JP2014173041A - Dopant for conductive polymer, composition for production of conductive polymer and conductive polymer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dopant for conductive polymers which can improve conductivity of a conductive polymer and enables production of a conductive polymer film having good adhesiveness to metal surfaces and a composition for production of a conductive polymer which contains the dopant for conductive polymers.SOLUTION: A dopant for conductive polymers contains a sulfonated product of a conjugated diene (co)polymer. The conjugated diene (co)polymer preferably contains repeating units derived from at least one compound selected from butadiene, isoprene, 2,3-dimethylbutadiene and piperylene.

Description

  The present invention relates to a conductive polymer dopant, a conductive polymer production composition containing the dopant, and a conductive polymer film prepared from the conductive polymer production composition.

  In recent years, a shortage of metals called rare metals such as indium, nickel, and tungsten has become serious. Conductive polymers have been attracting attention as an alternative to these rare metals, and they are used for transparent electrode materials in place of indium oxide (ITO), and for electrode applications in power storage devices used in mobile phones, laptop computers, etc. Has been actively conducted.

  Common conductive polymers include polypyrrole, polythiophene, polyaniline and the like. Each of these conductive polymers has a π-conjugated structure in the molecular structure, and π-conjugated is grown by polymerizing. However, these conductive polymers cannot obtain sufficient conductivity in a neutral state. Therefore, in order to obtain a conductive polymer having a good electric conductivity of 0.1 S / cm or more, it is essential to dope the conductive polymer with a dopant (electron acceptor or electron donor). Hereinafter, such a dopant is also referred to as “a conductive polymer dopant”.

  As such a dopant for a conductive polymer, a low molecular component or a high molecular component can be used. However, a method of doping a conductive polymer with a high molecular component is studied from the viewpoint of developing stable conductivity. Has been.

  For example, in Patent Documents 1 to 3, polyacrylic acid, polymethacrylic acid, polyvinyl sulfuric acid, polyvinyl sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfonic acid, poly-α-methyl sulfonic acid, polyethylene sulfonic acid are used as the conductive polymer. In addition, a method of doping a polymer component such as a fluorine-containing polymer having polyglutamic acid, polyaspartic acid, polyphosphoric acid, alginic acid, pectinic acid, sulfonic acid group or carboxylic acid group has been studied.

JP-A-63-135453 JP 7-331067 A JP 2008-45061 A

  However, even if the polymer component as described above is doped into the conductive polymer, the conductivity cannot be sufficiently improved. Further, when a conductive polymer film is formed on a metal surface such as aluminum used for an electrode of an electricity storage device such as a capacitor, the adhesion to the metal surface is insufficient.

In addition, sulfonated conjugated diene compounds such as polyisoprene sulfonic acid are usually used as sodium salts and potassium salts. Therefore, in order to use a conjugated diene (co) polymer prepared by using a sulfonated conjugated diene monomer as described in Patent Document 2 or Patent Document 3 as a dopant for a conductive polymer, π-conjugation In order to form a complex with the system conductive monomer, it is necessary to remove metal ions such as sodium and potassium as counter ions by ion exchange or the like. However, it is impossible in principle to completely remove such metal ions. As a result, there was a risk that the conjugated diene (co) polymer prepared using the sulfonated conjugated diene monomer during storage would be gelled or discolored due to residual metal ions.

  Therefore, some aspects according to the present invention can improve the conductivity of the conductive polymer by solving the above-mentioned problems, and can provide a conductive polymer film having good adhesion to the metal surface. The present invention provides a conductive polymer dopant and a composition for producing a conductive polymer containing the conductive polymer dopant.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the dopant for a conductive polymer according to the present invention is:
It includes a sulfonated product of a conjugated diene (co) polymer.

[Application Example 2]
In the conductive polymer dopant of Application Example 1,
The conjugated diene (co) polymer may have a repeating unit derived from at least one compound selected from the group consisting of butadiene, isoprene, 2,3-dimethylbutadiene and piperylene.

（上記式（１）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） [Application Example 3]
One aspect of the dopant for a conductive polymer according to the present invention is:
It includes a sulfonated product of a conjugated diene (co) polymer having a repeating unit represented by the following general formula (1).

(In the above formula (1), R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom-substituted alkyl having 1 to 6 carbon atoms. M ^{n +} represents a hydrogen ion, an onium ion, or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.)

（上記式（２）中、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） [Application Example 4]
In the conductive polymer dopant of Application Example 3,
The sulfonated product of the conjugated diene (co) polymer may further have a repeating unit represented by the following general formula (2).

(In the above formula (2), R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom-substituted alkyl having 1 to 6 carbon atoms. M ^{n +} represents a hydrogen ion, an onium ion, or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.)

[Application Example 5]
In the conductive polymer dopant of any one of Application Examples 1 to 4,
The conjugated diene (co) polymer may have a weight average molecular weight (Mw) of 300 or more and 1,000,000 or less.

[Application Example 6]
In the conductive polymer dopant of any one of Application Examples 1 to 5,
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene (co) polymer may be 3 or less.

[Application Example 7]
One aspect of the composition for producing a conductive polymer according to the present invention is:
It contains a dopant for a conductive polymer according to any one of Application Examples 1 to 6, and a precursor monomer of a π-conjugated conductive polymer.

[Application Example 8]
In the composition for producing a conductive polymer of Application Example 7,
The precursor monomer of the π-conjugated conductive polymer may be at least one monomer selected from the group consisting of pyrrole, thiophene, aniline, and derivatives thereof.

[Application Example 9]
One aspect of the composition for producing a conductive polymer according to the present invention is:
It contains a dopant for a conductive polymer according to any one of Application Examples 1 to 6, and a π-conjugated conductive polymer.

[Application Example 10]
In the composition for producing a conductive polymer of Application Example 9,
The π-conjugated conductive polymer may be at least one polymer selected from the group consisting of polypyrrole, polythiophene, polyaniline, and derivatives thereof.

