JP2020183493A - Complex composed of polythiophene-polystyrene sulfonate copolymer, and water dispersion containing the same - Google Patents

Abstract

To provide a novel complex composed of a polythiophene-polystyrene sulfonate copolymer, having better physical properties than those of conventionally well-known conductive polymer PEDOT: PSS.SOLUTION: The present invention provides a complex of a polythiophene containing a repeating unit selected from the group consisting of a thiophene repeating unit represented by formula (1) and a thiophene repeating unit represented by formula (2), and a polystyrene sulfonate copolymer containing a repeating unit of styrene sulfonic acid and a repeating unit of a vinyl monomer having a sulfobetaine residue (where R1 is H, or a 1-8C open-chain or branched alkyl group (the group may have a hydroxy group or a 1-8C alkoxy group)).SELECTED DRAWING: None

Description

The present invention relates to a novel composite composed of a polythiophene-polystyrene sulfonic acid copolymer and an aqueous dispersion containing the same.

Due to its high conductivity, the novel composite composed of the polythiophene-polystyrene sulfonic acid copolymer of the present invention is an antistatic material, a solid electrolyte for capacitors, various sensors, an organic electroluminescence material, a conductive fiber, an actuator and a thermoelectric conversion material. It can be applied to electrodes and the like.

Polymers having a π-conjugated double bond represented by polyacetylene, polythiophene, polyaniline, polypyrrole, etc. are known to become conductors (conductive polymers) by doping with acceptors and donors, and are used as antistatic agents and capacitors. Applications to solid electrolytes, conductive paints, electrochromic elements, transparent electrodes, transparent conductive films, chemical sensors, actuators, etc. are being studied. Among them, poly (3,4-ethylenedioxythiophene): poly, which is a conductive polymer obtained by polymerizing 3,4-ethylenedioxythiophene in the presence of a water-soluble polymer dopant such as polystyrene sulfonic acid (PSS): poly. The (4-styrene sulfonic acid) composite (hereinafter abbreviated as PEDOT: PSS) is the most advanced conductive polymer because it has both good conductivity and moldability. In particular, it has been put into practical use in solid electrolytic capacitors, but it is still highly conductive in order to further increase the capacity and reduce the ESR with the progress of conductivity and miniaturization of automobiles in recent years. Materials with excellent materials, substrate adhesion, and heat resistance are being developed.

Therefore, in order to deal with the above problems, a copolymer containing PSS to PSS, which is a homopolymer, is being studied. For example, a copolymer of styrene sulfonic acid (salt) and (meth) acrylamide monomer (Patent Documents 1 and 2), a copolymer of styrene sulfonic acid and (meth) acrylic acid monomer (Patent Document 3), and styrene sulfone. A copolymer of an acid (salt) and an unsaturated hydrocarbon-containing alkoxysilane compound (Patent Document 4) has been reported.

However, the specific description of the polystyrene sulfonic acid copolymer composed of the styrene sulfonic acid (salt) and the sulfobetaine residue having an unsaturated hydrocarbon bond according to the present invention, and the conductivity of the complex of them and polythiophene. There is no specific description of the impact.

JP-A-2017-218483 JP-A-2017-57267 Japanese Patent No. 5252669 Japanese Patent No. 5281209

The thiophenes described in Patent Documents 1 to 4 have improved substrate adhesion by using a PSS copolymer as an external dopant, but their conductivity tends to decrease as the amount of PSS in the copolymer decreases. was there.

The present invention has been made in view of the above background techniques, and an object of the present invention is to provide a novel polythiophene-polystyrene sulfonic acid copolymer having both high conductivity and high adhesion, and an aqueous dispersion containing the same. It is to be.

Another object of the present invention is to provide a novel polystyrene sulfonic acid copolymer for providing a conductive polymer having both high conductivity and high adhesion.

As a result of diligent studies to solve the above problems, the present inventors have found a polystyrene sulfonic acid copolymer containing a repeating unit of a vinyl monomer having a sulfobetaine residue instead of a conventionally known polystyrene sulfonic acid polymer. We have found that the polythiophene composite composition becomes highly conductive and the adhesion is improved by using it, and have completed the present invention.

That is, the present invention relates to a composite composed of a polythiophene-polystyrene sulfonic acid copolymer and an aqueous dispersion containing the same.
[1] A polythiophene containing at least one thiophene repeating unit selected from the group consisting of a thiophene repeating unit represented by the following formula (1) and a thiophene repeating unit represented by the following formula (2), and the following formula ( A complex with a polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by 3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the following formula (4).

(In the above formula, X independently represents an oxygen atom or -NH-, and R ¹ is a hydrogen atom and a chain or branched alkyl group having 1 to 8 carbon atoms (the group is hydroxy). It may have a group or an alkoxy group having 1 to 8 carbon atoms), where R ⁴ represents a hydrogen atom, a chain or branched alkyl group having 1 to 8 carbon atoms, and R ² and R. ³ independently represents a chain or branched alkyl group having 1 to 8 carbon atoms, m and n each independently represent an integer of 1 to 6, and M ⁺ are independent of each other. Represents an alkali metal ion selected from the group consisting of hydrogen ion, Li ion, Na ion and K ion, or a conjugated acid of an amine compound.
[2] The composite according to [1], wherein the content of the repeating unit of the styrene sulfonic acid represented by the formula (3) in the polystyrene sulfonic acid copolymer is 70 to 99.99 mol%. body.
[3] The composite according to [1], wherein the content of the repeating unit of the styrene sulfonic acid represented by the formula (3) in the polystyrene sulfonic acid copolymer is 90 to 99.9 mol%. body.
[4] The number of styrene sulfonic acid repeating units represented by the formula (3) is the total repeating unit of the thiophene repeating unit represented by the formula (1) and the thiophene repeating unit represented by the formula (2). The complex according to any one of [1] to [3], which is 1.0 to 3.0 times (mol ratio) the number.
[5] The complex according to any one of [1] to [4], wherein R ² , R ³ and R ⁴ are each independently a methyl group or an ethyl group.
[6] The complex according to [1], wherein the polystyrene sulfonate copolymer has a weight average molecular weight of 10,000 to 300,000 in terms of a sodium polystyrene sulfonate standard substance.
[7] An aqueous dispersion containing the complex according to any one of [1] to [6].
[8] The aqueous dispersion according to [7], further containing at least one conductivity improver selected from a water-soluble compound having a hydroxyl group, a water-soluble sulfoxide, a water-soluble amide compound, and a water-soluble compound having a lactone structure. ..
[9] Polystyrene containing a repeating structural unit of styrene sulfonic acid represented by the above formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4) in a solvent containing water. The composite according to any one of [1] to [5], wherein the thiophene compound represented by the following formula (5) is polymerized in the presence of a sulfonic acid copolymer in the presence of an oxidizing agent. How to make a body.

