JP6953362B2 - Self-healing conductive materials, conductive polymer compounds and polymerizable monomers - Google Patents

Description

The present invention relates to self-healing conductive materials, conductive polymer compounds and polymerizable monomers.

Conductive polymer materials are used for various purposes, and are indispensable materials in the electronics field such as fuel cells, solar cells, capacitors, touch panels, electromagnetic wave shields, antistatic films, organic LEDs, and transistors. .. Therefore, the utility value of the conductive polymer material is increasing more and more. For example, in the field of fuel cells, it is considered to apply the conductive polymer material as a constituent member such as a separator.

As represented by the electronics field in recent years, there is a strong demand for improved performance requirements and safety performance in various applications, and along with this, conductivity is excellent in durability and stable performance can be maintained for a long period of time. Development of sex materials is also required. From this point of view, for example, Patent Document 1 proposes an ionic conduction gel having a self-healing ability in which an electrolyte is encapsulated in a fibrous aggregate. According to this self-healing ion-conducting gel, when pinholes are generated, a sol-gel phase change is caused by a thermal response, and the pinholes generated in the electrolyte can be easily repaired, so that the durability of the material itself is durable. Is expected to improve.

Japanese Unexamined Patent Publication No. 2007-277133

However, with the technique disclosed in Patent Document 1, even if it is possible to repair a scratch such as a pinhole formed on a gel, it becomes difficult to repair as the scratch becomes larger, so that the self-healing performance is further improved. There was room for improvement, and there was room for improvement from the viewpoint of conductive performance.

The present invention has been made in view of the above, and an object of the present invention is to provide a self-healing conductive material having excellent conductive performance and excellent self-healing property.

As a result of intensive research to achieve the above object, the present inventor has obtained a conductive polymer having a functional group for forming one or two or more reversible bonds between polymer chains. It has been found that the above object can be achieved by using it, and the present invention has been completed.

（式（Ｈ１）中、ＣＤはシクロデキストリンから一つの水素原子又は水酸基が除された基を示し、シクロデキストリンは、α−シクロデキストリン、β−シクロデキストリン又はγ−シクロデキストリンである）
及び下記式（Ｈ２）

（式（Ｈ２）中、ＣＤは前記式（Ｈ１）のＣＤと同義である）
からなる群より選択される少なくとも１種の単量体単位であり、
前記ゲスト基を有する単量体単位は、下記式（Ｇ１）

（式（Ｇ１）中、Ｒ^Ｇはゲスト基を示す）
及び下記式（Ｇ２）

（式（Ｇ２）中、Ｒ^Ｇはゲスト基を示す）
からなる群より選択される少なくとも１種の単量体単位であり、
前記チオフェン骨格を有する単量体単位は、下記式（Ｃ１）

で表される単量体単位である、導電性高分子化合物。
項１１
下記式（ｈ１）

（式（ｈ１）中、ＣＤはシクロデキストリンから一つの水素原子又は水酸基が除された基を示し、シクロデキストリンは、α−シクロデキストリン、β−シクロデキストリン又はγ−シクロデキストリンである）
で表される、重合性単量体。
項１２
下記式（ｈ２）

（式（ｈ２）中、ＣＤはシクロデキストリンから一つの水素原子又は水酸基が除された基を示し、シクロデキストリンは、α−シクロデキストリン、β−シクロデキストリン又はγ−シクロデキストリンである）
で表される、重合性単量体。
項１３
下記式（ｇ１）

（式（ｇ１）中、Ｒ^Ｇはゲスト基を示す）
で表される、重合性単量体。
項１４
下記式（ｇ２）

（式（ｇ２）中、Ｒ^Ｇはゲスト基を示す）
で表される、重合性単量体。
項１５
基板上に該基板と共有結合して成膜されている、項１〜８のいずれか１項に記載の自己修復性導電性材料。
項１６
前記第１の高分子化合物及び前記第２の高分子化合物の少なくともいずれか一方は、前記基板と前記共有結合を形成可能な官能基を有する単量体単位を含み、
前記共有結合を形成可能な官能基と、基板表面の官能基とが共有結合を形成している、項１５に記載の自己修復性導電性材料。
項１７
前記共有結合を形成可能な官能基を有する単量体単位は、下記式Ａ１

で表される、項１６に記載の自己修復性導電性材料。 That is, the present invention can include, for example, the inventions described in the following sections.
Item 1
It is formed of a conductive polymer containing a first polymer compound and a second polymer compound as constituent components.
The conductive polymer is a self-healing conductive material in which polymer chains have functional groups for forming one type or two or more different types of reversible bonds.
Item 2
Item 2. The self-healing conductive material according to Item 1, wherein the conductive polymer forms one or two or more reversible bonds between polymer chains.
Item 3
The reversible bond is selected from the group consisting of electrostatic interaction, host-guest interaction, hydrophobic interaction, hydrogen bond, ionic bond, coordination bond, π-electron interaction and other intermolecular interactions. Item 2. The self-healing conductive material according to Item 1 or 2, which is at least one non-covalent bond.
Item 4
Item 3. The self-healing conductive material according to Item 3, wherein the non-covalent bond includes at least an electrostatic interaction and a host-guest interaction.
Item 5
One of the first polymer compound and the second polymer compound has a monomer unit having a host group and no monomer unit having a guest group, and the other has a guest group. Item 2. The self-healing conductive material according to Item 4, which has a monomer unit having a monomer unit and does not have a monomer unit having a host group.
Item 6
Item 4. Self-repair according to Item 4, wherein either the first polymer compound or the second polymer compound has both a monomer unit having a host group and a monomer unit having a guest group. Conductive conductive material.
Item 7
Item 2. Self-healing conductivity according to Item 4, wherein both the first polymer compound and the second polymer compound have both a monomer unit having a host group and a monomer unit having a guest group. Sex material.
Item 8
The conductive polymer has a monomer unit having a styrene sulfonic acid skeleton, a monomer unit having a thiophene skeleton, a monomer unit having an aniline skeleton, a monomer unit having a phenylene vinylene skeleton, and an acetylene skeleton. Item 2. The self-healing conductive material according to any one of Items 1 to 7, which comprises at least one monomer unit selected from the group consisting of monomer units.
Item 9
Item 2. The self-healing conductive material according to any one of Items 1 to 8, which is formed in a film shape.
Item 10
It has one or both of a monomer unit having a host group and a monomer unit having a guest group, and a monomer unit having a thiophene skeleton.
The monomer unit having the host group has the following formula (H1).

(In formula (H1), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
And the following formula (H2)

(In the formula (H2), CD is synonymous with the CD of the formula (H1))
It is at least one monomer unit selected from the group consisting of
The monomer unit having a guest group is represented by the following formula (G1).

(In equation (G1), ^RG indicates a guest group)
And the following formula (G2)

(In equation (G2), ^RG indicates a guest group)
It is at least one monomer unit selected from the group consisting of
The monomer unit having the thiophene skeleton has the following formula (C1).

A conductive polymer compound which is a monomer unit represented by.
Item 11
The following formula (h1)

(In formula (h1), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
A polymerizable monomer represented by.
Item 12
The following formula (h2)

(In formula (h2), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
A polymerizable monomer represented by.
Item 13
The following formula (g1)

(In formula (g1), ^RG indicates a guest group)
A polymerizable monomer represented by.
Item 14
The following formula (g2)

(In formula (g2), ^RG indicates a guest group)
A polymerizable monomer represented by.
Item 15
Item 2. The self-healing conductive material according to any one of Items 1 to 8, which is covalently bonded to the substrate and formed on the substrate.
Item 16
At least one of the first polymer compound and the second polymer compound contains a monomer unit having a functional group capable of forming the covalent bond with the substrate.
Item 15. The self-healing conductive material according to Item 15, wherein the functional group capable of forming a covalent bond and the functional group on the surface of the substrate form a covalent bond.
Item 17
The monomer unit having a functional group capable of forming the covalent bond is represented by the following formula A1.

Item 16. The self-healing conductive material represented by.

The conductive polymer material of the present invention has excellent conductive performance by containing a conductive polymer having a functional group for forming one or two or more different types of reversible bonds between polymer chains. And has excellent self-healing properties.

The conductive polymer of the present invention has excellent conductive performance and is also excellent in self-healing property, and is therefore suitable for forming a conductive polymer material.

The results of the self-repair test of the conductive polymer film obtained in Example 3-6, (a) shows an image of the film surface before repair, and (b) shows an image of the film surface after repair. (C) shows the measurement result of the scratch area before repair, and (d) shows the measurement result of the scratch area after repair. It is a schematic diagram explaining the state which the conductive polymer which introduced the anchor-containing monomer unit was formed on the substrate, and the functional group in the anchor-containing monomer unit and the functional group of the substrate S surface It is a schematic diagram explaining the state which reacts and forms a covalent bond.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the expressions "contains" and "includes" include the concepts of "contains", "includes", "substantially consists" and "consists of only".

The self-healing conductive material of the present invention is formed of a conductive polymer containing a first polymer compound and a second polymer compound as constituent components, and the conductive polymer is a polymer chain. Each has a functional group for forming one or more reversible bonds. In other words, the conductive polymer may form one or two or more reversible bonds between the conductive polymer chains. The self-healing conductive material of the present invention is a material having excellent conductivity and self-healing property. In the following, the self-healing conductive material of the present invention may be simply referred to as "conductive material".

The conductive polymer contains two types of polymer compounds, that is, a first polymer compound and a second polymer compound as constituent components. As the mode in which the reversible bond between the conductive polymer chains is formed, the mode in which the reversible bond is formed between the first polymer compounds and the mode in which the reversible bond is formed between the second polymer compounds. Aspects, or a mode in which a reversible bond is formed between the first polymer compound and the second polymer compound can be mentioned. The mode in which the reversible bond is formed between the conductive polymer chains may be one of these three modes or a combination of two or more.