[Application Example 11]
In the composition for producing a conductive polymer according to any one of Application Example 7 to Application Example 10,
Further, water, a compound having a hydroxyl group, a compound having an amide group, a compound having a sulfo group, a compound having two or more carboxyl groups, a compound having one or more hydroxyl groups and one or more carboxyl groups, an imide It can contain at least one selected from the group consisting of a compound having a group, a lactam compound, a glycidyl compound, an amino compound, and an ether compound.

[Application Example 12]
One aspect of the conductive polymer film according to the present invention is:
It is obtained by polymerizing the composition for producing a conductive polymer of any one of Application Examples 7 to 11.

  According to the dopant for a conductive polymer according to the present invention, the conductivity of the conductive polymer can be improved, and a conductive polymer film having good adhesion to a metal surface such as aluminum can be produced. Become. In addition, the conductive polymer dopant according to the present invention is stable because it does not contain sodium or potassium, and is stable for batteries, capacitors, capacitors, display element electrodes, electrochromic display element materials, conductive films, and planar heating elements. It can be used for applications such as electromagnetic shielding materials.

^H 1 -NMR chart of sodium polyisoprene sulfonic acid. ^H 1 -NMR chart of sulfonated polyisoprene styrene copolymer.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included. In the present specification, “(meth) acrylic acid” is a concept encompassing both “acrylic acid” and “methacrylic acid”.

1. Conductive Polymer Dopant The conductive polymer dopant according to the present embodiment contains a sulfonated product of a conjugated diene (co) polymer. The “conjugated diene (co) polymer” in the present invention is a concept encompassing both a homopolymer of a conjugated diene monomer and a copolymer of a conjugated diene monomer and another monomer. In addition, the “sulfonated product of conjugated diene (co) polymer” in the present invention refers to a polymer obtained by synthesizing a conjugated diene (co) polymer and then sulfonating some groups of the conjugated diene (co) polymer. A conjugated diene (co) polymer obtained by polymerizing a sulfonated conjugated diene monomer is not included.

（上記式（３）および上記式（４）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） 1.1. Structure of conjugated diene (co) polymer synthesized from sulfonated conjugated diene monomer For example, obtained by polymerizing sulfonated conjugated diene monomer described in JP-A-7-331067 and JP-A-2008-45061 The resulting conjugated diene (co) polymer has repeating units represented by the following general formula (3) and the following general formula (4).

(In the above formula (3) and the above formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or carbon. Represents a fluorine atom-substituted alkyl group of formulas ¹ to 6. M ^{n +} represents a hydrogen ion, an onium ion or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.

（上記式（５）および上記式（６）中、＊は結合手を表す。） As an example of a conjugated diene (co) polymer synthesized from a sulfonated conjugated diene monomer, a sodium polyisoprene sulfonate synthesized from a sodium isoprene sulfonate monomer will be described as an example. When the sodium isoprenesulfonate monomer is radically polymerized, sodium polyisoprenesulfonate having repeating units represented by the following general formula (5) and the following general formula (6) is obtained.

(In the above formula (5) and the above formula (6), * represents a bond.)

FIG. 1 is an H ¹ -NMR chart of sodium polyisoprene sulfonate. In the H ¹ -NMR chart of FIG. 1, the assignment of each peak is as follows.
1.70 ppm: CH ₃ — (structure of the above formula (5))
1.92 ppm: CH ₃ — (structure of the above formula (6))
2.1-2.9 ppm: —CH ₂ — (structure of the above formula (5) and the above formula (6))
3.1-4.3 ppm: -CH- (structure of the above formula (5))
5.4 ppm: -CH = (structure of the above formula (6))
6.18 ppm: -CH = (structure of the above formula (5))

  When the number of repeating units represented by the above formula (5) in the obtained sodium polyisoprene sulfonate is m and the number of repeating units represented by the above formula (6) is n, the ratio of m to n is: m / n = 44/56. The ratio between m and n hardly changed even when the polymerization conditions were changed.

（上記式（７）および上記式（８）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。＊は結合手を表す。） 1.2. On the other hand, the structure of the sulfonated product of the conjugated diene (co) polymer. On the other hand, the conjugated diene (copolymer) used as the raw material of the sulfonated product of the conjugated diene (co) polymer contained in the conductive polymer dopant according to the present embodiment. The polymer has a repeating unit represented by the following general formula (7) and the following general formula (8).

(In the above formula (7) and the above formula (8), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or carbon. Represents a fluorine atom-substituted alkyl group of formulas 1 to 6. * represents a bond.)

（上記式（９）および上記式（１０）中、＊は結合手を表す。） As an example of a conjugated diene (co) polymer that is a raw material of a sulfonated product of a conjugated diene (co) polymer, a polyisoprene synthesized from isoprene will be described as an example. Polyisoprene obtained by polymerizing isoprene has repeating units represented by the following general formula (9) and the following general formula (10).

(In the above formula (9) and the above formula (10), * represents a bond.)

  The polyisoprene obtained by anionic polymerization of isoprene is represented by the number of repeating units represented by the general formula (9), m, and the general formula (10) by adjusting the type and amount of the randomizer. When the number of repeating units is n, the ratio between m and n can be arbitrarily changed. The randomizer is a compound having functions such as controlling the microstructure of a conjugated diene moiety in a polymer and controlling the composition distribution of monomer units in the polymer. The randomizer is not particularly limited, and can be selected from known compounds generally used as conventional randomizers, such as dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydro Examples include ethers such as furylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, and 1,2-dipiperidinoethane, and tertiary amines.

（上記式（１）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） The sulfonated product of the conjugated diene (co) polymer contained in the conductive polymer dopant according to the present embodiment can be produced by sulfonating the conjugated diene (co) polymer. The sulfonated product of the conjugated diene (co) polymer thus obtained has a repeating unit represented by the following general formula (1).

(In the above formula (1), R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom-substituted alkyl having 1 to 6 carbon atoms. M ^{n +} represents a hydrogen ion, an onium ion, or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.)

（上記式（２）中、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） The sulfonated conjugated diene (co) polymer contained in the conductive polymer dopant according to the present embodiment is represented by the following general formula (2) in addition to the repeating unit represented by the general formula (1). It may have a repeating unit.