(In the formula, R ¹ is a hydrogen atom or a chain or branched alkyl group having 1 to 8 carbon atoms (the group may have a hydroxy group or an alkoxy group having 1 to 8 carbon atoms). Represents.)
[10] A polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by the following formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the following formula (4).

(In the above formula, X independently represents an oxygen atom or -NH-, R ⁴ represents a hydrogen atom, a chain or branched alkyl group having 1 to 8 carbon atoms, and R ² , And R ³ each independently represent a chain or branched alkyl group having 1 to 8 carbon atoms, m each independently represents an integer of 1 to 6, and n each independently represents. Represents 4, 5, or 6, and M ⁺ independently represents an alkali metal ion selected from the group consisting of hydrogen ion, Li ion, Na ion, and K ion, or a conjugated acid of an amine compound.)

Since the composite made of the polythiophene-polystyrene sulfonic acid copolymer of the present invention has higher conductivity and substrate adhesion than the conventional PEDOT-PSS, it has a higher capacity and lower capacity as a solid electrolyte of a solid electrolytic capacitor. It is expected that it can contribute to ESR. In addition, it can be expected to be applied to transparent electrodes, transparent conductive films, chemical sensors, actuators and the like.

¹ H-NMR of the polystyrene sulfonic acid copolymer obtained in Example 1 _(D 2 O) spectrum ¹ H-NMR of the polystyrene sulfonic acid copolymer obtained in Example 2 _(D 2 O) spectrum ¹ H-NMR of the polystyrene sulfonic acid copolymer obtained in Example 3 _(D 2 O) spectrum

Hereinafter, the present invention will be described in detail.

The present invention comprises a polythiophene containing at least one thiophene repeating unit selected from the group consisting of the thiophene repeating unit represented by the above formula (1) and the thiophene repeating unit represented by the above formula (2), and the above formula. A complex with a polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4). Copolymerized with an aqueous dispersion, a repeating unit of styrene sulfonic acid represented by the above formula (3), and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4). It relates to a copolymer.

In the above formulas (1) and (2), R ¹ has a hydrogen atom and a chain or branched alkyl group having 1 to 8 carbon atoms (the group has a hydroxy group or an alkoxy group having 1 to 8 carbon atoms). It may be).

The chain or branched alkyl group having 1 to 8 carbon atoms is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and the like. Examples thereof include a pentyl group, a neopentyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, a 2-ethylhexyl group and the like.

The alkoxy group having 1 to 8 carbon atoms is not particularly limited, but for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a pentyloxy group, and a neopentyl group. Examples thereof include an oxy group, a sec-butoxy group, a t-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, a 2-ethylhexyloxy group and the like.

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-butyl group, or an n-hexyl group, and is preferably a hydrogen atom, a methyl group, or an ethyl group in terms of excellent adhesion. ..

M ⁺ in the above formula (3) independently represents an alkali metal ion selected from the group consisting of hydrogen ion, Li ion, Na ion and K ion, or a conjugate acid of an amine compound.

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, but for example, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine and the like (the above is the general formula N (R). ⁵ ) Amine compounds having sp3 mixed orbitals of (amine compounds represented by (R ⁶ ) and (R ⁷ )), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridinepyridine (above, pyridines), Amine compounds having sp2 mixed orbitals such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-methylimidazole (above, imidazoles) and the like. Can be mentioned.

The R ^{5 to} R ⁷ each independently represent a hydrogen atom or an alkyl group having a total carbon number of 1 to 18 which may have a substituent. Of these, R ^{5 to} R ⁷ are more preferably hydrogen atoms or alkyl groups having a total carbon number of 1 to 10 which may have a substituent, respectively, and each of them is independently hydrogen. It is more preferably an atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

Here, the alkyl group having a total carbon number of 1 to 18 which may have a substituent is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and the like. 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 Examples thereof include a group, a hydroxyethoxyethyl group, a hydroxyethoxyethoxyethyl group, a benzyl group, a phenethyl group, an aminoethyl group and the like.

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

Among them, as the substituent ^R 5 to R ^7, more preferably, each independently, a hydrogen atom, a methyl group, or ethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2 , An alkyl group having a hydroxy group such as a 3-dihydroxypropyl group can be mentioned.

Regarding M ⁺ , alkali metal ions selected from the group consisting of hydrogen ions, Li ions, Na ions and K ions, or R ^{5 to} R ⁷ are independently hydrogen atoms and methyls in terms of excellent adhesion. N ⁺ (R ⁵ ) (R ⁶ ) (R), which is a group selected from a group, an ethyl group, or a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2,3-dihydroxypropyl group. It is preferably an ammonium ion represented by ⁷ ), and independently, hydrogen ion, Li ion, Na ion, K ion, ammonium ion, methyl ammonium ion, dimethyl ammonium ion, trimethyl ammonium ion, ethyl ammonium ion, It is preferably diethylammonium ion, triethylammonium ion, monoethanolammonium ion, diethanolammonium ion, or triethanolammonium ion.

In the above formula (4), X independently represents an oxygen atom or -NH-. Of these, an oxygen atom is preferable because it has excellent adhesion.

R ² and R ³ in the above formula (4) each independently represent a chain or branched alkyl group having 1 to 8 carbon atoms.

The chain or branched alkyl group having 1 to 8 carbon atoms is not particularly limited, and is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or a pentyl. Groups, neopentyl groups, n-butyl groups, sec-butyl groups, t-butyl groups, n-hexyl groups, cyclohexyl groups, 2-ethylhexyl groups and the like can be mentioned.

From the viewpoint of ease of synthesis and availability, R ² and R ³ are preferably hydrogen atoms, methyl groups, ethyl groups, n-butyl groups, or n-hexyl groups, respectively, and are independent of each other. It is preferably a hydrogen atom, a methyl group, or an ethyl group.

Further, R ⁴ in the above formula (4) independently represents a hydrogen atom or a chain or branched alkyl group having 1 to 8 carbon atoms.

Regarding the chain or branched alkyl group having 1 to 8 carbon atoms, for example, the same group as the chain or branched alkyl group having 1 to 8 carbon atoms exemplified in R ² and R ³ described above may be mentioned. Can be done.

R ⁴ is synthesized, and the ease of availability, each independently, a hydrogen atom, a methyl group, an ethyl group, preferably an n- butyl group, or n- hexyl group, each independently, a hydrogen atom , Methyl group, or ethyl group is preferable.

In the above equation (4), m and n each independently represent an integer of 1 to 6.

Regarding m, from the viewpoint of ease of synthesis and availability, it is preferably 2 to 5, more preferably 2, 3 or 4, and even more preferably 3.