In the present specification, the description of "polymer compounds" refers to the first polymer compound, the second polymer compound, and the first polymer compound and the second polymer compound. Include.

A reversible bond is formed by pairing functional groups for forming a reversible bond. The type of reversible bond is not particularly limited, and for example, a bond in which binding and dissociation can occur repeatedly reversibly can be selected. In the conductive polymer, the polymer compounds are bonded to each other by a reversible bond, so that the bond and dissociation between the polymer compounds can occur reversibly. As a result, the conductive material can exhibit self-healing performance. That is, even if the conductive material is scratched, one polymer compound existing in the wound portion and the other polymer compound are re-bonded (or interacted) by a reversible bond, which causes a re-bonding (or interaction). The wound can be closed and repaired to the same or similar condition as the original condition.

Further, even if the conductive material is cut, even if the cut surfaces are brought into contact with each other again, the polymer compounds are reversibly bonded to each other (or interact with each other). As a result, the conductive material once cut can be reattached and the conductive material can self-repair.

Reversible bonds are selected from the group consisting of, for example, electrostatic interactions, host-guest interactions, hydrophobic interactions, hydrogen bonds, ionic bonds, coordination bonds, π-electron interactions, and other intermolecular interactions. It is preferably at least one non-covalent bond. Since these non-covalent bonds are reversible bonds and can easily bond and dissociate, the self-healing property of the conductive material is more likely to be exhibited.

As a reminder, the fact that two or more types of non-covalent bonds are included means that the polymer compounds form non-covalent bonds at two or more locations with each other, and each of them. It means that there are two or more types of non-covalent bonds that are different from each other.

The functional group for forming a non-covalent bond (hereinafter, abbreviated as "non-covalent functional group") is not particularly limited as long as the above-mentioned various non-covalent bonds can be formed.

When the non-covalent bond is an electrostatic interaction, the combination of the non-covalent functional groups includes a styrene sulfonic acid skeleton and a thiophene skeleton. In this case, sulfonic acid site of styrene sulfonic acid skeleton (SO 3 ^_-) are negative charges, thiophene site thiophene skeleton serves as the positive charge, thereby electrostatic interactions can be formed.

In addition, as the functional group for forming the electrostatic interaction, a combination of various functional groups having a positive charge on one side and a negative charge on the other side can be adopted. Examples of the functional group capable of imparting a positive charge include pyrrole and aniline, and examples of the functional group capable of imparting a negative charge include a hydroxyl group, a carboxy group and the like, as well as a functional group derived from boric acid, phosphoric acid, arsenic acid and boronic acid. Can be exemplified.

When the non-covalent bond is a host-guest interaction, the combination of non-covalent functional groups may include a host group and a guest group. A host-guest interaction is a bond formed between a host group and a guest group.

A host group is, for example, a group formed by a host molecule. That is, the host group is a group formed by removing one atom or a substituent (for example, hydrogen, a hydroxyl group, etc.) from the host molecule.

Host molecules include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, calix [6] allene sulfonic acid, calix [8] allene sulfonic acid, 12-crown-4, 18-crown-6, [6]. ] Paracyclophane, [2,2] paracyclophane, cucurbituril [6] uryl and cucurbituril [8] uryl, cucurbituril [7] uryl and pillar [n] arelain (n is an integer of 5 to 15) At least one of these is exemplified. The host molecule may further have a substituent. Examples of the substituent include a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, a hydroxyl group which may be protected, and the like.

The host group is preferably a group obtained by removing one hydrogen atom or a hydroxyl group from α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin. In this case, since a more stable host-guest interaction is likely to be formed, the self-healing property of the finally obtained conductive material is likely to be exhibited.

A guest group is a group formed by a guest molecule. That is, the guest group is a group formed by removing one atom or a substituent (for example, hydrogen, a hydroxyl group, etc.) from the guest molecule.

Examples of the guest group include a linear or branched hydrocarbon group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, a heteroaryl group, an organic metal complex and the like, and these have one or more substituents. May be. More specific guest groups include chain or cyclic alkyl groups having 4 to 18 carbon atoms. The cyclic alkyl group may have a cage-shaped structure. Examples of the substituent include a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, a hydroxyl group which may be protected, and the like.

Guest groups include, for example, alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives having cyclic alkyl groups or phenyl groups; cinnamic acid derivatives; aromatic compounds and their alcohol derivatives; amine derivatives; ferrocene derivatives; Azobenzene; naphthalene derivative; anthracene derivative; pyrene derivative: perylene derivative; clusters composed of carbon atoms such as fullerene; at least one selected from the group of dansyl compounds is a group formed from an exemplary guest molecule. May be good.

The guest group is preferably at least one selected from the group of n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, t-butyl group, isobornyl group and adamantyl group.

As a combination of a host group and a guest group, when the host molecule constituting the host group is α-cyclodextrin, the guest group is a group of n-butyl group, n-hexyl group, n-octyl group and n-dodecyl group. When the host molecule constituting the host group is β-cyclodextrin, the guest group is selected from the group of adamantyl group, hydroxyl group-substituted adamantyl group, ethyl group-substituted adamantyl group, and isobornyl group. When the host molecule constituting the host group is γ-cyclodextrin, the guest group is preferably at least one selected from the group such as n-octyl group, n-dodecyl group and cyclododecyl group. ..

Other types of reversible bonds include interactions between boronic acid and catechol, alkoxyamine bonds, disulfide bonds, imine bonds, bonds formed by the Diels-Alder reaction, bonds formed by the olefin cross metathesis reaction, and the like. be able to. The bond formed by the Diels-Alder reaction is formed, for example, by the reaction of a conjugated diene with a dienophile.

The non-covalent bond preferably includes at least an electrostatic interaction and a host-guest interaction. In other words, in the conductive polymer, it is preferable that the polymer compounds are bonded to each other by non-covalent bonds of at least both electrostatic interaction and host-guest interaction. In this case, the excellent reversibility of the host-guest interaction can further increase self-healing and, in addition, increase conductivity. Other non-covalent bonds can be included even if the non-covalent bond includes at least an electrostatic interaction and a host-guest interaction. Alternatively, the conductive polymer may be formed by non-covalent bonds of polymer compounds with each other only by electrostatic interaction and host-guest interaction.

The polymer compounds may have a chemically crosslinked structure as long as the effects of the present invention are not impaired.

The conductive polymer contains a monomer unit capable of imparting conductivity. That is, the first polymer compound and the second polymer compound that form the conductive polymer contain a monomer unit that can impart conductivity. The monomer unit referred to in the present specification indicates a repeating structural unit in a polymer formed when the monomer is polymerized, and does not indicate the monomer itself. Further, the “monomer unit derived from monomer A” as used herein means a repeating structural unit constituting a polymer obtained by polymerizing monomer A.

The monomer unit that can impart conductivity (hereinafter, abbreviated as "conductive monomer unit") is not particularly limited, and is used, for example, for forming a known conductive polymer. The monomer unit is widely applicable. Examples of the conductive monomer unit include a monomer unit having a styrene sulfonic acid skeleton, a monomer unit having a thiophene skeleton, a monomer unit having an aniline skeleton, a monomer unit having a phenylene vinylene skeleton, and the like. A monomer unit having an acetylene skeleton can be mentioned. The conductive monomer unit referred to in the present specification excludes the monomer unit having a host group and the monomer unit having a guest group, which will be described later.

Examples of the monomer unit having a styrene sulfonic acid skeleton include a monomer unit derived from a styrene sulfonate such as sodium styrene sulfonate and potassium styrene sulfonate. They can also have substituents. Examples of the monomer unit having a styrene sulfonic acid skeleton include a monomer unit in which sulfonic acid is bonded to the para position of styrene.

Examples of the monomer unit having a thiophene skeleton include thiophene, 2,3-dihydrothieno [3,4-b] [1,4] dioxin (also known as 3,4-ethylenedioxythiophene, which is referred to as EDOT). ) Etc., and examples thereof include monomer units derived from. They can also have substituents.

Examples of the monomer unit having an aniline skeleton include a monomer unit derived from aniline. Aniline can also have a substituent.

Examples of the monomer unit having a phenylene vinylene skeleton include a monomer unit derived from phenylene vinylene. Phenylene vinylene can also have a substituent.

Examples of the monomer unit having an acetylene skeleton include a monomer unit derived from acetylene. Phenylene vinylene can also have a substituent.

The conductive polymer is a monomer unit having a styrene sulfonic acid skeleton, a monomer unit having a thiophene skeleton, a monomer unit having an aniline skeleton, a monomer unit having a phenylene vinylene skeleton, and a simple unit having an acetylene skeleton. It preferably contains at least one monomeric unit selected from the group consisting of metric units. In this case, the conductive polymer can have high conductivity, and the conductive performance of the conductive material is further enhanced.

The conductive polymer preferably has both a monomer unit having a styrene sulfonic acid skeleton and a monomer unit having a thiophene skeleton. More specifically, one of the first polymer compound and the second polymer compound forming the conductive polymer has a monomer unit having a styrene sulfonic acid skeleton, and the other has a thiophene skeleton. It is preferable to have a monomer unit having. In this case, in addition to further enhancing the conductive performance of the conductive material, the electrostatic interaction (that is, non-covalent bond) between the styrene sulfonic acid skeleton and the thiophene skeleton also works effectively, so that self-healing property is also exhibited. Easy to be done. Further, when the conductive polymer has both a monomer unit having a styrene sulfonic acid skeleton and a monomer unit having a thiophene skeleton, it is not a first polymer compound and a second polymer compound. There is also an advantage that the introduction of a covalently bondable functional group is easy in production.