(In the above formula (2), R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom-substituted alkyl having 1 to 6 carbon atoms. M ^{n +} represents a hydrogen ion, an onium ion, or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.)

（上記式（１１）中、Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） As an example of a sulfonated product of a conjugated diene (co) polymer, a sulfonated product of polyisoprene synthesized from isoprene will be described as an example. A polymer having a repeating unit represented by the following general formula (11) is obtained by sulfonating polyisoprene.

(In the above formula (11), M ^{n +} represents a hydrogen ion, an onium ion or an n-valent metal ion. N represents an integer of 1 to 3. * represents a bond.)

（上記式（１２）中、Ｍ^ｎ+は水素イオン、オニウムイオンあるいはｎ価の金属イオンを表す。ｎは１〜３の整数を表す。＊は結合手を表す。） In addition, the sulfonated product of polyisoprene synthesized from isoprene has a repeating unit represented by the following general formula (12).

(In the above formula (12), M ^{n +} represents a hydrogen ion, an onium ion or an n-valent metal ion. N represents an integer of 1 to 3. * represents a bond.)

FIG. 2 is a H ¹ -NMR chart of a sulfonated product of polyisoprene styrene copolymer. In the H ¹ -NMR chart of FIG. 2, since there are uncertain elements, all peaks cannot be assigned, but the assigned peaks are considered as follows.
1.67 ppm: CH ₃ — (structure of the above formula (11) and the above formula (12))
3.42 ppm: -CH- (structure of the above formula (12))
5.14 ppm: -CH = (structure of the above formula (11))
5.32 ppm: -CH = (structure of the above formula (12))
・ 7.21 ppm: Hydrogen in the benzene nucleus of styrene

By comparing the H ¹ -NMR chart and H ¹ -NMR chart of FIG. 2 in FIG. 1, a polyisoprene sulfonic acid obtained by polymerizing sodium monomers isoprene sulfonic acid, obtained by sulfonating a polyisoprene It is clear that the resulting sulfonated polyisoprene has a different structure. Further, according to the H ¹ -NMR chart of FIG. 2, the sulfonated polyisoprene styrene copolymer has a hydroxyl group in addition to the repeating units represented by the general formula (11) and the general formula (12). This suggests that the structure may be included, and it is assumed that the structure is complex. From the above, it was shown that the conjugated diene (co) polymer synthesized from the sulfonated conjugated diene monomer and the sulfonated product of the conjugated diene (co) polymer are greatly different in structure.

  Furthermore, the structural ratio of the repeating units of the general formula (7) and the general formula (8) can be controlled by controlling the polymerization conditions of the conjugated diene (co) polymerization. Therefore, a sulfonated product in which the structural ratio of the repeating units of the general formula (7) and the general formula (8) is controlled can be arbitrarily synthesized. Thereby, the distance and density of the sulfonic acid group acting as a dopant can be freely controlled.

1.3. Conjugated diene (co) polymer The conjugated diene (co) polymer used as the raw material of the sulfonated product of the conjugated diene (co) polymer contained in the conductive polymer dopant according to the present embodiment is derived from a conjugated diene compound. In addition to the repeating unit, the repeating unit derived from the aromatic vinyl compound, the repeating unit derived from the (meth) acrylate ester, the repeating unit derived from the unsaturated carboxylic acid, and the α, β-unsaturated nitrile compound. You may have a repeating unit. Hereinafter, each repeating unit will be described in detail.

1.3.1. Repeating units derived from conjugated diene compounds Specific examples of conjugated diene compounds include conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, piperylene, 2-chlorobutadiene, 2-phenylbutadiene, and 2,3-diphenylbutadiene. Compound: Fluorinated conjugated diene compounds such as hexafluorobutadiene, trifluoromethyl-2-butadiene, ditrifluoromethyl-2,3-butadiene, etc. can be mentioned, and one or more selected from these compounds Can do. Among these, at least one conjugated diene compound selected from the group consisting of butadiene, isoprene, 2,3-dimethylbutadiene and piperylene is preferable, butadiene and isoprene are more preferable, and isoprene is particularly preferable.

  The content ratio of the repeating unit derived from the conjugated diene compound is preferably 50 to 100 parts by mass, and more preferably 80 to 100 parts by mass when all repeating units are 100 parts by mass. When the content ratio of the repeating unit derived from the conjugated diene compound is within the above range, the density of the sulfonic acid group can be easily increased by sulfonating the synthesized conjugated diene (co) polymer by means described later. Can do. As a result, it is possible to function as a dopant that can greatly improve the conductivity of the conductive polymer.

1.3.2. Repeating unit derived from aromatic vinyl compound The conjugated diene (co) polymer may have a repeating unit derived from an aromatic vinyl compound. The conjugated diene (co) polymer has a repeating unit derived from an aromatic vinyl compound, so that the affinity with the conductive polymer can be further improved and the dopant can efficiently act as an electron donor. Can function as.

  Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like, and one or more selected from these can be used. Can do. Among the above, the aromatic vinyl compound is particularly preferably styrene.

  The content ratio of the repeating unit derived from the aromatic vinyl compound is preferably 0 to 50 parts by mass, and more preferably 0 to 20 parts by mass when the total repeating units are 100 parts by mass.

1.3.3. Repeating unit derived from (meth) acrylic acid ester The conjugated diene (co) polymer may have a repeating unit derived from (meth) acrylic acid ester. When the conjugated diene (co) polymer has a repeating unit derived from a (meth) acrylic acid ester, mixing with other resins or joining with different materials becomes easy. Further, random copolymerization or block copolymerization can be selected by changing the copolymerization method.

  Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, Di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid propylene glycol, tri (meth) Examples include trimethylolpropane acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, ethylene di (meth) acrylate, and the like. It can be one or more selected.

  When the conjugated diene (co) polymer has a repeating unit derived from a (meth) acrylic acid ester, the content ratio of the repeating unit derived from the conjugated diene compound is 20 when all repeating units are 100 parts by mass. It is preferable to set it as a mass part or more, and it is more preferable that it is 50-99 mass parts. When the content ratio of the repeating unit derived from the conjugated diene compound is less than 50 parts by mass, the addition amount of sulfuric anhydride may be reduced and the conductive performance may not be satisfied.