Regarding n, from the viewpoint of ease of synthesis and availability, it is preferably 3 to 6, more preferably 3, 4, or 5, and even more preferably 3 or 4.

From the viewpoint of novelty, the polystyrene sulfonic acid copolymer of the present invention preferably has n of 4, 5, or 6, more preferably 4, or 5. Is more preferable.

The polystyrene sulfonic acid copolymer containing the repeating unit of styrene sulfonic acid represented by the above formula (3) and the repeating unit of vinyl monomer having a sulfobetaine residue represented by the above formula (4) is particularly limited. However, for example, a copolymer represented by the following formula (8) can be exemplified.

^(Wherein, R ^2, R ^{3, R} 4, m, and for n is, ^{R 2,} R 3 in the formula ^{(4), R} 4, m, and n is as defined above .a and b, optionally Represents a positive real number of.)
The copolymer represented by the formula (8) may be a random copolymer or a block copolymer.

The copolymer is not particularly limited, but for example, those represented by the following formulas (8-1) to (8-48) can be specifically exemplified. The copolymer may be a random copolymer or a block copolymer, and the following a and b represent arbitrary positive real numbers.

In the formulas (8) and (8-1) to (8-48), the relationship between a and b is such that {a ÷ (a + b)} × 100 is 70 to 70 from the viewpoint of improving adhesion and conductivity. It is preferably 0.01, more preferably {a ÷ (a + b)} × 100 is 80 to 0.1, and preferably {a ÷ (a + b)} × 100 is 90 to 0.1. More preferred.

A polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by the above formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4) is obtained by the following formula ( It can be produced by copolymerizing a styrene sulfonic acid monomer represented by 6) and a vinyl monomer having a sulfobetaine residue represented by the following formula (7).

^{(Wherein, X, M +, R 2} , R 3, R 4, m, and n are the same as defined above formula (3) and (4). The same applies to the preferred ranges.)
The styrene sulfonic acid monomer represented by the above formula (6) is not particularly limited, and examples thereof include lithium p-styrene sulfonate, sodium p-styrene sulfonate, potassium p-styrene sulfonate, and the like. A commercially available product can be used.

The vinyl monomer having a sulfobetaine residue represented by the above formula (7) is not particularly limited, but for example, N- (meth) acryloyloxyalkyl-N, N-dimethylammoniumalkyl-α-sulfo. Betaines, N- (meth) acrylamidealkyl-N, N-dialkylammonium alkyl-α-sulfobetaines can be mentioned.

Examples of N- (meth) acryloyloxyalkyl-N and N-dimethylammonium alkyl-α-sulfobetaines include N- (meth) acryloyloxymethyl-N, N-dimethylammonium methyl-α-sulfobetaine and N- ( Meta) acryloyloxymethyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N- (meth) acryloyloxymethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxymethyl- N, N-dimethylammonium butyl-α-sulfobetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammonium Ethyl-α-sulfobetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammonium butyl-α-sulfobetaine , N- (meth) acryloyloxypropyl-N, N-dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N- (meth) Acryloyloxypropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammoniumbutyl-α-sulfobetaine, N- (meth) acryloyloxybutyl-N, N-Dimethylammonium Methyl-α-sulfobetaine, N- (meth) acryloyloxybutyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N- (meth) acryloyloxybutyl-N, N-dimethylammoniumpropyl- Examples thereof include α-sulfobetaine, N- (meth) acryloyloxybutyl-N, and N-dimethylammonium butyl-α-sulfobetaine.

Examples of N- (meth) acrylamidealkyl-N and N-dialkylammoniumalkyl-α-sulfobetaines include N- (meth) acrylamidepropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, or N-. Examples thereof include (meth) acrylamidepropyl-N and N-dimethylammonium butyl-α-sulfobetaine.

As the vinyl monomer having a sulfobetaine residue represented by the above formula (7), a commercially available product can be used, or a vinyl monomer produced based on a generally known production method can be used.

A polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by the above formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4) is described in the above formula (4). It is preferable to produce by copolymerizing a styrene sulfonic acid monomer represented by 6) and a vinyl monomer having a sulfobetaine residue represented by the above formula (7) in a solvent in the presence of a radical initiator.

Regarding the polystyrene sulfonic acid copolymer of the present invention, a monomer other than the styrene sulfonic acid monomer represented by the above formula (6) and the vinyl monomer having a sulfobetaine residue represented by the above formula (7) (No. 1). It may be a copolymer containing a repeating unit of (trivinyl monomer).

The tertiary vinyl monomer is not particularly limited, but for example, methyl acrylate, ethyl acrylate, butyl acrylate, aminoethyl acrylate, N-vinylcarbazole, phenoxyethyl acrylate, methyl methacrylate, and methacrylic. Ethyl acrylate, dimethyl acrylamide, dimethyl aminopropyl acrylamide, acryloyl morpholine, hydroxyethyl acrylamide, isopropyl acrylamide, 4-t-butyl cyclohexyl acrylate, dimethyl aminopropyl acrylamide methyl chloride quaternary salt, dimethyl aminoethyl acrylate benzyl chloride quaternary salt, etc. Can be mentioned.

The radical polymerization initiator is preferably a water-soluble radical polymerization initiator and is not particularly limited, but for example, persulfates such as hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate. , 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- ( 2-Hydroxyethyl) propionamide], 2,2'-azobis {2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- (2-imidazolin-2-yl) ) Propane] disulfate dihydrate, 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] tetrahydrate Rate, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy Examples thereof include azo-based initiators such as ethyl] propionamide}.

The amount of the radical initiator used is usually preferably in the range of 0.001 to 10 mol%, more preferably 0, with respect to the total amount of the monomers represented by the above formulas (6) and (7). It is in the range of 0.01 to 5 mol%.

The solvent is preferably a solvent containing water, and is not particularly limited, but may be water alone, a mixture of water and a water-soluble organic solvent, or an aqueous solution of water and a water-soluble solid. It may be.

The aqueous organic solvent is not particularly limited as long as it is soluble in water, and examples thereof include alcohols, ether compounds, ester compounds, and amide compounds, and alcohols are preferable. Examples of the alcohol include lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and sec-butanol, and glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.

When the solvent is a mixture of water and a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 0.1 to 30 wt%, more preferably 1 to 20 wt%.

The polymerization conditions are not particularly limited, but it is preferable to heat at 20 to 150 ° C. for 4 to 50 hours in an inert gas atmosphere, and appropriately depending on the polymerization solvent, monomer composition, and water-soluble radical polymerization initiator species. It is preferable to adjust.

