55.5 g (370 mmol) of sodium iodide and the total amount of the compound A were added to a 1 L separable flask, and the mixture was heated and stirred overnight under reflux. After cooling to room temperature, the reaction solution was concentrated and extracted by adding 500 mL of dichloromethane and 300 mL of water. The aqueous layer was extracted again with 100 mL of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated to give a yellow oil. Further, purification was performed using silica gel chromatography (solvent: hexane / toluene = 10/1 to 5/1) to isolate 29.6 g of a light brown oil (yield = 58 mol%). It was confirmed to be Intermediate A by ¹³ C-NMR.
¹³ C-NMR (CDCl ₃ ): δ (ppm) 98.86, 71.97, 70.60, 70.25, 66.62, 62.14, 30.55, 25.41, 19.45, 2 .96
Next, after charging 5.13% (128 mmol) of 60% sodium hydride and 150 mL of dimethylformamide in a 300 mL eggplant-shaped flask under a nitrogen atmosphere, 14.75 g of (2,3-dihydrothieno [3,4] was added at room temperature. -B] [1,4] dioxin-2-yl) methanol [abbreviated as HMEDOT] was added with stirring. Thereafter, after maintaining at the same temperature for 15 minutes, the reaction solution was heated to 60 ° C. and then stirred at the same temperature for 1 hour. After cooling to room temperature, 29.3 g of the intermediate A was added dropwise so that the reaction temperature did not exceed 35 ° C. Next, the reaction solution was aged overnight, and then extracted with 400 mL of ethyl acetate and 500 mL of saturated brine. The obtained organic layer was concentrated and then purified by silica gel chromatography (solvent: hexane / toluene = 5/1 to 1/1) to isolate 7.5 g of a light brown oil (yield = 23%). It was confirmed to be Intermediate B by ¹³ C-NMR.

¹³ C-NMR (CDCl ₃ ): δ (ppm) 141.61, 141.52, 99.66, 99.57, 98.98, 72.65, 71.26, 70.72, 70.64, 70 59, 69.67, 66.67, 66.16, 62.25, 30.59, 24.45, 19.51
Next, 7.5 g (19.3 mmol) of the intermediate B, 16 g of Amberlite IR120B (acid type), and 70 mL of methanol are added to a 200 mL eggplant type flask, and the reaction solution is stirred overnight at room temperature under a nitrogen stream. did. Amberlite IR120B (acid type) was prepared by converting the corresponding Na type into an acid type with a 7% hydrochloric acid aqueous solution and then washing with acetone and chloroform. The reaction solution was filtered and concentrated, and then purified by silica gel chromatography (solvent: hexane / toluene = 4/6 to 0/10) to isolate 4.5 g of a viscous pale yellow oil (yield). (Rate = 76 mol%, HPLC purity = 99.5%). It was confirmed to be TEG3OH by ¹ H-NMR and ¹³ C-NMR.

  It has been found that TEG3OH dissolves 10 parts by weight or more with respect to 100 parts by weight of water at 30 ° C. or lower.

¹³ C-NMR (CDCl ₃ ): δ (ppm) 141.57, 141.46, 99.70, 99.62, 72.62, 72.54, 71.18, 70.70, 70.52, 70 .36, 69.66, 66.12, 61.77
¹ H-NMR (CDCl ₃ ): δ (ppm) 6.33 (m, 2H), 4.24 to 4.36 (m, 2H), 4.07 (dd, 1H), 3.60 to 3. 80 (m, 14H), 2.57 (br s, 1H)

Example 1 Synthesis of a copolymer (H-type polymer A) represented by the following formula (5) 3-[(2,3-dihydrothieno [3, synthesized by the method described in WO 2014/007299 4, -b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonic acid sodium 6.02 g (18.2 mmol), TEG3OH 0.57 g (1.9 mmol) described above ) And 50 g of water were added to a 100 mL round bottom flask equipped with a mechanical stirrer, and then 1.77 g (10.9 mmol) of anhydrous iron (III) chloride was added with stirring under a nitrogen atmosphere. After stirring at room temperature for 20 minutes, a mixed solution consisting of 8.64 g (36.3 mmol) of sodium persulfate and 25 g of water was added dropwise so that the reaction solution temperature was kept at 30 ° C. or lower. After stirring for 3 hours after completion of dropping, 510 g of distilled water was added to prepare an aqueous polymer solution having a concentration of about 1% by weight.