1.3.4. Repeating Unit Derived from Unsaturated Carboxylic Acid The conjugated diene (co) polymer may have a repeating unit derived from an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, and one selected from these. That can be the end. In particular, at least one selected from acrylic acid, methacrylic acid and itaconic acid is preferable.

1.3.5. Repeating unit derived from an α, β-unsaturated nitrile compound The conjugated diene (co) polymer may have a repeating unit derived from an α, β-unsaturated nitrile compound. Specific examples of the α, β-unsaturated nitrile compound include vinylcyan compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide and the like. It can be more than a seed.

1.3.6. Other repeating units The conjugated diene (co) polymer may have repeating units derived from the following compounds other than those described above. Examples of such compounds include fluorine-containing compounds having an ethylenically unsaturated bond such as vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene; ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylolacrylamide. Acid alkyl amides; Vinyl acetates, vinyl acetates, vinyl propionates, etc .; Acid anhydrides of ethylenically unsaturated dicarboxylic acids; Monoalkyl esters; Monoamides; Aminoethylacrylamide, dimethylaminomethylmethacrylamide, Methylaminopropylmethacrylamide Examples thereof include aminoalkylamides of ethylenically unsaturated carboxylic acids such as, and can be one or more selected from these.

1.3.7. Synthesis of Conjugated Diene (Co) polymer The method for synthesizing the conjugated diene (co) polymer is not particularly limited, but can be synthesized by conventionally known anionic polymerization or radical polymerization. Anionic polymerization is preferred from the viewpoints of molecular weight adjustment, molecular weight distribution control, microstructure control and copolymerization with other monomers.

  The weight average molecular weight (Mw) of the conjugated diene (co) polymer is preferably 300 or more and 1,000,000 or less, and 1,000 or more and 500,000 or less from the viewpoint of solubility in a solvent and conductivity. More preferably, it is 10,000 or more and 300,000 or less. The weight average molecular weight (Mw) of the conjugated diene (co) polymer can be determined by converting the measured value by gel permeation chromatography (GPC) into standard polystyrene.

  Further, the molecular weight distribution of the conjugated diene (co) polymer is usually represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The closer the Mw / Mn ratio is to 1, the sharper the distribution is. The larger the Mw / Mn ratio is, the more low molecular weight polymer is increased and the physical properties are lowered. Therefore, Mw / Mn is preferably 3 or less, more preferably 1 or more and 3 or less, and particularly preferably 1 or more and 2 or less. In addition, the number average molecular weight (Mn) of a conjugated diene (co) polymer can be calculated | required by converting the measured value by gel permeation chromatography (GPC) into standard polystyrene.

  The microstructure of the conjugated diene (co) polymer can be adjusted by the type and amount of electron donating compounds such as ether compounds and amine compounds during polymerization. Examples of ether compounds that can be added during polymerization include diethyl ether, dioxane, dibutyl ether, tetrahydrofuran, bistetrahydrofurylpropane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and the like. Examples of the amine compound include amine compounds such as pyridine, piperazine, trimethylamine, triethylamine, tributylamine, and tetramethylethylenediamine. Among these, tetrahydrofuran and dioxane are preferable.

  By adjusting the vinyl content of the microstructure, the length of the molecule and the distance of the sulfonic acid group when sulfonated can be adjusted. This is very important in forming a complex with a π-conjugated conductive monomer.

1.3.8. Method for producing sulfonated product of conjugated diene (co) polymer The sulfonated product of conjugated diene (co) polymer contained in the conductive polymer dopant according to the present embodiment is the above-described formula (13) as described above. The conjugated diene (co) polymer and sulfuric anhydride are reacted to obtain a sultone compound (intermediate) of the conjugated diene (co) polymer, and then the sultone compound of the conjugated diene (co) polymer is hydrolyzed. Can be manufactured.

（上記式（１３）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のフッ素原子置換アルキル基を表す。＊は結合手を表す。ＤＯＸはジオキサンを表す。）

(In the above formula (13), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or fluorine having 1 to 6 carbon atoms. Represents an atom-substituted alkyl group, * represents a bond, and DOX represents dioxane.)

  The reaction product of the above formula (13) is a sultone compound (intermediate) of a conjugated diene (co) polymer. A sulfonated product of a conjugated diene (co) polymer can be produced by reacting the sultone compound with water to hydrolyze the sultone compound.

  As the sultone agent, preferably sulfuric acid anhydride alone is used, and more preferably a complex of anhydrous sulfuric acid and an electron donating compound is used. Here, examples of the electron-donating compound include ethers such as N, N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran and diethyl ether; amines such as pyridine, piperazine, trimethylamine, triethylamine and tributylamine; dimethyl sulfide, diethyl Examples thereof include sulfides such as sulfides; nitrile compounds such as acetonitrile, ethyl nitrile, and propyl nitrile. Among these, N, N-dimethylformamide and dioxane are preferable. These electron donating compounds may be used alone or in combination of two or more.

  The added amount of the sultone agent is usually 0.3 to 2 mol, preferably 0.5 to 1.5 mol in terms of sulfuric anhydride, with respect to 1 mol of the conjugated diene unit in the conjugated diene (co) polymer. is there. If it is less than 0.3 mol, the amount of unreacted conjugated diene units increases, and if it exceeds 2 mol, the amount of unreacted sulfuric anhydride increases.

  In the sultonation, a solvent inert to sulfuric acid anhydride, which is a sulfonating agent, can be used. Examples of such solvents include halogenated hydrocarbons such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, and dichloromethane; nitro compounds such as nitromethane and nitrobenzene; and aliphatics such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane. A hydrocarbon is mentioned. These solvents can be used alone or in combination of two or more.

  The reaction temperature during the sultonation is usually -30 to 100 ° C, preferably -10 to 40 ° C. If it is less than −30 ° C., the sultoneation reaction is slow and is not economical, and if it exceeds 100 ° C., side reactions occur and the product may be blackened or insolubilized.