The amount of the repeating unit of the styrene sulfonic acid monomer represented by the above formula (6) in the polystyrene sulfonic acid copolymer is not particularly limited, but is 70 to 99. With respect to the total amount of the charged monomers. It is preferably 99 mol%, more preferably 80 to 99.9 mol%, and even more preferably 90 to 0.1 mol% from the viewpoint of improving adhesion and conductivity.

The weight average molecular weight of the polystyrene sulfonate copolymer thus obtained is preferably several thousand to 500,000, more preferably 10,000 to 300,000 in terms of sodium polystyrene sulfonate standard substance. More preferably, it is 10,000 to 100,000.

Further, in order for the polystyrene sulfonic acid copolymer to act as an external dopant and a dispersant for polythiophene, it is preferable to bring it into contact with a cation exchange resin to convert it into an acid form. The contact method between the polystyrene sulfonic acid copolymer and the cation exchange resin may be either a column method or a batch method. The cation exchange resin is not particularly limited, but a strongly acidic cation exchange resin is preferable, and a sulfonic acid type strongly acidic cation exchange resin is more preferable. Commercially available products can be used as the ion exchange resin, for example, Diaion (registered trademark) UBK-550, Diaion (registered trademark) SK1B (manufactured by Mitsubishi Chemical Corporation), Amberlite (registered trademark) IR120B, Amber. Light (registered trademark) 200C, Dowex (registered trademark) MSC-1 (manufactured by Dow), Duolite C26 (manufactured by Roam & Haas), LEWATTI (registered trademark) S108H, SP-112 (manufactured by Rankses) It can be preferably used.

The polystyrene sulfonic acid copolymer of the present invention may be any polymer such as a block polymer, an alternating polymer, a random polymer, and a graft polymer.

Further, the polystyrene sulfonic acid copolymer of the present invention may be further purified by a separation operation such as a reprecipitation method or ultrafiltration.

The polystyrene sulfonic acid copolymer of the present invention is excellent in adhesion, and the content of the repeating unit of styrene sulfonic acid represented by the formula (3) in the polystyrene sulfonic acid copolymer is 70 to 99.99 mol. %, More preferably 80 to 99.9 mol%, and even more preferably 90 to 99.9 mol%.

The complex of the present invention comprises a polythiophene containing at least one thiophene repeating unit selected from the group consisting of the thiophene repeating unit represented by the above formula (1) and the thiophene repeating unit represented by the above formula (2). , A complex with a polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by the above formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4). However, with respect to the complex, the number of styrene sulfonic acid repeating units represented by the formula (3) is the thiophene repeating unit represented by the formula (1) and the thiophene repeating unit represented by the formula (1) in that the composite is excellent in adhesion and conductivity. It is preferable that the complex satisfies the relationship that the total number of repeating units of the thiophene repeating unit represented by the formula (2) is 1.0 to 3.0 times (mol ratio). It is more preferable that the complex satisfies the relationship of fold to 2.5 times (mol ratio).

The complex of the present invention is a repeating structural unit of styrene sulfonic acid represented by the above formula (3) and a repeating vinyl monomer having a sulfobetaine residue represented by the above formula (4) in a solvent containing water. It can be produced by polymerizing a thiophene compound represented by the following formula (5) in the presence of a polystyrene sulfonic acid copolymer containing a unit in the presence of an oxidizing agent (hereinafter referred to as "the main polymerization reaction"). it can.

(In the formula, R ¹ is a hydrogen atom or a chain or branched alkyl group having 1 to 8 carbon atoms (the group may have a hydroxy group or an alkoxy group having 1 to 8 carbon atoms). Represents.)
R ¹ in the above formula (5) is a hydrogen atom, a chain or branched alkyl group having 1 to 8 carbon atoms (even if the group has a hydroxy group or an alkoxy group having 1 to 8 carbon atoms). Good).

The chain or branched alkyl group having 1 to 8 carbon atoms is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and the like. Examples thereof include a pentyl group, a neopentyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, and a 2-ethylhexyl group.

The alkoxy group having 1 to 8 carbon atoms is not particularly limited, but for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a pentyloxy group, and a neopentyl group. Examples thereof include an oxy group, a sec-butoxy group, a t-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, a 2-ethylhexyloxy group and the like.

The solvent used in this polymerization reaction is a solvent containing water, and is not particularly limited, but water or a mixture of water and a water-soluble solvent can be used. Examples of water include pure water, and distilled water and ion-exchanged water may be used. Examples of the water-soluble solvent include monohydric alcohols such as methanol, ethanol, propanol and n-butanol, polyhydric alcohols such as ethylene glycol and propylene glycol, and non-polar solvents such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone. Can be mentioned.

The solvent may be degassed or replaced with an inert gas such as nitrogen.

The amount of the solvent used in this polymerization reaction is not particularly limited as long as the thiophene compound represented by the above formula (5) can be dissolved or uniformly dispersed, but is represented by, for example, the above formula (5). The range of 10 to 1000 times by weight is preferable, and the range of 100 to 500 times by weight is more preferable with respect to the charged amount of the thiophene compound.

The oxidizing agent used in this polymerization reaction is preferably one that promotes oxidative polymerization by an oxidative dehydrogenation reaction, and is not particularly limited, but for example, persulfates, iron salts (III), and iron salts. Examples thereof include (II), hydrogen peroxide, permanganate, bicarbonate, cerium (IV) sulfate, oxygen and the like, and these may be used alone or in combination of two or more. You may.

Here, the persulfates are not particularly limited, and specific examples thereof include persulfate, ammonium persulfate, sodium persulfate, and potassium persulfate.

The iron salt (III) is not particularly limited, but specifically, FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , iron perchlorate, iron para-toluenesulfonate (III), or the like. Is exemplified. The iron salt (II) is not particularly limited, and specific examples thereof include FeCl ₂ , FeSO ₄ , iron acetate (II), and the like. These iron salts may use anhydrides or hydrates.

The permanganate is not particularly limited, and specific examples thereof include sodium permanganate, potassium permanganate, and magnesium permanganate.

The dichromate is not particularly limited, and specific examples thereof include ammonium dichromate and potassium dichromate.

Of these oxidizing agents, a combination system of either FeSO ₄ or Fe ₂ (SO ₄ ) ₃ and persulfates is particularly preferable.

The amount of the oxidizing agent used in this polymerization reaction is not particularly limited, but may be 0.5 to 10 times the number of moles of the thiophene compound represented by the above formula (5). preferable. More preferably, it is 0.8 to 5.0 times the molar amount. More preferably, it is 1.0 to 2.0 times the molar amount.

The amount of the polystyrene sulfonic acid copolymer used in this polymerization reaction is 0.5 to 5.0 times that of the thiophene compound represented by the above formula (5) in the styrene sulfonic acid residue in the copolymer. The amount is preferably in the range of molars, and more preferably in the range of 1.0 to 3.0 times the molar amount.