Specific examples of the case where the conductive polymer has both a monomer unit having a styrene sulfonic acid skeleton and a monomer unit having a thiophene skeleton include, for example, the styrene sulfonic acid skeleton is a styrene sulfonate unit and thiophene. It is a combination in which the skeleton is an EDOT unit. Examples of the styrene sulfonate include sodium styrene sulfonate, potassium styrene sulfonate and the like. For example, the sodium styrene sulfonate unit forms sodium polystyrene sulfonate (PSSNa) and acts as a so-called "dampant" in the conductive polymer.

The first polymer compound and the second polymer compound can be formed, for example, only by the conductive monomer unit. In this case, one of the first polymer compound and the second polymer compound is formed only of the monomer unit having a styrene sulfonic acid skeleton, and the other is formed only by the monomer unit having a thiophene skeleton. be able to. Specific examples of this form include sodium polystyrene sulfonate (PSSNa) in one of the first polymer compound and the second polymer compound, and the PEDOT polymer (PEDOT) in the other. In the following, this form will be abbreviated as "first form".

In the first form, PSSNa exhibits anionic properties due to sulfonic acid, and PEDOT exhibits cationic properties due to the thiophene skeleton, so that electrostatic interaction acts between PSSNa and PEDOT. As a result, PSSNa and PEDOT are bonded in a non-covalent bond to form a conductive polymer. Since the conductive polymer of the first form has PSSNa and PEDOT, it has excellent conductivity, and self-healing property can be exhibited by the electrostatic interaction between the two. As described above, PSSNa exerts a function as a "dopant" in the conductive polymer. In the conductive polymer material of the first form, for example, the sulfonate ion of PSSNa and the thiophene skeleton are functional groups for forming a reversible bond in the conductive polymer.

Both PSSNa and PEDOT can be produced by known methods. For example, PSSNa can be obtained by a polymerization reaction of sodium styrene sulfonate. PEDOT can be obtained by a polymerization reaction of sodium styrene sulfonate. PSSNa and PEDOT. Commercially available PSSNa and PEDOT can also be used.

The first polymer compound and the second polymer compound can each form other monomeric units, particularly reversible bonds (eg, non-covalent bonds), in addition to the conductive monomeric units. It can have a monomeric unit with a possible functional group. In this case, the conductive polymer is excellent in conductivity and self-healing property due to the presence of the conductive monomer unit as described above, and further has self-healing performance due to the presence of other non-covalent bonds. Can be reinforced. Other non-covalent bonds include, for example, host-guest interactions.

For example, one of the first polymer compound and the second polymer compound has a monomer unit having a host group and no monomer unit having a guest group, and the other has a guest group. It can be in a form having a monomer unit having a monomer unit and not having a monomer unit having a host group. In the following, this form will be abbreviated as "second form". The host group and the guest group are functional groups for forming a reversible bond, respectively.

In the second form, both the first polymer compound and the second polymer compound also have a conductive monomer unit. For example, in the second form, one of the polymer compound and the second polymer compound contains a monomer unit having a styrene sulfonic acid skeleton, and the other contains a monomer unit having a thiophene skeleton. Can be. The polymer compound containing the monomer unit having a styrene sulfonic acid skeleton exerts a function as a "lactone" in the conductive polymer.

In the second form, the polymer compound containing a monomer unit having a styrene sulfonic acid skeleton has a CC bond as the main chain of the monomer unit having a host group or a guest group from the viewpoint of easy production. It is preferable to have. Further, in the second form, from the viewpoint that the polymer compound containing the monomer unit having a thiophene skeleton can be easily produced, the main chain of the monomer unit having a host group or a guest group has the same thiophene skeleton. Is preferable.

In the second form, in addition to the electrostatic interaction caused by the conductive monomer unit acting between the first polymer compound and the second polymer compound, the bond between the host group and the guest group That is, the host-guest interaction can also play a role of non-covalent bond. That is, in the second form, the polymer chains of the conductive polymer can be bonded by two types of non-covalent bonds, electrostatic interaction and host-guest interaction. This further enhances the self-healing performance of the conductive polymer material. Therefore, in the conductive polymer material of the second form, for example, the sulfonate ion of PSSNa and the thiophene skeleton are functional groups for forming a reversible bond in the conductive polymer, and in addition, a host group. And the guest group is also a functional group for forming a reversible bond.

As a further example of the conductive polymer, either one of the first polymer compound and the second polymer compound has both a monomer unit having a host group and a monomer unit having a guest group. It can also be in the form. In the following, this form will be abbreviated as "third form".

In the third form, both the first polymer compound and the second polymer compound also have a conductive monomer unit. For example, in the third form, one of the first polymer compound and the second polymer compound contains a monomer unit having a styrene sulfonic acid skeleton, and the other contains a monomer unit having a thiophene skeleton. It can be a structure.

In the third embodiment, when the polymer compound containing a monomer unit having a styrene sulfonic acid skeleton contains a monomer unit having a host group and a guest group, the host group and the guest group are easy to produce. The main chain of the monomer unit having is preferably a CC bond. Further, in the third embodiment, when the polymer compound containing the monomer unit having a thiophene skeleton contains the monomer unit having a host group and a guest group, the host group and the guest group are easy to produce. The main chain of the monomeric unit having is preferably a thiophene skeleton.

In the third form, of the first polymer compound and the second polymer compound, the polymer compound containing the monomer unit having a host group and the monomer unit having a guest group is further conductive. It is preferable that the polymer compound contains a monomer unit and the other polymer compound is formed only by the conductive monomer unit. In this case, a host-guest interaction occurs between the polymer compounds containing the monomer unit having a host group and the monomer unit having a guest group, and further, the monomer unit having a host group and the guest An electrostatic interaction also occurs between the polymer compound containing the monomer unit having a group and the other polymer compound. That is, the polymer chains of the conductive polymer can be bonded by two types of non-covalent bonds, electrostatic interaction and host-guest interaction. This further enhances the self-healing performance of the conductive polymer material.

In the third form, the polymer compound containing the monomer unit having a host group and the monomer unit having a guest group contains the monomer unit having a styrene sulfonic acid skeleton, and the other polymer compound is It preferably contains a monomeric unit having a thiophene skeleton. In this case, the self-repair rate is particularly likely to improve. The polymer compound containing the monomer unit having a styrene sulfonic acid skeleton exerts a function as a "lactone" in the conductive polymer. In the conductive polymer material of the third form, for example, in addition to each of the sulfonic acid ion and the thiophene skeleton being a functional group for forming a reversible bond in the conductive polymer, a host group and a guest group are also included. It is a functional group for forming a reversible bond.

As a further example, both the first polymer compound and the second polymer compound can be in the form of having both a monomer unit having a host group and a monomer unit having a guest group. In the following, this form will be abbreviated as "fourth form".

In the fourth form, both the first polymer compound and the second polymer compound also have a conductive monomer unit. For example, in the fourth form, one of the first polymer compound and the second polymer compound contains a monomer unit having a styrene sulfonic acid skeleton, and the other contains a monomer unit having a thiophene skeleton. It can be a structure.

In the fourth form, the polymer compound containing a monomer unit having a styrene sulfonic acid skeleton also has a CC bond in the main chain of the monomer unit having a host group and a guest group from the viewpoint of easy production. It is preferable to have. Further, in the fourth form, the polymer compound containing the monomer unit having a thiophene skeleton has the same thiophene skeleton as the main chain of the monomer unit having a host group and a guest group from the viewpoint of easy production. Is preferable. The polymer compound containing the monomer unit having a styrene sulfonic acid skeleton exerts a function as a "lactone" in the conductive polymer. In the conductive polymer material of the fourth form, for example, in addition to each of the sulfonic acid ion and the thiophene skeleton being a functional group for forming a reversible bond in the conductive polymer, a host group and a guest group are also included. It is a functional group for forming a reversible bond.

In the fourth form, since both the first polymer compound and the second polymer compound have both a monomer unit having a host group and a monomer unit having a guest group, the first polymer compound A host-guest interaction occurs between the second polymer compounds and in any combination of the first polymer compound and the second polymer compound. Further, in the fourth form, an electrostatic interaction between the first polymer compound and the second polymer compound occurs. That is, the polymer chains of the conductive polymer can be bonded by two types of non-covalent bonds, electrostatic interaction and host-guest interaction. As a result, in the fourth form, the conductivity and the self-repairing performance are particularly excellent.

In the present invention, the type of the monomer unit having a host group contained in the conductive polymer is not particularly limited, and known monomer units can be widely adopted.

As the monomer unit having a host group, for example, a single amount derived from a polymerizable monomer represented by the general formula (h3) described below (hereinafter, abbreviated as “host group-containing polymerizable monomer”). The body unit can be mentioned.

In formula (h3), Ra represents a hydrogen atom or a methyl group, and R ¹ has a hydroxyl group, a thiol group, an alkoxy group which may have one or more substituents, and one or more substituents. It may have a thioalkoxy group, an alkyl group which may have one or more substituents, an amino group which may have one substituent, and one or more substituents. A divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of a good amide group, an aldehyde group and a carboxyl group, and ^RH represents a host group. The type of host group is the same as described above.

In the formula (h3), when R ¹ is a divalent group formed by removing one hydrogen atom from an alkoxy group, an alkoxy group having 1 to 10 carbon atoms is exemplified as the alkoxy group. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a pentyloxy group, a hexyloxy group and the like, and these are linear and branched chains. It may be any of.

In the formula (h3), when R ¹ is a divalent group formed by removing one hydrogen atom from a thioalkoxy group, a thioalkoxy group having 1 to 10 carbon atoms is exemplified as the thioalkoxy group. Specific examples thereof include methylthio group, ethylthio group, propylthio group, isoppilthio group, butylthio group, isobutylthio group, sec-butylthio group, pentylthio group, hexylthio group and the like, which are linear and branched chains. It may be in any form.