2. Conductive polymer manufacturing composition The conductive polymer manufacturing composition according to the present embodiment includes a conductive polymer dopant containing a sulfonated product of the above-described conjugated diene (co) polymer, and a π-conjugated system. A precursor monomer of a conductive polymer. It is considered that a complex is formed when a precursor monomer of a π-conjugated conductive polymer is added to a sulfonated product of a conjugated diene (co) polymer.

  Even if the precursor monomer of the π-conjugated conductive polymer is polymerized alone, it does not increase so much, and only a low molecular weight polymer can be obtained. However, by polymerizing a complex of a precursor monomer of a π-conjugated conductive polymer and a sulfonated product of a conjugated diene (co) polymer, the sulfonated product of the conjugated diene (co) polymer becomes a base point, and a template (template) ) Is considered to increase the molecular weight of the π-conjugated conductive polymer to grow the conjugated system and improve the conductivity.

  Examples of the precursor monomer of the π-conjugated conductive polymer include pyrrole, thiophene, aniline, and derivatives thereof from the viewpoints of conductivity and stability.

  Examples of the pyrrole and derivatives thereof include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3 , 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxy Examples include pyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, and 3-methyl-4-hexyloxypyrrole.

  Examples of the thiophene and derivatives thereof include thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, and 3-decyl. Thiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxy Thiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxy Thiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylene Dioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4 -Carboxythiophene, 3-methyl- - carboxyethyl thiophene, and 3-methyl-4-carboxybutyl thiophene.

  Examples of the aniline and derivatives thereof include aniline, 2-methylaniline, 3-isobutylaniline, 2-aniline sulfonic acid, and 3-aniline sulfonic acid.

The complex is formed by adding a precursor monomer of a π-conjugated conductive polymer to a sulfonated product of a conjugated diene (co) polymer. The precursor monomer of the π-conjugated conductive polymer is used as a solvent. It is preferable to dissolve and add to the solution. Solvents that dissolve the π-conjugated conductive polymer precursor monomer include ethers such as dioxane, dibutyl ether, tetrahydrofuran, and diethyl ether; halogenated hydrocarbons such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, and dichloromethane; nitromethane Nitro compounds such as nitrobenzene, and aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane. These solvents can be used alone or in combination of two or more.

  The addition amount of the precursor monomer of the π-conjugated conductive polymer is usually 0.5 to 2 mol, preferably 0.8 to 1. mol per mol of the sulfonated product of the conjugated diene (co) polymer. 2 moles. The reaction temperature is usually −10 to 50 ° C., preferably 0 to 40 ° C.

  Further, when forming the complex, water may be further added simultaneously with or after the addition of the precursor monomer of the π-conjugated conductive polymer.

  In place of the precursor monomer of the above-mentioned π-conjugated conductive polymer, polypyrroles, polythiophenes, polyanilines, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes Π-conjugated conductive polymers such as polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes and polythiazyl compounds can also be used. Among these, from the viewpoints of conductivity and stability, at least one polymer selected from the group consisting of polypyrrole, polythiophene, polyaniline, and derivatives thereof is preferable.

  When the π-conjugated conductive polymer is added, the addition amount is usually 0.5 as a monomer unit of the π-conjugated conductive polymer with respect to 1 mol of the sulfonated conjugated diene (co) polymer. It is -2 mol, Preferably it is 0.8-1.2 mol. The reaction temperature is usually −10 to 50 ° C., preferably 0 to 40 ° C.

  The composition for producing a conductive polymer according to the present embodiment can be used as an aqueous solution, but can also be used as a mixture of water and an organic solvent or a solution of an organic solvent. By using an organic solvent in the composition for producing a conductive polymer according to the present embodiment, the conductivity of the obtained conductive polymer film may be greatly improved. The improvement in conductivity is due to the fact that polar solvents such as ethylene glycol and dimethyl sulfoxide weaken the electrostatic interaction between polyion complexes, thereby strengthening the interaction between π-conjugated conductive polymers and promoting crystallization. it is conceivable that.

  Such organic solvents include compounds having two or more hydroxyl groups, compounds having amide groups, phenols, alcohols, compounds having sulfo groups, compounds having two or more carboxyl groups, one or more compounds Examples thereof include a compound having a hydroxyl group and one or more carboxyl groups, a compound having an imide group, a lactam compound, a glycidyl compound, an amino compound, and an ether compound.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and catechol. , Cyclohexanediol, diethylene glycol monoethyl ether, glycerin, pentaerythritol, sorbitol, arabitol and the like. Among these, ethylene glycol, diethylene glycol and sorbitol are preferable.

  Examples of the compound having an amide group include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, N- Methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-vinylpyrrolidone, propionamide, propioluamide, butyramide, isobutyramide, methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutar Amide, Adipamide, Cinnamamide, Glucolamide, Lactamide, Glyceramide, Tartaramide, Citrulamide, Glyoxylamide Plubuamide, acetoacetamide, dimethylacetamide, benzylamide, anthranilamide, ethylenediaminetetraacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea 1,3-dimethylurea, 1,3-diethylurea and derivatives thereof.

  Examples of phenols include cresol, phenol, xylenol and the like.

  Examples of alcohols include methanol, ethanol, propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, amyl alcohol, and the like.

  Examples of the compound having a sulfo group include dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide and the like.

  Examples of the compound having two or more carboxyl groups include maleic acid, fumaric acid, itaconic acid, citraconic acid, malonic acid, 1,4-butanedicarboxylic acid, succinic acid, adipic acid, citric acid, phthalic acid, terephthalic acid, Isophthalic acid, tetrahydrophthalic acid, 5-sulfoisophthalic acid, 5-hydroxyisophthalic acid, methyltetrahydrophthalic acid, 4,4'-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic acid, naphthalenedicarboxylic acid, tri Examples include merit acid and pyromellitic acid.

  Examples of the compound having one or more hydroxyl groups and one or more carboxyl groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

  Examples of the compound having an imide group include 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1 , 8-bismaleimide octane, N-carboxyheptylmaleimide and the like.

  Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  Examples of the glycidyl compound include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, acrylic acid glycidyl ether, and glycidyl methacrylate methacrylate. It is done.