The pressure of this polymerization reaction may be normal pressure, reduced pressure, or pressurized.

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

The reaction temperature of this polymerization reaction is, for example, a temperature at which the thiophene compound represented by the above formula (5) can be oxidatively polymerized, and is not particularly limited, but is preferably in the range of −10 to 100 ° C., preferably 10 to 60. The ° C range is more preferred.

The reaction time of this polymerization reaction is, for example, the time during which the oxidative polymerization of the thiophene compound represented by the above formula (5) sufficiently proceeds, and is not particularly limited, but is preferably in the range of 0.5 to 200 hours. , 0.5-80 hours is more preferred.

The reaction method of this polymerization reaction is not particularly limited, but for example, the thiophene compound represented by the above formula (5) is previously dissolved in water or a mixture of water and a water-soluble solvent, and the compound is oxidized. The agent may be added dropwise at once or slowly, and conversely, an aqueous solution of the thiophene compound represented by the above formula (5) may be added dropwise to the aqueous solution of the oxidizing agent at once or slowly. When two or more kinds of oxidizing agents are used, each oxidizing agent may be added in sequence.

In this polymerization reaction, the viscosity of the liquid tends to increase with the addition of the oxidizing agent, so it is necessary to uniformly stir the entire liquid. For the stirring blades, propeller blades, paddle blades, Max Blend (registered trademark) blades (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), full zone (registered trademark) blades (manufactured by Shinko Environmental Solutions Co., Ltd.), and disc turbine blades can be used and react. A plurality of baffles may be installed inside the reaction vessel in order to mix the inside of the container more uniformly. In addition, a homomixer, a homogenizer, etc. used for emulsification and dispersion may also be used in combination.

Further, in this polymerization reaction, a polystyrene sulfonic acid copolymer is used as an external dopant, but in order to further increase the carrier density of polythiophene and improve the conductivity, an acceptor-type dopant is further added to carry out the main polymerization reaction. You may go.

The accepting dopant is not particularly limited, but for example, inorganic acids such as hydrochloric acid, nitrate and sulfuric acid, organic carboxylic acids such as formic acid, acetic acid, oxalic acid and trifluoroacetic acid, methanesulfonic acid and ethanesulfonic acid. , Benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid and other organic sulfonic acids can be exemplified.

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

A typical isolation and purification method for the complex of the present invention is, for example, a method in which the aqueous dispersion after the polymerization reaction is directly contacted with a cation and / or an anion exchange resin, and if necessary, ultrafiltration. An example of a method of desalting and purification using a membrane separation method such as filtration or dialysis can be exemplified. As the cation exchange resin, the sulfonic acid type strongly acidic cation exchange resin mentioned above, and as the anion exchange resin, Amberlite (registered trademark) IRA93 (organo), Amberlist (registered trademark) A21 (Dow Chemical). ), LEWATTI (registered trademark) 35A, LEWATTI (registered trademark) MP62, LEWATTI (registered trademark) MP62WS (manufactured by LANXESS) and the like can be exemplified.

The aqueous dispersion containing the composite of the present invention can be molded into various uses.

The above aqueous dispersion may be subjected to ultrasonic irradiation and homogenization treatment (for example, use of a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, etc.), if necessary. When the homogenization treatment is performed, it is preferable to carry out the homogenization treatment while cooling the polymer in order to prevent thermal deterioration.

Further, a polythiophene-polystyrene sulfonic acid copolymer can also be obtained as a powder by crudely concentrating the obtained aqueous dispersion and adding it to a poor solvent such as acetone to precipitate it.

Further, when forming a salt with various ammonium salts, for example, in an aqueous dispersion of the above acid type polythiophene-polystyrene sulfonic acid copolymer, a stock solution of various amine compounds or ammonium salts, an aqueous solution thereof, or other suitable solution. by adding those diluted with a solvent can be easily ^{M +} converts _NH ^{4 +} or ^{N + (R 5) (R} 6) to ^{(R 7)} a is an ammonium salt type optically active polythiophenes. If necessary, the obtained aqueous solution can be added to a poor solvent such as acetone to obtain a powdered ammonium salt-type polythiophene-polystyrene sulfonic acid copolymer.

The composite of the present invention preferably contains water in terms of excellent operability, and preferably contains water and is an aqueous dispersion.

The concentration of the complex in the aqueous dispersion containing the complex of the present invention in the aqueous dispersion is not particularly limited, but is usually preferably 20% by weight or less, more preferably 10% by weight or less. From the viewpoint of viscosity, it is more preferably 5% by weight or less.

Further, the aqueous dispersion of the complex of the present invention further contains at least one conductivity improver selected from a water-soluble compound, a water-soluble sulfoxide, a water-soluble amide compound, and a water-soluble compound having a lactone structure. Is preferable.

As the conductivity improver, known ones can be used. For example, amides such as N, N-dimethylacetamide, N-methylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylformanilide, N-methylpyrrolidone, pyrrolidone; tetramethylene sulfone, dimethyl sulfoxide, etc. Sulfone compounds or sulfoxide compounds; sugar alcohols such as sorbitol and mannitol; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol and triethylene glycol can be mentioned.

The amount of the conductivity improver added is 0.5 to 20 wt%, preferably 1.0 to 10 wt% with respect to the aqueous dispersion.

A conductive coating can be produced using the aqueous dispersion of the present invention. For example, a conductive film can be easily obtained by applying and drying an aqueous dispersion on a base material. Examples of the base material 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, an inkjet printing method and the like.

The present invention will be described in more detail with reference to the following examples, but the present invention is not construed as being limited thereto. The analytical instruments and measurement methods used in this example are listed below.
[NMR measurement]
Equipment: JEM-ECZ400S manufactured by JEOL Ltd.
[Measurement of surface resistivity]
Equipment: Mitsubishi Chemical Corporation Loresta GP MCP-T600.
[Film thickness measurement]
Equipment: DEKTAK XT manufactured by BRUKER.
[Particle size measurement]
Equipment: Microtrac Nanotrac UPA-UT151 manufactured by Nikkiso Co., Ltd.
[GPC measurement]
Equipment: Tosoh GPC8020
Column: G6000PWXL + G3000PWXL (7.8 × 3000) + Guard column PWH
Detector: RI-8020
Eluent: 0.2M phosphate buffer (pH = 6.8) / CH ₃ CN = 9/1 Volume ratio Flow rate: 0.6mL / min
Injection volume: 50 μL (about 0.1 wt%)
Temperature: 40 ° C
Standard sample: Sodium polystyrene sulfonate (Polymer Standards)
Service GmbH)
[Viscosity measurement]
Complete Viscometer / BROOKFIELD VISCOMETER DV-1 Prime
[Conductivity measurement]
1.0 mL of an aqueous dispersion containing a polythiophene-polystyrene sulfonic acid copolymer complex is applied to a 30 mm square non-alkali glass plate, dried overnight at room temperature, and then heated at 150 ° C. for 30 minutes on a hot plate. Obtained a conductive polymer film. It was calculated from the film thickness and surface resistance value based on the following formula.