In the formula (h3), when R ¹ is a divalent group formed by removing one hydrogen atom from an alkyl group, an alkyl group having 1 to 30 carbon atoms is exemplified as the alkyl group. Examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group and the like. It may be either linear or branched.

In formula (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, the nitrogen atom of the amino group. Can bond with carbon atoms in the main chain (C = C bond).

In formula (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, the carbon atom of the amide group. Can bond with the carbon atom of the main chain (C = C bond).

In formula (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group is the carbon atom of the main chain (C = C bond). Can be combined with.

In formula (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from the carboxyl group, the carbon atom of the carboxyl group is the carbon atom of the main chain (C = C bond). Can be combined with.

In the formula (h3), R ¹ is a divalent group formed by removing one hydrogen atom from an amide group which may have a hydroxyl group, a carboxyl group and one substituent. That is, it is preferably one of -O- (ether bond), -COO- (ester bond) and -CO-NH- (amide bond), respectively, and in particular, even if it has one substituent. It is preferably a divalent group (-CO-NH-) formed by removing one hydrogen atom from a good amide group.

The host group-containing polymerizable monomer is preferably, for example, a (meth) acrylic acid ester derivative or a (meth) acrylamide derivative. Specific examples thereof include 6- (meth) acrylamide-α-cyclodextrin, 6- (meth) acrylamide-β-cyclodextrin, α-cyclodextrin (meth) acrylate, β-cyclodextrin (meth) acrylate, and α-. Cyclodextrin (meth) acrylate, β-cyclodextrin (meth) acrylate, and styrene can be mentioned. The host group-containing polymerizable monomer can be produced by a known method. As used herein, "(meth) acrylic" means "acrylic or methacryl". That is, for example, the description of "(meth) acrylic acid" is synonymous with the description of "acrylic acid or methacrylic acid".

As the monomer unit having a guest group, for example, a single amount derived from a polymerizable monomer represented by the general formula (g3) described below (hereinafter, abbreviated as “guest group-containing polymerizable monomer”). The body unit can be mentioned.

In formula (g3), Ra represents a hydrogen atom or a methyl group, and R ² has a hydroxyl group, a thiol group, an alkoxy group which may have one or more substituents, and one or more substituents. It may have a thioalkoxy group, an alkyl group which may have one or more substituents, an amino group which may have one substituent, and one or more substituents. It represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of a good amide group, an aldehyde group and a carboxyl group, and ^RG represents a guest group. The types of guest groups are the same as described above.

Wherein (g3), the definition of ^{R 2} has the same meaning as ^{R 1} in the formula (h3), is also similar manner binding of the main chain (C = C bond).

In formula (g3), R ² is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, that is, -CO-NH. -Or, it is preferably a divalent group formed by removing one hydrogen atom from the carboxyl group, that is, -COO-.

The guest group-containing polymerizable monomer is preferably, for example, a (meth) acrylic acid ester derivative or a (meth) acrylamide derivative. Specific examples thereof include n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, and n-dodecyl (meth) acrylate. , 1-acrylamide adamantan, N-dodecyl (meth) acrylamide, t-butyl (meth) acrylate, n-dodecyl (meth) acrylate, 1-acrylamide adamantan, N- (1-adamantyl) (meth) acrylamide, N Examples thereof include −benzyl (meth) acrylamide, N-1-naphthylmethyl (meth) acrylamide, ethoxylated o-phenylphenol acrylate, phenoxypolyethylene glycol acrylate, isostearyl acrylate, nonylphenol EO adduct acrylate, and isobornyl acrylate. The host group-containing polymerizable monomer can be produced by a known method. The guest group-containing polymerizable monomer can be produced by a known method.

As another example of the monomer unit containing a host group, the monomer unit represented by the general formula (H1) described later can be mentioned.

In formula (H1), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin.

The monomer unit represented by the general formula (H1) has a host group (CD). In addition, since the monomer unit represented by the general formula (H1) has a thiophene skeleton, it can impart conductivity and also functions as a positive charge. That is, the monomer unit represented by the general formula (H1) is a conductive polymer as compared with the monomer unit derived from the host group-containing polymerizable monomer represented by the above formula (h3). Can be imparted with high conductivity and can form two types of non-covalent bonds, electrostatic interaction and host-guest interaction. A conductive polymer having such a monomer unit can impart excellent conductivity to the conductive material and can also enhance self-healing property.

The monomer unit represented by the general formula (H1) is, for example, the following formula (h1).

(In formula (h1), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
It can be formed by the polymerization of the polymerizable monomer represented by.

The method for producing the polymerizable monomer represented by the formula (h1) is not particularly limited. For example, the polymerizable monomer represented by the general formula (h1) can be produced by reacting 3,4-thiophenedicarboxylic acid anhydride with aminocyclodextrin. The reaction conditions are not particularly limited, and for example, reaction conditions of a known acid anhydride and an amine compound can be adopted. Examples of the aminocyclodextrin include 6-amino-β-cyclodextrin.

As a further example of the monomer unit containing a host group, there is a monomer unit represented by the general formula (H2) described later.

In formula (H2), CD is synonymous with CD of formula (H1).

The monomer unit represented by the general formula (H2) has a host group (CD). In addition, since the monomer unit represented by the general formula (H2) has a thiophene skeleton, it can impart conductivity and also functions as a positive charge. That is, the monomer unit represented by the general formula (H2) is a conductive polymer as compared with the monomer unit derived from the host group-containing polymerizable monomer represented by the above formula (h3). Can be imparted with high conductivity and can form two types of non-covalent bonds, electrostatic interaction and host-guest interaction. A conductive polymer having such a monomer unit can impart excellent conductivity to the conductive material and can also enhance self-healing property.

The monomer unit represented by the general formula (H2) is, for example, the following formula (h2).

(In the formula (h2), CD is synonymous with the CD of the formula (h1))
It can be formed by the polymerization of the polymerizable monomer represented by.

The monomer unit containing a host group contained in the conductive polymer may be used alone or may contain two or more different types.

As another example of the monomer unit containing a guest group, the monomer unit represented by the general formula (G1) described later can be mentioned.

(In equation (G1), ^RG indicates a guest group)

The type of guest group ( ^RG ) is the same as that of the guest group described above.

The monomer unit represented by the general formula (G1) has a guest group. In addition, since the monomer unit represented by the general formula (G1) has a thiophene skeleton, it can impart conductivity and also functions as a positive charge. That is, the monomer unit represented by the general formula (G1) is a conductive polymer as compared with the monomer unit derived from the guest group-containing polymerizable monomer represented by the general formula (g3). Can be imparted with high conductivity and can form two types of non-covalent bonds, electrostatic interaction and host-guest interaction. The conductive polymer having such a monomer unit can impart excellent conductivity to the conductive material and can also enhance self-repairing property.

The monomer unit represented by the general formula (G1) is, for example, the following formula (g1).

(In formula (g1), ^RG indicates a guest group)
It can be formed by the polymerization of the polymerizable monomer represented by. R ^G has the same meaning as ^{R G} of formula (G1).

The method for producing the polymerizable monomer represented by the formula (g1) is not particularly limited. For example, the polymerizable monomer represented by the general formula (g1) can be produced by reacting ^{3,4-thiophenedicarboxylic acid anhydride with RG-} NH _2. The reaction conditions are not particularly limited, and for example, reaction conditions of a known acid anhydride and an amine compound can be adopted. ^{Examples of RG-} NH ₂ include 1-adamantylamine and the like.

As another example of the monomer unit containing a guest group, there is a monomer unit represented by the general formula (G2) described later.

(In equation (G2), ^RG indicates a guest group)

The type of guest group ( ^RG ) is the same as that of the guest group described above.

The monomer unit represented by the general formula (G2) has a guest group. In addition, since the monomer unit represented by the general formula (G2) has a thiophene skeleton, it can impart conductivity and also functions as a positive charge. That is, the monomer unit represented by the general formula (G2) is a conductive polymer as compared with the monomer unit derived from the guest group-containing polymerizable monomer represented by the general formula (g3). Can be imparted with high conductivity and can form two types of non-covalent bonds, electrostatic interaction and host-guest interaction. The conductive polymer having such a monomer unit can impart excellent conductivity to the conductive material and can also enhance self-repairing property.

The monomer unit represented by the general formula (G2) is, for example, the following formula (g2).

(In formula (g2), ^RG indicates a guest group)
It can be formed by the polymerization of the polymerizable monomer represented by. R ^G has the same meaning as ^{R G} of formula (G2).

The monomer unit containing a guest group contained in the conductive polymer may be used alone or may contain two or more different types.

In the first polymer compound and the second polymer compound, the content of each monomer unit contained in each polymer compound can be appropriately selected.

For example, in the case of the conductive polymers of the second form, the third form and the fourth form, the monomer unit having a host group is 0. It can be 5 to 10 mol%, preferably 1 to 5 mol%, more preferably 2 to 4 mol%. In these cases, the conductive polymer can have particularly excellent conductivity and self-healing performance.

Further, in the case of the conductive polymers of the second form, the third form and the fourth form, the monomer unit having a guest group is 0. It can be 5 to 10 mol%, preferably 1 to 5 mol%, more preferably 2 to 4 mol%. In these cases, the conductive polymer can have particularly excellent conductivity and self-healing performance.

The method for producing the first polymer compound and the second polymer compound is not particularly limited, and for example, known polymerization reactions can be widely adopted. For example, if the monomer for forming the monomer unit is a radically polymerizable monomer, the same conditions as those of known radical polymerization can be adopted.