Examples of amino compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine,
Examples include 2,4,6-trimethylpyridine and 3-cyano-5-methylpyridine.

  Examples of the ether compound include ethylene carbonate, propylene carbonate, dioxane, diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

  Among these compounds, ethylene glycol, diethylene glycol, sorbitol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, and dimethyl sulfoxide are preferable. By using these solvents, the film formation state becomes smooth and the conductive performance is improved.

  The composition for producing a conductive polymer according to the present embodiment may contain a known dopant for a conductive polymer in addition to the sulfonated product of the conjugated diene (co) polymer described above. Specific examples of such dopants include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, Examples include polyacrylic acid and polymethacrylic acid.

3. Conductive polymer film The conductive polymer film according to the present embodiment is obtained by polymerizing the above-described composition for producing a conductive polymer.

  Polymerization is achieved by adding a polymerization initiator to the above-described composition for producing a conductive polymer, and then heating to a predetermined temperature and holding it for a predetermined time. Examples of the polymerization initiator include peroxides such as hydrogen peroxide, ozone and benzoyl peroxide; persulfate compounds such as ammonium persulfate, sodium persulfate and potassium persulfate; azo compounds such as azoisobutyronitrile; silver oxide Metal oxides such as permanganic acid, chromic acid, hypochlorous acid, and other inorganic acids and salts thereof; perchlorates such as ferric perchlorate and cupric perchlorate; ferric chloride, Examples thereof include chlorides of transition metals such as cupric chloride and stannic chloride. Among these, hydrogen peroxide, ammonium persulfate and azoisobutyronitrile which do not contain a metal atom are preferable.

  After the composition for producing a conductive polymer according to the present embodiment is polymerized to obtain a conductive polymer, a conductive polymer film formed into a film shape may be used. The composition for producing a conductive polymer according to the embodiment may be poured into a mold for use in which the composition is used and polymerized therein may be used as it is.

  Moreover, you may form a conductive polymer film on a base material by apply | coating the composition for conductive polymers which concerns on this Embodiment on a base material, and making it dry. In this case, examples of the material for the base material include metals such as copper, aluminum, and tantalum; resins such as triacetyl cellulose, polyethylene terephthalate, polycarbonate, and polyester; and glass.

  The method for applying to the substrate is not particularly limited, for example, bar coating, doctor blade coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, Known methods such as dip coating, offset printing, flexographic printing, and screen printing can be used. The drying conditions are not particularly limited, and may be removed by heating and drying at a temperature of 30 to 200 ° C. for 1 hour to 3 days. Thereafter, an operation for completely removing volatile components by vacuum drying may be performed.

The conductive polymer film thus obtained is very excellent in conductivity, and has good adhesion even when formed on a metal surface such as aluminum as well as glass.

4). EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

Moreover, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this example are the results of measurement by gel permeation chromatography (GPC). In the case of a conjugated diene (co) polymer, polystyrene is used. In the case of a sulfonated product of a conjugated diene (co) polymer, it is converted using a calibration curve prepared using sodium polystyrenesulfonate as a standard sample. Here, the measurement conditions of GPC are as follows.
Column A: G3000PWxL (manufactured by Tosoh Corporation)
Column B: GMPWxL (manufactured by Tosoh Corporation)
-Column C: GMPWxL (manufactured by Tosoh Corporation)
Columns were connected in series in the order of A to C, and a sample was introduced from the column A side.
Detector: Tosoh Corporation, differential refractometer RI-8012
Eluent: Water / acetonitrile / sodium sulfate = 2,100 / 900/15 (weight ratio) Flow rate: 1.0 mL / min Temperature: 40 ° C.
Sample concentration: 0.2%
Sample injection volume: 300 μL

  In addition, for the measurement of the amount of sulfonic acid, a 20% aqueous solution of a sulfonated product (salt) of each conjugated diene (co) polymer was prepared, and the dialysis membrane (manufactured by Hansui Chemicals Cotton, Cellulose Diolizer Tubing-VT351) Using a sample purified by removing molecular components, this sample was ion-exchanged with a cation exchange resin (Amperite IR-118 (H), manufactured by Organo Corporation), converted into an acid form, and the amount of sulfonic acid was determined. Obtained from potentiometric titration.

4.1. Example 1
4.1.1. Synthesis of isoprene copolymer A pressure-resistant reaction vessel having an internal volume of 3 L was charged with 1,000 g of dehydrated cyclohexane, 10 g of tetrahydrofuran, 61 g of isoprene, and 10.4 g of styrene, and the internal temperature was kept at 60 ° C. Was added and polymerization was carried out at 60 to 100 ° C. for 2 hours. After completion of the polymerization, 1.0 g of isopropyl alcohol was added to stop the reaction, and then volatile components such as cyclohexane were removed under reduced pressure to obtain an isoprene copolymer. When the obtained isoprene copolymer was diluted with 100 g of dioxane to prepare a polymer solution and subjected to GPC measurement by the above method, the weight average molecular weight (Mw) was 20,000 and the Mw / Mn ratio was 1. 25.

4.1.2. Manufacture of sulfonated product of isoprene copolymer First, 80 g of anhydrous sulfuric acid was added to 400 g of dioxane in a separate container while keeping the internal temperature at 20 to 25 ° C., and then stirred for 2 hours to obtain an anhydrous sulfuric acid-dioxane solution. Next, by adding the dioxane solution of the isoprene copolymer obtained above to the anhydrous sulfuric acid-dioxane solution over 1 hour while keeping the solution temperature at 15 to 20 ° C., the solution of the sulfonated product of the isoprene copolymer Got. A part (small amount) was extracted, neutralized with an aqueous sodium hydroxide solution, and subjected to GPC measurement by the above method. As a result, the weight average molecular weight (Mw) of the sulfonated product of the obtained isoprene copolymer was 36. The acid amount was 5.2 meq / g.