Conductivity [S / cm] = 10 ⁴ / (Surface resistivity [Ω / □] x Film thickness [μm])
[Adhesion test]
An adhesion test was carried out by a cross-cut method (JIS K 5600-5-6) on a conductive polymer film prepared under the same conditions as the conductivity measurement. Classifications 0 to 2 were good judgments, and classifications 3 to 5 were bad judgments.

Good: Classification 0-2
Defective: Classification 3-5
Example 1 (Synthesis of polystyrene sulfonic acid copolymer)

In a 200 ml glass flask equipped with a reflux condenser and a paddle type stirrer, 50.0 g of pure water, 3.45 g of sodium styrene sulfonate (14.8 mmol, manufactured by Toso Finechem, hereinafter abbreviated as NaSS) and 3- (methacryloylamino). In formula (4), 4.53 g (14.8 mmol, X = -NH-, m = 3, n = 4, R ² = R ³ = R ⁴ = methyl group) of propyl dimethyl (4-sulfobutyl) ammonium hydrooxide. After adding the represented repeating unit monomer (hereinafter abbreviated as comonomer A), 65.8 mg of ammonium persulfate was added under a nitrogen atmosphere, and the mixture was heated in an oil bath at 70 ° C. for 20 hours. When 1 g of the obtained aqueous solution was reprecipitated in 40 ml of acetone, a white polymer (polystyrene sulfonic acid copolymer) was precipitated. The polystyrene sulfonic acid copolymer was filtered and dried, and then the weight average molecular weight was measured by GPC. As a result, Mw = 201,000 and the polydispersity PDI was 1.9. Further, the ratio of the styrene sulfonic acid repeating unit in the polystyrene sulfonic acid copolymer was 51.6 mol% by 1H-NMR. The ratio of styrene sulfonic acid repeating units in the polystyrene sulfonic acid copolymer is ¹ H-NMR (see FIG. 1) for aromatic protons (part A in FIG. 1) and methylene protons (part B in FIG. 1). It was calculated by the following formula from the ratio of.

Ratio of styrene sulfonic acid repeating unit (mol%) = 12 x [A integral value] / (4 x [B integral value] + 12 x [A integral value]) x 100
Next, water was added to the obtained reaction solution to prepare a diluted solution of 111 g, and then the solution was passed through 35 ml of a cation exchange resin (trade name: Lewatti S108H manufactured by LANXESS Co., Ltd.). As a result, 128 g (content of styrene sulfonic acid repeating unit in the copolymer = 39.1% by weight) of a 5.2 wt% polystyrene sulfonic acid copolymer (abbreviated as copolymer A) aqueous solution was synthesized.

Example 2 (Synthesis of polystyrene sulfonic acid copolymer)
The same operation as in Example 1 was carried out except that NaSS and copolymer A were changed to 6.56 g (28.1 mmol) and 0.95 g (3.11 mmol), respectively, and 4.51 wt% polystyrene sulfonate was performed. 128 g of an aqueous acid copolymer (abbreviated as copolymer B) aqueous solution was synthesized.

When the weight average molecular weight of the copolymer was measured by GPC, Mw = 239,000 and the polydispersity PDI was 2.4. Further, by 1H-NMR (FIG. 2), the ratio of the polystyrene sulfonic acid repeating unit in the polymer was 91.4 mol% (content of the polystyrene sulfonic acid repeating unit in the copolymer = 86.5% by weight).

Example 3 (Synthesis of polystyrene sulfonic acid copolymer)
The same operation as in Example 1 was carried out except that NaSS and copolymer A were changed to 7.5 g (32.1 mmol) and 0.52 g (1.69 mmol), respectively, and 4.51 wt% polystyrene sulfone was used. 114 g of an aqueous acid copolymer (abbreviated as copolymer C) aqueous solution was synthesized.

When the weight average molecular weight of the obtained polystyrene sulfone copolymer was measured by GPC, Mw = 239,000 and the polydispersity PDI was 2.4. Further, when the ratio of the styrene sulfonic acid repeating unit in the polymer was measured by 1H-NMR (FIG. 3), the ratio was 95.9 mol% (content of polystyrene sulfonic acid repeating unit in the copolymer = 93). .4% by weight).

Example 4 (Synthesis of Polythiophene-Polystyrene Sulfonic Acid Copolymer)
20.5 g of an aqueous solution containing the copolymer B synthesized in Example 2 in a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube and a mechanical stirrer (copolymer B solid content = 0.92 g, copolymer B (weight)) / 3,4-ethylenedioxythiophene (weight) = 2.31), dimethyl sulfoxide 0.22 g (2.82 mmol), to iron sulfate _{(III) · nH 2 O 32mg} (3,4- ethylene dioxythiophene 2 mol%), 0.40 g of 3,4-ethylenedioxythiophene (2.82 mmol, 3,4-ethylenedioxythiophene is hereinafter abbreviated as EDOT) and 39.39 g of water, and then the inside of the system is added. Nitrogen substitution. Next, a mixed solution consisting of 648 mg (2.83 mmol) of ammonium persulfate and 18.8 g of water was added dropwise at room temperature with a syringe, and then stirred for 20 hours at room temperature (EDOT concentration in the reaction solution = 0.5 wt). %).

Next, 6 g of a cation exchange resin (trade name Lewatt S108H manufactured by LANXESS Co., Ltd.) and 6 g of an anion exchange resin (trade name Lewatt MP62WS manufactured by LANXESS Co., Ltd.) were added and stirred for 1 hour. The ion exchange resin is No. After filtering with 2 filter papers, the dispersion treatment is carried out with an ultrasonic homogenizer (US-300T manufactured by Nippon Seiki Co., Ltd.) to obtain a dispersed aqueous solution containing 0.81 wt% of a polythiophene-polystyrene sulfonic acid copolymer complex. 148.8 g was obtained. The particle size D50 of the polythiophene-polystyrene sulfonic acid copolymer composite of the dispersed aqueous solution was 13.5 nm.

A solution obtained by adding 90 mg of ethylene glycol to 3 g of the obtained dispersed aqueous solution was applied to a 33 mm square glass substrate by the cast method, and the conductivity of the obtained thin film was measured and the adhesion test was performed. The conductivity was 434 S / cm (film thickness = 4.9 μm, surface resistance = 4.7 Ω / □). Adhesion was good. The results are summarized in Table 1.