In radical polymerization, for example, a mixture containing a polymerizable monomer may be polymerized in an aqueous solvent in the presence of a polymerization initiator. When the conductive polymer is in the second form, the mixture containing the polymerizable monomer is a mixture of a styrene sulfonate and the above formula (h3), or a styrene sulfonate and the above formula (g3). A mixture with and is exemplified. When the conductive polymer is in the third form or the fourth form, the mixture containing the polymerizable monomer is a mixture of styrene sulfonate, the formula (h3), and the formula (g3). Illustrated. Examples of the styrene sulfonate are sodium styrene sulfonate.

The aqueous solvent used in radical polymerization is, for example, water. In addition, the aqueous solvent may be a lower alcohol or a mixed solvent of a lower alcohol and water.

The amount of the aqueous solvent used is not particularly limited, and for example, it is preferable to use the aqueous solvent so that the concentration of the totally polymerizable monomer used in the polymerization reaction is 0.01 M or more, and it is 0.1 M or more. As described above, it is more preferable to use an aqueous solvent, and it is particularly preferable to use an aqueous solvent so as to have a concentration of 0.2 M or more. From the viewpoint of easily maintaining good polymerization reactivity, it is preferable to use an aqueous solvent so that the concentration of the total polymerizable monomer used in the polymerization reaction is 10 M or less.

Examples of the polymerization initiator used in radical polymerization include ammonium persulfate (hereinafter, also referred to as APS), persulfate such as potassium persulfate and sodium persulfate, and azobisisobutyronitrile (hereinafter, AIBN). (Sometimes referred to as), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (hereinafter sometimes referred to as VA-044), 1,1'-azobis (cyclohexanecarbo). Nitrile), di-tert-butylperoxide, tert-butylhydroperoxide, benzoyl peroxide, photopolymerization initiator (Irgacure (registered trademark) series, etc.) and the like. The polymerization initiator used in radical polymerization is preferably any one of APS, persulfates such as potassium persulfate and sodium persulfate, and VA-044.

In the mixture used in radical polymerization, the concentration of the polymerization initiator can be 0.5 to 5 mol% with respect to the total amount of the polymerizable monomers. In carrying out the radical polymerization reaction, other additives may be added if necessary. Examples of other additives include polymerization accelerators and cross-linking agents. Examples of the polymerization accelerator include N, N, N', N'-tetramethylethylenediamine and the like. The concentration of the polymerization accelerator can be, for example, 0.5 to 5 mol% with respect to the total amount of the polymerizable monomer.

The conditions of the radical polymerization reaction can be carried out under appropriate conditions according to the polymerizable property of the monomer used, the amount used, the half-life temperature of the polymerization initiator, and the like. For example, the mixture can be stirred at 0-100 ° C, preferably 20-25 ° C. The time of the polymerization reaction can be 1 to 24 hours, preferably 12 to 24 hours. When a photopolymerization initiator is used as the polymerization initiator, the polymerization reaction can be carried out, for example, by irradiating the mixture with UV light having a wavelength of 200 to 400 nm.

In the radical polymerization reaction, before starting the polymerization reaction, a monomer such as a polymerizable monomer having a host group represented by the above formula (h3) or the like and a monomer represented by the above formula (g3) or the like are represented in advance. It is possible to have a step (heating step) of heating a mixture with a monomer such as a polymerizable monomer having a guest group. By this heating step, the interaction between the host group and the guest group can occur to form a clathrate compound (clathrate complex) between the monomers. As a result, the mixture of the polymerizable monomers tends to be uniform, the polymerization reaction proceeds rapidly, and the host-guest interaction in the conductive polymer also tends to be formed.

Whether or not the clathrate compound is formed can be determined, for example, by visually observing the state after heating. Specifically, if no clathrate compound is formed, the mixture is in a suspended state or in a phase-separated state when left to stand, but when a clathrate compound is formed, it has a viscosity such as gel or cream. Can be in a state of having.

In the heating step, the heating temperature can be, for example, 20 to 100 ° C., and the preferred heating temperature is 50 to 80 ° C. The heating time in the heating step can be, for example, 1 minute to 12 hours, and a more preferable reaction time is 15 minutes to 1 hour. The heating means is also not particularly limited, and examples thereof include a method using a hot stirrer and a method using a constant temperature bath. Sonication can also be applied with or in place of heating.

When the heating step contains a monomer other than the polymerizable monomer having a host group and the polymerizable monomer having a guest group, the monomer can be added after the completion of the heating step. Alternatively, it can be added to the mixture of polymerizable monomers before the heating step. The addition of the polymerizable monomer of the raw material used for the polymerization reaction such as the aqueous solvent and the polymerization initiator to the mixture may be performed either before the heating step or after the heating step.

The method for producing the first polymer compound and the second polymer compound can also be produced by a method other than radical polymerization. For example, when the polymer compound has a thiophene skeleton, it can be produced by carrying out a polymerization reaction of a mixture of monomers having a thiophene skeleton in the presence of an organic metal salt catalyst. Hereinafter, this polymerization reaction is abbreviated as "second polymerization method".

In the second polymerization method, for example, a mixture containing a polymerizable monomer may be polymerized in an alcohol solvent in the presence of a catalyst. When the conductive polymer is in the second form, the mixture containing the polymerizable monomer is the polymerizable monomer represented by the formula (h1) or the polymerizable monomer represented by the formula (g1). An example is a mixture of a monomer and a compound having a thiophene skeleton (excluding the polymerizable monomer represented by the formula (h1) and the polymerizable monomer represented by the formula (g1)). .. When the conductive polymer is in the third form or the fourth form, the mixture containing the polymerizable monomer is represented by the polymerizable monomer represented by the formula (h1) and the formula (g1). An example is a mixture of a polymerizable monomer and a compound having a thiophene skeleton (excluding the polymerizable monomer represented by the formula (h1) and the polymerizable monomer represented by the formula (g1)). Will be done. Examples of the compound having a thiophene skeleton include EDOT. In the second polymerization method, the polymerizable monomer represented by the formula (h2) can be used in place of or in combination with the polymerizable monomer represented by the formula (h1). Further, in the second polymerization method, the polymerizable monomer represented by the formula (g2) can be used in place of or in combination with the polymerizable monomer represented by the formula (g1).

In the second polymerization method, examples of the catalyst include organic metal salts such as iron (III) paratoluenesulfonate; persulfates such as APS, potassium persulfate and sodium persulfate; and the like. Regardless of whether the catalyst of the organometallic salt or the persulfate is used, the finally obtained conductive polymer can have the same performance.

In the second polymerization method, examples of the alcohol include lower alcohols such as methanol and ethanol.

The polymerization conditions of the second polymerization method are not particularly limited, and for example, a known polymerization method of a thiophene compound performed in the presence of an organometallic salt catalyst, for example, a known method such as electrolytic polymerization can be widely adopted. ..

In the second polymerization method as well, the clathrate compound may be formed by a heating step as in the case of the radical polymerization. The conditions of the heating step are the same as in the case of the radical polymerization.

As an example, the polymer compound obtained by the second polymerization method includes one or both of the monomer unit represented by the formula (H1) and the monomer unit represented by the formula (G1), and the following. Equation (C1)

The monomer unit represented by is included as a constituent unit. Hereinafter, the polymer compound having such a structure will be referred to as “polymer compound A”.

Since the polymer compound A has a thiophene skeleton in the constituent unit, it can itself be a conductive polymer compound. In this case, excellent conductivity can be exhibited by using a polymer compound having a monomer having a styrene sulfonic acid skeleton such as sodium styrene sulfonate as a dopant.

When the polymer compound A contains one of the structural unit represented by the formula (H1) and the structural unit represented by the formula (C1), the polymer compound A has the second form. It can be a first polymer compound or a second polymer compound constituting a conductive polymer. In this case, the monomer unit represented by the formula (H2) can be used in place of or in combination with the monomer unit represented by the formula (H1).

When the polymer compound A contains both structural units of the monomer unit represented by the formula (H1) and the monomer unit represented by the formula (G1), the polymer compound A is a third component. It can be a first polymer compound or a second polymer compound constituting the conductive polymer of the form. In this case, the monomer unit represented by the formula (H2) can be used in place of or in combination with the monomer unit represented by the formula (H1), and the unit amount represented by the formula (G1) can be used. The monomer unit represented by the formula (G2) can be used in place of or in combination with the body unit.

Further, when the polymer compound A contains a monomer unit represented by the formula (H1), a monomer unit represented by the formula (G1), and a constituent unit represented by the formula (C1). Can be the first polymer compound and the second polymer compound constituting the conductive polymer of the fourth form. In this case, the monomer unit represented by the formula (H2) can be used in place of or in combination with the monomer unit represented by the formula (H1), and the unit amount represented by the formula (G1) can be used. The monomer unit represented by the formula (G2) can be used in place of or in combination with the body unit.

As the conductive polymer, for example, the first polymer compound and the second polymer compound are individually produced, and the obtained first polymer compound and the second polymer compound are respectively produced. It can be prepared by mixing. When mixing the first polymer compound and the second polymer compound, for example, both can be mixed in a solid state, or both can be mixed in a solution state. Alternatively, a method of adding the other polymer compound in a solid state to a solution of one polymer compound may be used.

The conductive polymer is prepared so that the conductive monomer unit contained in the first polymer compound and the conductive monomer unit contained in the second polymer compound have an arbitrary molar ratio. For example, when one conductive monomer unit is a sodium styrene sulfonate unit (hereinafter abbreviated as "NaSS unit") and the other conductive monomer unit is an EDOT unit (EDOT unit), the NaSS unit / EDOT The unit (molar ratio) is preferably 0.1 to 20, more preferably 0.2 to 10, more preferably 0.3 to 5, and particularly preferably 0.4 to 1.