4.1.3. Production of Composition for Conductive Polymer Production After adding 128 g of 3,4-ethylenedioxythiophene and 500 mL of distilled water to the sulfonated solution of the isoprene copolymer obtained above and stirring at 40 ° C. for 1 hour, Dioxane was removed by an evaporator to obtain a composition for producing a conductive polymer containing a complex of a sulfonated isoprene copolymer and 3,4-ethylenedioxythiophene.

4.1.4. Production of Conductive Polymer Film 1.3 g of ammonium persulfate was added to 100 g of the 10% aqueous solution for producing a conductive polymer composition obtained above and polymerized at 80 ° C. for 3 hours. The sodium content in the obtained solution was 1 ppm or less. Next, this solution was diluted 10 times, dropped several drops on a glass substrate, applied by a doctor blade method, and dried by heating at 60 ° C. for 1 day. Thereafter, it is further vacuum-dried at 150 ° C. for 1 hour, thereby conducting a 10 μm-thick conductive film containing a sulfonated isoprene copolymer as a dopant and poly-3,4-ethylenedioxythiophene as a π-conjugated conductive polymer. A functional polymer film was prepared.

4.1.5. Evaluation of conductive polymer film The conductive polymer film obtained as described above was evaluated by the following evaluation method.

<Evaluation method of electrical conductivity>
The electrical conductivity of the conductive polymer film formed on the glass substrate was measured with a low resistivity meter (Lorestar GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). When the electrical conductivity is 0.1 S / cm or more, it can be determined that the electrical conductivity is good, and when the electrical conductivity is less than 0.1 S / cm, it can be determined that the electrical conductivity is poor. As a result, the electric conductivity was 0.21 S / cm, and it was confirmed that the electric conductivity was good.

<Evaluation of adhesion>
When using a conductive polymer film as an electrode material for an electricity storage device such as a capacitor, if the adhesiveness with a conductive metal such as aluminum is insufficient, it may not function as an electrode and cause a failure. is there. Therefore, the adhesion between the conductive metal and the conductive polymer film is important. Therefore, the adhesion between the aluminum substrate and the conductive polymer film was evaluated by the following method.

  1.3 g of ammonium persulfate was added to 100 g of the 10% aqueous solution for producing a conductive polymer obtained above and polymerized at 80 ° C. for 3 hours. This solution was diluted 10 times, dropped several times on an aluminum substrate, applied by a doctor blade method, and dried by heating at 60 ° C. for 1 day. Thereafter, it is further vacuum-dried at 150 ° C. for 1 hour, thereby conducting a 10 μm-thick conductive film containing a sulfonated isoprene copolymer as a dopant and poly-3,4-ethylenedioxythiophene as a π-conjugated conductive polymer. A functional polymer film was prepared. The conductive polymer film thus obtained was subjected to a cross-cut peel test in accordance with JIS K5400.

  Specifically, using a cutter, eleven cuts from the surface of the conductive polymer film to the depth reaching the aluminum substrate were made at 1 mm intervals both vertically and horizontally, and the thin film was divided into a grid-like 100-mass region. An adhesive tape (manufactured by Terraoka Co., Ltd., product number “650S”) was applied to the entire surface of these 100 square areas and immediately peeled off, and the number of remaining squares was counted. When the number of remaining squares was 100, the adhesion was judged to be good, and when there was even one peel, the adhesion was judged to be poor. As a result, no peeling was observed, and it was confirmed that the film had good adhesion.

4.2. Example 2
4.2.1. Synthesis of isoprene polymer An isoprene polymer was obtained in the same manner as in Example 1 except that 1,000 g of dehydrated cyclohexane, 10 g of tetrahydrofuran and 68 g of isoprene were charged into a pressure-resistant reaction vessel having an internal volume of 3 L. The obtained isoprene polymer was diluted with 100 g of dioxane to prepare a polymer solution, and GPC measurement was performed by the above method. The weight average molecular weight (Mw) was 17,000, and the Mw / Mn ratio was 1.17. Met.

4.2.2. Production of sulfonated product of isoprene polymer A solution of a sulfonated product of isoprene polymer was prepared in the same manner as in Example 1 except that the "isoprene polymer" obtained above was used instead of the "isoprene copolymer". Obtained. A part (small amount) was extracted, neutralized with an aqueous sodium hydroxide solution, and subjected to GPC measurement by the above method. As a result, the weight average molecular weight (Mw) of the sulfonated product of the obtained isoprene polymer was 35, The acid amount was 5.8 meq / g.

4.2.3. Production of Composition for Conductive Polymer Production Same as Example 1 except that “solution of sulfonated product of isoprene copolymer” obtained above was used instead of “solution of sulfonated product of isoprene copolymer” Thus, a composition for producing a conductive polymer containing a sulfonated product of an isoprene polymer and a complex of 3,4-ethylenedioxythiophene was obtained.

4.2.4. Production of Conductive Polymer Film 1.3 g of ammonium persulfate was added to 100 g of the 10% aqueous solution for producing a conductive polymer composition obtained above and polymerized at 80 ° C. for 3 hours. The sodium content in the obtained solution was 1 ppm or less. Next, this solution was diluted 10 times, dropped several drops on a glass substrate or an aluminum substrate, applied by the doctor blade method, and dried by heating at 60 ° C. for 1 day. Thereafter, it is further vacuum-dried at 150 ° C. for 1 hour, thereby conducting a 10 μm-thickness conductive film containing a sulfonated isoprene polymer as a dopant and poly-3,4-ethylenedioxythiophene as a π-conjugated conductive polymer. A polymer film was prepared.

4.2.5. Evaluation of Conductive Polymer Film When the electric conductivity was evaluated in the same manner as in Example 1, the electric conductivity was 0.30 S / cm, and it was confirmed that the electric conductivity was good. Moreover, when adhesiveness was evaluated like Example 1, peeling was not observed in the cross-cut peel test, but it has confirmed having favorable adhesiveness.