Example 5 (Synthesis of Polythiophene-Polystyrene Sulfonic Acid Copolymer)
18.8 g of an aqueous solution containing the copolymer C synthesized in Example 3 in a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube and a mechanical stirrer (copolymer C solid content = 0.85 g, copolymer C (weight)) / EDOT (wt) = 2.1), 2 mol% relative to dimethyl sulfoxide 0.22 g (2.82 mmol), iron sulfate _{(III) · nH 2 O 32mg} (3,4- ethylenedioxythiophene), 3, After adding 0.40 g (2.82 mmol) of 4-ethylenedioxythiophene and 53.9 g of water, the inside of the system was replaced with nitrogen. Next, a mixed solution consisting of 648 mg (2.83 mmol) of ammonium persulfate and 6.0 g of water was added dropwise at room temperature with a syringe, and then stirred for 20 hours at room temperature (EDOT concentration in the reaction solution = 0.5 wt). %).

By ion exchange treatment and dispersion treatment in the same manner as in Example 4, 168.59 g of a dispersed aqueous solution containing a 0.64 wt% polythiophene-polystyrene sulfonic acid copolymer complex was obtained. The particle size D50 of the polythiophene-polystyrene sulfonic acid copolymer composite of the dispersed aqueous solution was 13.4 nm.

A solution obtained by adding 90 mg of ethylene glycol to 3 g of the obtained dispersed aqueous solution was applied to a 33 mm square glass substrate by the cast method, and the conductivity of the obtained thin film was measured and the adhesion test was performed. The conductivity was 578 S / cm (film thickness = 4.36 μm, surface resistance = 3.97 Ω / □). Adhesion was good. The results are summarized in Table 1.

Example 6 (Synthesis of Polythiophene-Polystyrene Sulfonic Acid Copolymer)
21.31 g of an aqueous solution containing the copolymer C synthesized in Example 3 in a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube and a mechanical stirrer (copolymer C solid content = 0.96 g, copolymer C (weight)) / EDOT (wt) = 2.4), 2 mol% relative to dimethyl sulfoxide 0.22 g (2.82 mmol), iron sulfate _{(III) · nH 2 O 32mg} (3,4- ethylenedioxythiophene), 3, After adding 0.40 g (2.82 mmol) of 4-ethylenedioxythiophene and 51.4 g of water, the inside of the system was replaced with nitrogen. Next, a mixed solution consisting of 648 mg (2.83 mmol) of ammonium persulfate and 6.0 g of water was added dropwise at room temperature with a syringe, and then stirred for 20 hours at room temperature (EDOT concentration in the reaction solution = 0.5 wt). %).

By ion exchange treatment and dispersion treatment in the same manner as in Example 4, 159.5 g of a dispersed aqueous solution containing 0.79 wt% of a polythiophene-polystyrene sulfonic acid copolymer complex was obtained. The particle size D50 of the polythiophene-polystyrene sulfonic acid copolymer composite of the dispersed aqueous solution was 9.4 nm.

A solution obtained by adding 90 mg of ethylene glycol to 3 g of the obtained dispersed aqueous solution was applied to a 33 mm square glass substrate by the cast method, and the conductivity of the obtained thin film was measured and the adhesion test was performed. The conductivity was 557 S / cm (film thickness = 4.53 μm, surface resistance = 3.97 Ω / □). Adhesion was good. The results are summarized in Table 1.

Example 7 (Synthesis of Polythiophene-Polystyrene Sulfonic Acid Copolymer)
23.18 g of an aqueous solution containing the copolymer C synthesized in Example 3 in a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube and a mechanical stirrer (copolymer C solid content = 1.05 g, copolymer C (weight)) / EDOT (wt) = 2.6), 2 mol% relative to dimethyl sulfoxide 0.22 g (2.82 mmol), iron sulfate _{(III) · nH 2 O 32mg} (3,4- ethylenedioxythiophene), 3, After adding 0.40 g (2.82 mmol) of 4-ethylenedioxythiophene and 49.5 g of water, the inside of the system was replaced with nitrogen. Next, a mixed solution consisting of 648 mg (2.83 mmol) of ammonium persulfate and 6.0 g of water was added dropwise at room temperature with a syringe, and then stirred for 20 hours at room temperature (EDOT concentration in the reaction solution = 0.5 wt). %).

By ion exchange treatment and dispersion treatment in the same manner as in Example 4, 162.04 g of a dispersed aqueous solution containing 0.81 wt% of a polythiophene-polystyrene sulfonic acid copolymer complex was obtained. The particle size D50 of the polythiophene-polystyrene sulfonic acid copolymer composite of the dispersed aqueous solution was 13.7 nm.

A solution obtained by adding 90 mg of ethylene glycol to 3 g of the obtained dispersed aqueous solution was applied to a 33 mm square glass substrate by the cast method, and the conductivity of the obtained thin film was measured and the adhesion test was performed. The conductivity was 517 S / cm (film thickness = 4.52 μm, surface resistance = 4.28 Ω / □). Adhesion was good. The results are summarized in Table 1.

Comparative Example 1 (Synthesis of PEDOT-PSS)
An aqueous solution obtained by diluting 50 g of sodium polystyrene sulfonate (manufactured by Toso Finechem Co., Ltd., trade name Polynas PS-50, weight average molecular weight: about 230,000, 22% by mass) with water 5 times is used as a cation exchange resin (LANXESS). Made by Co., Ltd. Trade name Lewattit S108H) A liquid was passed through 160 mL to obtain 220 g of a 3.4 wt% polystyrene sulfonate homopolymer aqueous solution.

In a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube and a mechanical stirrer, 23.5 g of a 3.4 wt% polystyrene sulfonate homopolymer aqueous solution (polystyrene sulfonate homopolymer (weight) / EDOT (weight) = 2.0), sulfuric acid. After adding 32 mg of iron (III) and nH ₂ O (2 mol% with respect to EDOT), 0.40 g (2.82 mmol) of EDOT and 36.6 g of water, the inside of the system was replaced with nitrogen. Next, a mixed solution consisting of 648 mg (2.83 mmol) of ammonium persulfate and 18.8 g of water was added dropwise at room temperature with a syringe, and then stirred for 20 hours at room temperature (EDOT concentration in the reaction solution = 0.5 wt). %).

By ion exchange treatment and dispersion treatment in the same manner as in Example 4, 157.6 g of a dispersed aqueous solution containing a 0.54 wt% polythiophene-polystyrene sulfonate homopolymer complex was obtained. The particle size D50 of the polythiophene-polystyrene sulfonic acid homopolymer complex of the dispersed aqueous solution was 17.1 nm.