Next, the polymer aqueous solution was subjected to ultrafiltration using a hollow fiber membrane (manufactured by Spectrum, molecular weight cut-off = 10,000, membrane area = 0.079 m ² ), and the obtained aqueous solution was further added in advance. Amberlite 120B 250 mL (manufactured by Organo), which had been converted to the acid form with dilute hydrochloric acid, was passed through under the condition of space velocity = 1 hr ⁻¹ to obtain an H-type polymer aqueous solution.

  Further, the H-type polymer aqueous solution was concentrated by ultrafiltration using the same hollow fiber membrane as described above to obtain a copolymer (H-type polymer A) aqueous solution having a concentration of 0.9% by weight.

The aqueous solution of H-type polymer A (concentration: 0.9% by weight) was cast on an alkali-free glass plate (30 mm × 30 mm), and then annealed at 150 ° C. for 30 minutes to produce a film. The surface resistance, film thickness, and conductivity of the obtained film were 10.9Ω / □, 4.3 μm, and 213 S / cm, respectively. The particle diameter D ₅₀ of the H-type polymer A was 0.8 nm, which was outside the detection limit, and the viscosity of the 0.9 wt% aqueous solution was 42 mPa · s (20 ° C.).

Example 2 Synthesis of copolymer (H-type polymer B) represented by the following formula (6) A concentration of 0.9% by weight according to Example 1 except that 0.16 g (0.5 mmol) of TEG3OH was used. An aqueous solution of a copolymer (H-type polymer B) was obtained. Further, a film of H-type polymer B was prepared in the same manner as in Example 1, and the surface resistance, film thickness, and conductivity of the obtained film were measured. As a result, 11.0Ω / □, 3.9 μm, 233 S / cm, respectively. Met. Further, the particle diameter _{D 50} of the H-type polymer B represents 0.8nm detection ultrafiltration, the viscosity of the concentration of 0.9 wt% aqueous solution was 23mPa · s (20 ℃).

Example 3 Synthesis of copolymer (H-type polymer C) represented by the following formula (7) A concentration of 0.9% by weight according to Example 1 except that 1.38 g (4.54 mmol) of TEG3OH was used. An aqueous solution of a copolymer (H-type polymer C) was obtained. Further, a film of H-type polymer C was prepared in the same manner as in Example 1, and the surface resistance, film thickness, and conductivity of the obtained film were measured. As a result, 12.0Ω / □, 4.0 μm, 208 S / cm, respectively. Met. Further, H-type polymer C particle diameter _{D 50} of the showed 0.8nm detection ultrafiltration, the viscosity of the concentration of 0.9 wt% aqueous solution was 55mPa · s (20 ℃).

Comparative Example Synthesis of an aqueous copolymer solution was attempted according to Example 1 except that 6.0 g (19.7 mmol) of TEG3OH was used. However, it was clogged during ion exchange because of its high cohesiveness. Therefore, the target aqueous solution could not be obtained.

Example 4
Each of the aqueous solutions obtained in Examples 1 to 3 was applied to a PET substrate using a bar coater. As a result of measuring the surface resistance value of the laminated film obtained after drying, all the coating films showed a 10 ² Ω / □ level stably regardless of the measurement location, and the coating property was good.

Claims (5)

A thiophene monomer comprising a repeating unit represented by the following formula (M1) (hereinafter referred to as “thiophene monomer unit”) and a repeating unit represented by the following formula (M2) (hereinafter referred to as “comonomer unit”). A copolymer characterized in that the unit and the comonomer unit may be self-doped, and the ratio of thiophene monomer unit / comonomer unit (mol / mol) is 1 to 9999.

[Wherein R may be the same or different for each repeating unit, and represents a chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a fluorine atom. M may be different for each repeating unit and represents a hydrogen ion, an alkali metal ion, or a conjugate acid of an amine compound. q represents an integer of 1 to 4. ] A compound in which the amine compound is represented by N (R ¹ ) (R ² ) (R ³ ) (the R ^{1 to} R ³ are each independently a hydrogen atom or a total carbon number that may have a substituent) It represents an alkyl group having 1 to 6 carbon atoms), pyridine, or an imidazole compound which may have a chain, branched or cyclic alkyl group having 1 to 6 carbon atoms. The copolymer according to 1. The copolymer according to claim 1 or 2, wherein the ratio of thiophene monomer unit / comonomer unit (mol / mol) is 1 to 999. The thiophene compound represented by the following formula (1) and the thiophene compound represented by the following formula (2) are polymerized in water or an alcohol solvent in the presence of an oxidant. The manufacturing method of the copolymer as described in any one of these.

[Wherein, R represents a chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a fluorine atom. M represents a hydrogen ion, an alkali metal ion, or a conjugate acid of an amine compound. q is an integer of 1 to 4. ] An aqueous solution comprising the copolymer according to any one of claims 1 to 3.