The conditions for mixing the first polymer compound and the second polymer compound are not particularly limited. For example, the temperature at the time of mixing, the mixing time, the mixing means, and the like can be performed under appropriate conditions.

In a conductive polymer, polymer compounds form reversible bonds (for example, non-covalent bonds), so that one type of polymer chains or two or more different reversible bonds (for example, non-covalent bonds) can be formed. Can be formed. For example, in a conductive polymer, as described above, an electrostatic interaction between a negative charge of sulfonic acid and a positive charge of thiophene acts, and further, a host-guest interaction due to a bond between a host group and a guest group acts. Can work.

The conductive polymer may contain a polymer compound other than the first polymer compound and the second polymer compound as long as the effect of the present invention is not impaired.

The self-healing conductive material of the present invention is formed of the conductive polymer. The self-healing conductive material can be formed only of the conductive polymer, and can contain additives other than the conductive polymer as long as the effect of the present invention is not impaired.

As the additive, known additives that can be contained in the conductive material can be widely adopted, and examples thereof include an ultraviolet absorber, a light stabilizer, an antistatic agent, a dispersion stabilizer, and a lubricant.

The self-healing conductive material contains a conductive polymer in an amount of 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the self-healing conductive material. , 99% by mass or more is particularly preferable.

The self-healing conductive material can be formed in the form of a film. If the self-healing conductive material is in the form of a film, it can be used for various purposes used in the form of a film, a film, or the like. When the self-healing conductive material is in the form of a film, the thickness is not particularly limited and can be set to an appropriate thickness according to the application. For example, the self-healing conductive material can be adjusted to 1 nm to 1 cm, and can be adjusted to 1 μm to 100 μm in terms of good film forming property.

The method for forming the film-like self-healing conductive material is not particularly limited, and for example, a known film-forming method can be widely adopted. For example, a conductive polymer solution or dispersion is prepared, and a film-like self-healing conductive material is obtained by various film forming means such as a coating method, a casting method, and a spin coating method using this solution or dispersion. Can be formed. The solvent for preparing the solution or dispersion is not particularly limited, and an organic solvent such as water or alcohol can be widely used.

When the self-healing conductive material is in the form of a film, it is preferable that the self-healing conductive material is covalently bonded to the substrate to form a film. Specifically, it is preferable that the film-like self-healing conductive material forms a covalent bond with the functional group existing on the surface of the substrate. In this case, the adhesive force (adhesion) between the film-like self-healing conductive material and the substrate can be improved.

The covalent bond between the substrate and the film-like self-healing conductive material exists, for example, on the surface of the substrate and the functional group of the monomer unit in the conductive polymer contained in the self-healing conductive material. It is formed by reacting with a functional group.

From the viewpoint that the conductive polymer is more likely to form a covalent bond with the functional group on the surface of the substrate, the structural unit contained in the conductive molecule reacts with the functional group existing on the surface of the substrate to form a covalent bond. It is preferable to contain a monomeric unit capable of the above.

More preferably, in the self-healing conductive material, at least one of the first polymer compound and the second polymer compound has a single amount having a functional group capable of forming the covalent bond with the substrate. The functional group including the body unit and capable of forming the covalent bond and the functional group on the surface of the substrate form a covalent bond. The monomer unit having a functional group capable of forming the covalent bond with the substrate is hereinafter referred to as "anchor-containing monomer unit".

From the viewpoint that the conductive polymer is more likely to form a covalent bond with the functional group on the surface of the substrate, the anchor-containing monomer unit includes a compound derived from an acid anhydride, a halogen group (for example, F, Cl, Br, etc.). compounds having I), acyl halide (e.g., a compound having COCl group, compounds having a COBr group), a compound having an isocyanate group (NCO), a triflate group _(CF 3 SO ₃ ^- compound having a group), Examples thereof include a monomer unit derived from a compound having an epoxy group, a compound having a p-toluenesulfonic acid group, a compound having a methanesulfonic acid group, and the like.

As an example of the anchor-containing monomer unit (monomer unit having a functional group capable of forming the covalent bond), the following formula (A1)

を挙げることができる。この場合、第１の高分子化合物及び／又は第２の高分子化合物へのアンカー含有単量体単位の導入が容易であり、また、基板との共有結合も形成しやすくなる。式（Ａ１）で表されるアンカー含有単量体単位は、例えば、３，４−チオフェンジカルボン酸無水物に由来する構成単位である。

Can be mentioned. In this case, it is easy to introduce the anchor-containing monomer unit into the first polymer compound and / or the second polymer compound, and it is also easy to form a covalent bond with the substrate. The anchor-containing monomer unit represented by the formula (A1) is, for example, a structural unit derived from 3,4-thiophenedicarboxylic acid anhydride.

In the first polymer compound and the second polymer compound, the content of the anchor-containing monomer unit contained in each polymer compound can be appropriately selected.

For example, the anchor-containing monomer unit is 0. It can be 5-10 mol%, more preferably 1-5 mol%.

When the first polymer compound and the second polymer compound contain an anchor-containing monomer unit, the method for producing the polymer compound is not particularly limited. For example, a compound for forming an anchor-containing monomer unit (sometimes referred to as an "anchor molecule") is added to a polymerizable monomer for producing a first polymer compound and a second polymer compound. A predetermined amount is mixed and a polymerization reaction is carried out. Thereby, a polymer compound containing an anchor-containing monomer unit can be obtained.

On the other hand, the functional groups existing on the surface of the substrate include, for example, an alkenyl group, a vinyl group, -OH, -SH, -NH ₂ , -COOH, -SO ₃ H, -PO ₄ H, an isocyanate group, a glycidyl group, and an azide. Examples include a group, a boronic acid group, an alkynyl group and the like. In particular, as the functional group existing on the surface of the substrate, -OH, -NH ₂ , -COOH and the like are preferable, and in this case, a covalent bond with the conductive polymer is likely to be formed, and these functional groups are described later. It is possible to easily modify the surface of the substrate by surface treatment of the substrate.

The method for forming the covalently bondable functional group on the surface of the substrate is not particularly limited, and for example, a known method can be widely adopted. Alternatively, a commercially available substrate that already has a covalently bondable functional group on the surface can be adopted.

Examples of the method for forming a covalently bondable functional group on the surface of the substrate include a method of treating the surface of the substrate with a silane coupling agent, a method of irradiating with plasma, a method of ozone treatment, a method of base treatment, a method of acid treatment and the like. be able to. All of these methods can be performed under the same conditions as known methods.

In the method of irradiating plasma, the type of plasma is not particularly limited, and various high-density plasmas such as microwave plasma, plasma jet, induction-coupled plasma, and electron cyclotron resonance plasma can be mentioned, and in addition, oxygen plasma and nitrogen. Plasma, argon plasma and the like are also exemplified.

In the method of irradiating plasma, a known plasma irradiation device can be used. When irradiating the plasma, the nozzle may be rotated while irradiating the plasma, or the plasma may be irradiated by fixed point spraying. Plasma irradiation conditions such as output and irradiation time are also set as appropriate.

Plasma irradiation can be performed under various atmospheres, for example, under atmospheric pressure, a nitrogen atmosphere, and a mixed gas atmosphere of nitrogen and hydrogen. In the case of a mixed gas atmosphere of nitrogen and hydrogen, the mixing ratio of nitrogen and hydrogen may be appropriately set from the viewpoint of safety and the like. For example, the mixing ratio of nitrogen 100 to 97 vol% and hydrogen 0 to 3 vol% should be set. Can be done. In order to irradiate plasma under a nitrogen atmosphere or an atmosphere of nitrogen and hydrogen, for example, the substrate may be housed in a container such as glass, the inside of the glass may be purged with a predetermined gas, and then plasma irradiation may be performed.

The surface state of the substrate can be changed by appropriately changing the plasma irradiation conditions. For example, the surface condition (for example, surface hydrophilicity) of the substrate changes depending on the type of gas existing in the atmosphere, the type of substrate, the plasma irradiation time, and the plasma irradiation conditions (whether the nozzle is rotated or fixed point spraying). Can be done. For example, in XPS measurement before and after plasma irradiation, the intensity of the peak derived from the carbon atom may decrease and the intensity of the peak derived from the oxygen atom may increase. Furthermore, when plasma irradiation is performed in a nitrogen atmosphere, the peak intensity derived from nitrogen atoms can be increased.

The ozone treatment method is not particularly limited, and a known ozone treatment method can be adopted. For example, ozone treatment can be performed by allowing the substrate to stand in a commercially available ozone cleaner and irradiating it with ultraviolet rays in an oxygen atmosphere. When the substrate is ozone-treated, the ozone-treated portion of the substrate has a large proportion of oxygen atoms, and the hydrophilicity can be improved.

The base treatment method is not particularly limited, and a known base treatment method can be adopted. For example, the base treatment can be performed by immersing the substrate in a liquid in which a base is dissolved for a predetermined time. The type of base is not limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, and ammonia. Examples of the solvent for dissolving the base include water, a lower alcohol, and a mixed solvent of water and alcohol. When the substrate is base-treated, the hydrophilicity of the base-treated portion of the substrate can be improved.

The acid treatment method is not particularly limited, and a known acid treatment method can be adopted. For example, the acid treatment can be performed by immersing the substrate in a liquid in which an acid is dissolved for a predetermined time. The type of acid is not limited, and examples thereof include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid and citric acid. The solvent that dissolves the acid can be the same as the solvent that dissolves the base. When the substrate is acid-treated, the hydrophilicity of the acid-treated portion of the substrate can be improved.

Whether or not a functional group is introduced on the surface of the substrate can be determined by, for example, measurement of contact angle, XPS, IR, fluorescent X-ray, ICP emission spectrometry, analysis using TOF-SIMS, or the like. For example, when a functional group is introduced on the surface of the substrate, the contact angle changes, so that it is possible to confirm the presence or absence of the introduction of the functional group.