A solution prepared by adding 90 mg of ethylene glycol to 3 g of the obtained dispersed aqueous solution was applied to a 33 mm square glass substrate by the cast method, and the conductivity of the obtained thin film was measured. The conductivity was 325 S / cm (film thickness = 5.1 μm, surface resistance = 6.0 Ω / □). The results are summarized in Table 1.

Comparative Example 2 (Synthesis of polystyrene sulfonic acid-methacrylamide copolymer and polythiophene)

In Example 1, instead of using 3.45 g (14.8 mmol) of sodium styrene sulfonate and 4.53 g (14.8 mmol) of 3- (methacryloylamino) propyldimethyl (4-sulfobutyl) ammonium hydrooxide, styrene sulfonic acid. The same procedure as in Example 1 was carried out except that 6.56 g (28.1 mmol) of sodium and 0.40 g (3.11 mmol) of N-isopropylmethacrylate were used, and 5.1 wt% polystyrene sulfonic acid copolymer weight was carried out. 112.9 g of a coalescence (abbreviated as copolymer D) was synthesized. When the weight average molecular weight of the copolymer was measured by GPC, Mw = 183,000 and the polydispersity PDI was 2.0. According to 1H-NMR (FIG. 2), the monomer ratio of polystyrene sulfonic acid in the polymer was 90.8 mol% (content of styrene sulfonic acid repeating unit in copolymer = 93.4% by weight).

16.8 g of an aqueous solution containing the above-mentioned copolymer D (copolymer D solid content = 1.99 g, copolymer D (weight) / EDOT (weight) in a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube and a mechanical stirrer. ) = 2.1), 2 mol% relative to dimethyl sulfoxide 0.22 g (2.82 mmol), iron sulfate _{(III) · nH 2 O 32mg} (3,4- ethylenedioxythiophene), 3,4-ethylene di After adding 0.40 g (2.82 mmol) of oxythiophene and 43.1 g of water, the inside of the system was replaced with nitrogen. Next, a mixed solution consisting of 648 mg (2.83 mmol) of ammonium persulfate and 18.8 g of water was added dropwise at room temperature with a syringe, and then stirred for 20 hours at room temperature (EDOT concentration in the reaction solution = 0.5 wt). %).

6 g of a cation exchange resin (trade name Lewatt S108H manufactured by LANXESS Co., Ltd.) and 6 g of an anion exchange resin (trade name Lewatt MP62WS manufactured by LANXESS Co., Ltd.) were added and stirred for 1 hour. The ion exchange resin is No. After filtering with 2 filter papers, it was dispersed with an ultrasonic homogenizer (US-300T manufactured by Nippon Seiki Co., Ltd.) to obtain a dispersed aqueous solution containing a polythiophene-polystyrene sulfonic acid copolymer complex.

The particle size D50 of the polythiophene-polystyrene sulfonic acid copolymer composite of the dispersed aqueous solution was 18.1 nm.

A solution prepared by adding 90 mg of ethylene glycol to 3 g of the obtained dispersed aqueous solution was applied to a 33 mm square glass substrate by the cast method, and the conductivity of the obtained thin film was measured. The conductivity was 223 S / cm (film thickness = 5.2 μm, surface resistance = 8.6 Ω / □). The results are summarized in Table 1.

Claims (10)

Polythiophene containing at least one thiophene repeating unit selected from the group consisting of the thiophene repeating unit represented by the following formula (1) and the thiophene repeating unit represented by the following formula (2), and the following formula (3). A complex with a polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by the compound and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the following formula (4).
(In the above formula, X independently represents an oxygen atom or -NH-, and R ¹ is a hydrogen atom and a chain or branched alkyl group having 1 to 8 carbon atoms (the group is hydroxy). It may have a group or an alkoxy group having 1 to 8 carbon atoms), where R ⁴ represents a hydrogen atom, a chain or branched alkyl group having 1 to 8 carbon atoms, and R ² and R. ³ independently represents a chain or branched alkyl group having 1 to 8 carbon atoms, m and n each independently represent an integer of 1 to 6, and M ⁺ are independent of each other. Represents an alkali metal ion selected from the group consisting of hydrogen ion, Li ion, Na ion and K ion, or a conjugated acid of an amine compound. The composite according to claim 1, wherein the content of the repeating unit of the styrene sulfonic acid represented by the formula (3) in the polystyrene sulfonic acid copolymer is 70 to 99.99 mol%. The composite according to claim 1, wherein the content of the repeating unit of the styrene sulfonic acid represented by the formula (3) in the polystyrene sulfonic acid copolymer is 90 to 99.9 mol%. The number of styrene sulfonic acid repeating units represented by the formula (3) is 1 of the total number of repeating units of the thiophene repeating unit represented by the formula (1) and the thiophene repeating unit represented by the formula (2). The complex according to any one of claims 1 to 3, wherein the complex is 0.0 to 3.0 times (mol ratio). The complex according to any one of claims 1 to 4, wherein R ² , R ³ and R ⁴ are each independently a methyl group or an ethyl group. The composite according to claim 1, wherein the polystyrene sulfonate copolymer has a weight average molecular weight of 10,000 to 300,000 in terms of a sodium polystyrene sulfonate standard substance. An aqueous dispersion containing the complex according to any one of claims 1 to 6. The aqueous dispersion according to claim 7, further comprising at least one conductivity improver selected from a water-soluble compound having a hydroxyl group, a water-soluble sulfoxide, a water-soluble amide compound, and a water-soluble compound having a lactone structure. A polystyrene sulfonic acid copolymer containing a repeating structural unit of styrene sulfonic acid represented by the above formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the above formula (4) in a solvent containing water. The production of the complex according to any one of claims 1 to 5, wherein the thiophene compound represented by the following formula (5) is polymerized in the presence of a polymer in the presence of an oxidizing agent. Method.
(In the formula, R ¹ is a hydrogen atom or a chain or branched alkyl group having 1 to 8 carbon atoms (the group may have a hydroxy group or an alkoxy group having 1 to 8 carbon atoms). Represents) A polystyrene sulfonic acid copolymer containing a repeating unit of styrene sulfonic acid represented by the following formula (3) and a repeating unit of a vinyl monomer having a sulfobetaine residue represented by the following formula (4).
(In the above formula, X independently represents an oxygen atom or -NH-, R ⁴ represents a hydrogen atom, a chain or branched alkyl group having 1 to 8 carbon atoms, and R ² , And R ³ each independently represent a chain or branched alkyl group having 1 to 8 carbon atoms, m each independently represents an integer of 1 to 6, and n each independently represents. Represents 4, 5, or 6, and M ⁺ independently represents an alkali metal ion selected from the group consisting of hydrogen ion, Li ion, Na ion, and K ion, or a conjugated acid of an amine compound.)