4.3. Example 3
In the composition for producing a conductive polymer produced in Example 2, in the same manner as in Example 2 except that the composition for producing a conductive polymer added to contain 5% by mass of ethylene glycol was used. A 10 μm-thick conductive polymer film containing a sulfonated isoprene polymer as a dopant and poly-3,4-ethylenedioxythiophene as a π-conjugated conductive polymer was prepared. When the electrical conductivity of the conductive polymer film was measured in the same manner as in Example 1, it was confirmed that the electrical conductivity was 255 S / cm, and the electrical conductivity was significantly increased. From this, it became clear that high electroconductivity was provided by using a specific organic solvent for the composition for electroconductive polymer manufacture. Further, as a result of conducting a cross-cut peel test of the conductive polymer film in the same manner as in Example 1, it was confirmed that no peeling was observed and the film had good adhesion.

4.4. Example 4
12 g of poly-3,4-ethylenedioxythiophene was added to 1/10 of the sulfonated solution of the isoprene polymer obtained in Example 2, and water was added to make a 1% solution. Furthermore, ethylene glycol was added so as to be 5% by mass to obtain a composition for producing a conductive polymer. The sulfonated product of isoprene polymer was used as a dopant, and poly-3 was used as a π-conjugated conductive polymer in the same manner as in Example 2 except that the conductive polymer production composition thus obtained was used. A conductive polymer film having a film thickness of 10 μm containing 1,4-ethylenedioxythiophene was prepared. When the electrical conductivity of the conductive polymer film was measured in the same manner as in Example 1, it was confirmed that the electrical conductivity was 11 S / cm, indicating a high electrical conductivity. Further, as a result of conducting a cross-cut peel test of the conductive polymer film in the same manner as in Example 1, it was confirmed that no peeling was observed and the film had good adhesion.

4.5. Comparative Example 1
First, 0.4 g of ammonium persulfate was added to 100 g of a 40% aqueous solution of sodium isoprenesulfonate and polymerized at 80 ° C. for 3 hours to obtain sodium polyisoprenesulfonate having a weight average molecular weight of 30,000. The Mw / Mn ratio was 3.7.

  A cation exchange resin (Amperite IR-118 (H) manufactured by Organo Corporation) was added to 10 g of this 10% aqueous solution of sodium polyisoprenesulfonate to perform ion exchange to obtain polyisoprenesulfonic acid. The sodium content was 130 ppm.

  To this aqueous solution, 0.84 g of 3,4-ethylenedioxythiophene was added and stirred at 40 ° C. for 1 hour, and then 100 mg of ammonium persulfate was added and stirred at 80 ° C. for 3 hours. The obtained complex solution of polyisoprene sulfonic acid and poly-3,4-ethylenedioxythiophene was diluted 10 times, dropped several times on a glass substrate or an aluminum substrate, and applied by a doctor blade method. And then dried in a vacuum at 150 ° C. for 1 hour to obtain a complex film having a thickness of 10 μm.

  When the electrical conductivity was evaluated in the same manner as in Example 1, it was confirmed that the electrical conductivity was 0.08 S / cm, which was lower than those in Examples 1 to 4. Moreover, when adhesiveness was evaluated similarly to Example 1, peeling was recognized in the cross-cut peel test, and it has confirmed that adhesiveness became defect.

4.6. Summary From the above, it has been clarified that a conductive polymer film having high conductivity and good adhesion can be produced by using the conductive polymer dopant according to the present embodiment. On the other hand, when polyisoprene sulfonic acid produced by a conventional method was used as a dopant, the electrical conductivity was relatively low and the adhesion was poor.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

  INDUSTRIAL APPLICABILITY The present invention can be used in the industrial fields such as batteries, capacitors, capacitors, display element electrodes, electrochromic display element materials, conductive films, planar heating elements, and electromagnetic shielding materials in the electric and electronic industries. is there.

Claims (12)

  A conductive polymer dopant comprising a sulfonated product of a conjugated diene (co) polymer.   The conductivity according to claim 1, wherein the conjugated diene (co) polymer has a repeating unit derived from at least one compound selected from the group consisting of butadiene, isoprene, 2,3-dimethylbutadiene and piperylene. Polymer dopant. A conductive polymer dopant comprising a sulfonated product of a conjugated diene (co) polymer having a repeating unit represented by the following general formula (1).

(In the above formula (1), R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom-substituted alkyl having 1 to 6 carbon atoms. M ^{n +} represents a hydrogen ion, an onium ion, or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.) The conductive polymer dopant according to claim 3, wherein the sulfonated product of the conjugated diene (co) polymer further has a repeating unit represented by the following general formula (2).

(In the above formula (2), R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom-substituted alkyl having 1 to 6 carbon atoms. M ^{n +} represents a hydrogen ion, an onium ion, or an n-valent metal ion, n represents an integer of 1 to 3, and * represents a bond.)   The conductive polymer dopant according to any one of claims 1 to 4, wherein the conjugated diene (co) polymer has a weight average molecular weight (Mw) of 300 or more and 1,000,000 or less.   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene (co) polymer is 3 or less, according to any one of claims 1 to 5. Conductive polymer dopant.   The composition for conductive polymer manufacture containing the dopant for conductive polymers as described in any one of Claims 1 thru | or 6, and the precursor monomer of (pi) conjugated system conductive polymer.   The conductive polymer production according to claim 7, wherein the precursor monomer of the π-conjugated conductive polymer is at least one monomer selected from the group consisting of pyrrole, thiophene, aniline, and derivatives thereof. Composition.   The composition for electroconductive polymer manufacture containing the dopant for electroconductive polymers as described in any one of Claims 1 thru | or 6, and (pi) conjugated system conductive polymer.   The composition for producing a conductive polymer according to claim 9, wherein the π-conjugated conductive polymer is at least one polymer selected from the group consisting of polypyrrole, polythiophene, polyaniline, and derivatives thereof.   Further, water, a compound having a hydroxyl group, a compound having an amide group, a compound having a sulfo group, a compound having two or more carboxyl groups, a compound having one or more hydroxyl groups and one or more carboxyl groups, an imide The conductive polymer production according to any one of claims 7 to 10, comprising at least one selected from the group consisting of a group-containing compound, a lactam compound, a glycidyl compound, an amino compound, and an ether compound. Composition.   The electroconductive polymer film obtained by polymerizing the composition for electroconductive polymer manufacture as described in any one of Claims 7 thru | or 11.

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