As the type of substrate, it is preferable to use a substrate having a covalently bondable functional group on the substrate surface or a substrate into which a functional group can be introduced by the surface treatment, for example, a glass substrate, a metal substrate, a resin substrate, or an inorganic substrate. Examples include various substrates such as plates.

The self-healing conductive material can be in various shapes in addition to the film shape, and examples thereof include a substrate shape, a sheet shape, a block shape, a powder shape, and a fibrous shape.

The self-healing conductive material of the present invention has excellent conductivity and self-healing performance by containing the conductive polymer. For example, if the self-healing conductive material is in the form of a film, even if the film surface is cut or cut, the self-healing performance causes the wound to be closed or the cut parts to each other. Can adhere and be restored to the same or close state to the original state. Such self-healing properties are not limited to one time, and self-healing self-healing can be performed multiple times.

The self-healing conductive material of the present invention can be self-healed by natural healing, and other scratched self-healing conductive materials can be subjected to a high humidity environment (for example, an environment with a humidity of 60% RH or more). It is also possible to adopt a method of placing the wound on the wound or a method of adhering water to the wound to self-repair. Examples of the method of adhering water include a method of dropping water on the wound and a method of spraying water on the wound. In both the case of self-repair by natural healing and the case of self-repair by adhering water, it is preferable to carry out in a high humidity environment.

The self-healing conductive material of the present invention can have, for example, a self-healing rate of 20% or more. A preferable self-repair rate is 25% or more, a more preferable self-repair rate is 30% or more, a further preferable self-repair rate is 40% or more, and a particularly preferable self-repair rate is 50% or more. In the self-healing conductive material of the present invention, the self-healing rate may be 100%.

The self-healing conductive material of the present invention can have an electrical conductivity (conductivity) of 1.0 × ^10-5 S / cm or more. The self-healing conductive material is preferably 4.2 × ^10-5 S / cm, more preferably 5.4 × ^10-5 S / cm or more, and particularly preferably 8.0 × ^10-5 S / cm. That is all.

The self-healing conductive material of the present invention can be applied to various applications. For example, the self-healing material can be suitably used for various applications in the electronics field such as fuel cells, solar cells, capacitors, touch panels, electromagnetic wave shields, antistatic films, organic LEDs, and transistors.

As an application example of the self-healing conductive material of the present invention, a member for a separator of various batteries such as a fuel cell and a secondary battery can be mentioned. The separator is a member that is sandwiched between cells of a fuel cell and stacked, and plays a role of blocking fuel gas and air. In addition to the function of sealing each cell, it also has the function of sending fuel gas and air by creating a flow path through which gas flows.

By attaching the film of the self-healing conductive material of the present invention to the separator, conductivity can be imparted to the separator, and the self-healing property of the self-healing conductive material improves the durability of the separator. It can also be improved. Conventionally, a polymer film or the like may be attached to the separator, but in this case, if the usage time is long, the polymer film deteriorates and causes phenomena such as peeling and pinholes, resulting in a decrease in conductivity. Was a problem. However, when the separator has a film of the self-healing conductive material of the present invention, the self-healing property can maintain the uniform state of the film, and even if the film is damaged in the work of assembling the battery, it is repaired. Therefore, it is possible to solve the conventional problem, and it is possible to improve not only the durability of the separator but also the durability of the fuel cell and the secondary battery electrode.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the aspects of these Examples.

(Manufacturing Example 1)
Sodium p-styrene sulfonate (SSNa) and 6-acrylamide-βCD (AAm-βCD), which is a polymerizable monomer having a host group, have a molar ratio of SSNa: AAm-βCD of 98: 2. To prepare an aqueous solution having a total monomer concentration of 1 M. VA-044, which is a polymerization initiator, was added to this aqueous solution so as to be 5.0 mM, and the mixture was stirred at 50 ° C. for 12 hours. Then, methanol is added to the solution to perform reprecipitation, and the obtained precipitate is dried to obtain a polymer having a structure represented by the following formula (1-1) (number average degree of polymerization n is about 500). Obtained.

The obtained polymer was designated as AAm-βCD / PSSNa (x, y). x and y are the molar ratios of the polymerizable monomer having a host group and the polymerizable monomer having a guest group, respectively, and here, x = 2 and y = 0.

(Manufacturing Example 2)
According to the following scheme (2-1), 3,4-thiophene dicarboxylic anhydride (TDCA) and 154 mg (1 mmol), was dissolved 1-adamantyl amine _(NH 2 -Ad) to 151 mg (1 mmol) and the dry DMF10mL , Stirred overnight at 80 ° C. under a nitrogen atmosphere. Then, the solvent was distilled off, and the produced precipitate was dissolved in acetone at room temperature, an amount of hexane that did not cause a precipitate was added thereto, and the mixture was allowed to stand at 4 ° C. overnight. By recovering the precipitated precipitate, the target product (Thio-Ad) was obtained in a yield of 56%.

Next, in ethanol, 3,4-ethylenedioxythiophene (EDOT) and Thio-Ad as a polymerizable monomer having a guest group were added so that the molar ratio of EDOT: Thio-Ad was 98: 2. To prepare a solution having a total monomer concentration of 60 mM, iron paratoluenesulfonate (III) was added to a concentration of 160 mM, and the mixture was stirred at room temperature for 24 hours. Then, ethanol was removed to obtain a polymer having a structure represented by the following formula (2-2).

The obtained polymer was designated as Thio-Ad / PEDOT (x, y). x and y are the molar ratios of the polymerizable monomer having a host group and the polymerizable monomer having a guest group, respectively, and here, x = 0 and y = 2.

(Manufacturing Example 3)
In water, 6-acrylamide-βCD (AAm-βCD), which is a polymerizable monomer having a host group, and adamantan acrylamide (Ad-AAm), which is a polymerizable monomer having a guest group, are mixed in this molar amount. The amounts were mixed, sealed, and heated and stirred at 50 ° C. for 3 hours. The obtained solution was allowed to cool to room temperature, and sodium p-styrene sulfonate (SSNa) was mixed therein so that the molar ratio of SSNa: AAm-βCD: Ad-AAm was 96: 2: 2. A solution was prepared so that the total concentration of the monomers was 1 M. The polymerization initiator VA-044 was added to this solution so as to be 5.0 mM, and the mixture was stirred at 50 ° C. for 12 hours. Then, methanol is added to the solution to perform reprecipitation, and the obtained precipitate is dried to obtain a polymer having a structure represented by the following formula (3-1) (number average degree of polymerization n is about 500). Obtained.

The obtained polymer was designated as βCD / Ad / PSSNa (x, y). x and y are the molar ratios of the polymerizable monomer having a host group and the polymerizable monomer having a guest group, respectively, and here, x = 2 and y = 2.

(Manufacturing Example 4)
According to the following scheme (4-1), was dissolved TDCA62mg a (0.4 mmol) and 6-amino -β- cyclodextrin _{(NH 2 -β-CD) 454mg} (0.4mmol) in dry 4 ml of DMF, under a nitrogen atmosphere The mixture was stirred at 80 ° C. overnight. Then, the solvent was distilled off, and the produced precipitate was dissolved in 10 mL of water at room temperature and purified by HP-20 of DIAION (water: methanol = 50:50 elution). The resulting liquid was evaporated and then lyophilized. The obtained solid was dissolved in water again and reprecipitated with acetone. The precipitate was collected and dried under reduced pressure to obtain the desired product (Thio-βCD) in a yield of 55%.

Then, in ethanol, 3,4-ethylenedioxythiophene (EDOT), Thio-βCD as a monomer having a host group, and Thio-Ad as a monomer having a guest group were added to EDOT: Thio-. Mix so that the molar ratio of βCD: Thio-Ad is 96: 2: 2, prepare a solution so that the total concentration of the monomers is 60 mM, and add iron (III) paratoluenesulfonate to a concentration of 160 mM. After the addition, the mixture was stirred at room temperature for 24 hours. Then, ethanol was removed to obtain a polymer having a structure represented by the following formula (4-2).

The obtained polymer was designated as βCD / Ad / PEDOT (x, y). x and y are the molar ratios of the polymerizable monomer having a host group and the polymerizable monomer having a guest group, respectively, and here, x = 2 and y = 2.

(Example 1-1)
PEDOT produced by a known method as the first polymer compound and PSSNa produced by a known method as the second polymer compound were prepared, and these were combined with the SSNa monomer unit and the PEDOT monomer unit. An aqueous solution was prepared so that the molar ratio of the above was 0.5: 1. This aqueous solution was prepared so that the concentration of PEDOT was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. From the obtained suspension, a film of a conductive polymer having a thickness of about 100 μm was formed on a glass substrate by a drop casting method.

(Example 1-2)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 1-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 1: 1. Formed in.

(Example 1-3)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 1-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 5: 1. Formed in.

(Example 1-4)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 1-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 10: 1. Formed in.

(Example 1-5)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 1-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 20: 1. Formed in.

(Example 2-1)
The Ratio-Ad / PEDOT (x, y) obtained in Production Example 2 as the first polymer compound, and the AAm-βCD / PSSNa (x, y) obtained in Production Example 1 as the second polymer compound. , And these were mixed so that the molar ratio of the SSNa monomer unit and the PEDOT monomer unit was 0.5: 1 to prepare an aqueous solution. This aqueous solution was prepared so that the concentration of Thio-Ad / PEDOT (x, y) was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. From the obtained suspension, a film of a conductive polymer having a thickness of about 100 μm was formed on a glass substrate by a drop casting method.

(Example 2-2)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 2-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 1: 1. Formed in.

(Example 2-3)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 2-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 5: 1. Formed in.

(Example 2-4)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 2-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 10: 1. Formed in.

(Example 2-5)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 2-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 20: 1. Formed in.

(Example 3-1)
ΒCD / Ad / PEDOT (x, y) obtained in Production Example 4 was prepared as the first polymer compound, and PSSNa was prepared as the second polymer compound. An aqueous solution was prepared so as to have a ratio of 0.5: 1 with the molecular unit. This aqueous solution was prepared so that the concentration of βCD / Ad / PEDOT was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. From the obtained suspension, a film of a conductive polymer having a thickness of about 100 μm was formed on a glass substrate by a drop casting method.

(Example 3-2)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 3-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 1: 1. Formed in.

(Example 3-3)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 3-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 5: 1. Formed in.

(Example 3-4)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 3-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 10: 1. Formed in.

(Example 3-5)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 3-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 20: 1. Formed in.

(Example 3-6)
PEDOT was prepared as the first polymer compound, and βCD / Ad / PSSNa (x, y) obtained in Production Example 3 was prepared as the second polymer compound. An aqueous solution was prepared so as to have a ratio of 0.5: 1 with the molecular unit. This aqueous solution was prepared so that the concentration of PEDOT was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. From the obtained suspension, a film of a conductive polymer having a thickness of about 100 μm was formed on a glass substrate by a drop casting method.

(Example 3-7)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 3-6 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 1: 1. Formed in.

(Example 3-8)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 3-6 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 5: 1. Formed in.

(Example 3-9)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 3-6 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 10: 1. Formed in.

(Example 3-10)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 3-6 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 20: 1. Formed in.

(Example 4-1)
The βCD / Ad / PEDOT (x, y) obtained in Production Example 4 as the first polymer compound, and the βCD / Ad / PSSNa (x, y) obtained in Production Example 3 as the second polymer compound. , And these were mixed so as to have a ratio of SSNa monomer unit and PEDOT monomer unit in a ratio of 0.5: 1 to prepare an aqueous solution. This aqueous solution was prepared so that the concentration of βCD / Ad / PEDOT was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. From the obtained suspension, a film of a conductive polymer having a thickness of about 100 μm was formed on a glass substrate by a drop casting method.

(Example 4-2)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 4-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 1: 1. Formed in.

(Example 4-3)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 4-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 5: 1. Formed in.

(Example 4-4)
A conductive polymer film was placed on the glass substrate in the same manner as in Example 4-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 10: 1. Formed in.

(Example 4-5)
A conductive polymer film was formed on a glass substrate in the same manner as in Example 4-1 except that the SSNa monomer unit and the EDOT monomer unit were mixed so as to have a molar ratio of 20: 1. Formed in.

(Evaluation of conductivity)
The conductivity of the obtained conductive polymer film was evaluated by the 4-probe method. For measurement, Mitsubishi Chemical Analytech Co., Ltd. "Lorester GP" or "Lorester GX" is used, the probe type is PSP probe, the distance between terminals is 1.5 mm, the terminal pin tip is 0.26R, and the terminal spring pressure is set. The conductivity was measured at 70 g / piece.

(Self-healing evaluation)
A cutter knife is applied to the conductive polymer film (film area 3 to 5 cm ² ) obtained in each example and comparative example so as to have a length of 5 to 20 mm, a width of 10 to 30 μm, and a depth of 2 to 20 μm. I hurt it. Then, at 25 ° C., using a Keyence Corp. 3D laser microscope "VK-X250", by observing the wounds were measured and the area _{S 0} of the wound. This measurement was performed by the "VK-X analysis application" attached to the 3D laser microscope.

Next, the damaged conductive polymer film is ^{housed in a petri dish having a volume of 190 cm 3} , and a Kimwipe sufficiently moistened with water (20 to 30 mL) is placed on the edge of the petri dish and the lid is closed. It was allowed to stand at room temperature (25 ° C.) for 12 hours (however, 10 minutes in Examples 5-1 to 5-9). At this time, the relative humidity in the petri dish was 60 to 80% RH. _{Then, the area S 1} of the scratch was measured with a three-dimensional laser laser microscope in _{the same manner as S 0.}

For the self-repair rate, the self-repair rate was calculated by the area of the wound before and after self-repair, specifically, the calculation formula {(S _0- S ₁ ) / S ₀ } × 100.

Table 1 shows the results of the conductivity evaluation and the self-healing property evaluation.

In Example 1 (first form), the polymer chains of the conductive polymer form a non-covalent bond by electrostatic interaction, and Example 2 (second form) and Example 3 (third form). ) And Example 4 (fourth form), since non-covalent bonds are formed by electrostatic interaction and host-guest interaction, it was also found that excellent self-healing performance is exhibited. Further, since all the conductive polymers have a conductive monomer unit, it was also recognized that they have excellent conductivity. In particular, in Examples 3-6 and 4-1 it was considered that the electrostatic interaction and the host-guest interaction were effectively acting, so that remarkable self-healing performance was observed.

FIG. 1 shows the results of a self-repair test of the conductive polymer film obtained in Example 3-6, (a) is an image of the film surface before repair, and (b) is a film after repair. An image of the surface is shown, (c) shows the measurement result of the scratch area before repair, and (d) shows the measurement result of the scratch area after repair. From the comparison of FIGS. 1 (a) and 1 (b) and the comparison of (c) and (d), the conductive polymer film obtained in Example 3-6 had almost no scratches due to the self-repairing function. You can see that.

(Introduction of anchor-containing monomer unit)
(Example 5-1)
PSSNa produced by a known method is prepared as a second polymer compound, and in an aqueous solution in which PSSNa is 40 mM, EDOT and TDCA (TDCA is a compound for forming an anchor-containing monomer unit). The total concentration of the mixture with (3,4-thiophenedicarboxylic acid anhydride) was 40 mM. The molar ratio of EDOT to TDCA was 98: 2. Ammonium persulfate was added thereto to a concentration of 80 mM, and the mixture was stirred at room temperature (25 ° C.) for 24 hours. As a result, a first polymer compound was generated, and a conductive polymer containing the first polymer compound and the second polymer compound was obtained.

Next, an aqueous solution of the conductive polymer was prepared so that the concentration of the second polymer compound was 90 mM, and a suspension was obtained by irradiating ultrasonic waves as needed. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-2)
As the first polymer compound, βCD / Ad / PEDOT (2,2), which is a polymer represented by the formula (4-2), was prepared as the second polymer compound with PSSNa produced by a known method. ..

Next, an aqueous solution was prepared in which the first polymer compound and the second polymer compound were mixed so that the molar ratio of the SSNa monomer unit and the EDOT monomer unit was 0.5: 1. bottom. This aqueous solution was prepared so that the concentration of βCD / Ad / PEDOT (2,2) was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-3)
PSSNa (second polymer compound) produced by a known method is prepared, and in an aqueous solution in which PSSNa is 40 mM, EDOT, Thio-βCD represented by the formula (4-1), and the formula ( The total concentration of Thio-Ad represented by 2-1) and TDCA was dissolved so as to be 40 mM. Ammonium persulfate is added thereto to a concentration of 80 mM, and the mixture is stirred at room temperature (25 ° C.) for 24 hours to produce a first polymer compound, and the first polymer compound and the second high molecular compound are produced. A polymer material containing a molecular compound was obtained. The obtained first polymer compound has the following formula (5-3).

It is indicated by, and is expressed as PEDOT (y, y, z) (the same applies hereinafter). Y, y, z in parentheses in PEDOT (y, y, z) indicate the molar ratio of the polymerizable monomer having a host group, the polymerizable monomer having a guest group, and the anchor-containing monomer unit in this order. Here, y = 2, y = 2, z = 5, that is, PEDOT (2,2,5).

Next, an aqueous solution containing the first polymer compound and the second polymer compound is prepared so that the concentration of PEDOT (2, 2, 5) is 90 mM, and if necessary, ultrasonic waves are applied to the suspension. A turbid liquid was obtained. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-4)
AAm-βCD / PSSNa (2,0) (second polymer compound) represented by the formula (1-1) obtained in Production Example 1 and Ratio- represented by the formula (2-2). An aqueous solution prepared by mixing Ad / PEDOT (0,2) (first polymer compound) so that the molar ratio of SSNa monomer unit and PEDOT monomer unit is 0.5: 1. Prepared. This aqueous solution was prepared so that the concentration of PEDOT (0,2,0) was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-5)
In an aqueous solution containing 40 mM of AAm-βCD / PSSNa (2,0) (second polymer compound) represented by the formula (1-1) obtained in Production Example 1, the EDOT and the formula (1) The total concentration of Thio-Ad represented by 2-1) and TDCA was dissolved so as to be 40 mM. Ammonium persulfate is added thereto to a concentration of 80 mM, and the mixture is stirred and stirred at room temperature (25 ° C.) for 24 hours to generate a first polymer compound, and the first polymer compound and the second polymer compound are produced. A polymer material containing a polymer compound was obtained. The obtained first polymer compound was designated as PEDOT (y, y, z). Y, y, z in parentheses in PEDOT (y, y, z) indicate the molar ratio of the polymerizable monomer having a host group, the polymerizable monomer having a guest group, and the anchor-containing monomer unit in this order. Here, y = 0, y = 2, z = 5, that is, PEDOT (0,2,5).

Next, an aqueous solution containing the first polymer compound and the second polymer compound was prepared so that the concentration of PEDOT (0, 2, 5) was 90 mM, and ultrasonic waves were applied as needed. A suspension was obtained by irradiation. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-6)
ΒCD / Ad / PSSNa (2,2) (second polymer compound) represented by the formula (3-1) obtained in Production Example 3 and PEDOT (first high molecular weight compound) produced by a known method. A molecular compound) was mixed so that the molar ratio of the SSNa monomer unit and the PEDOT monomer unit was 0.5: 1 was prepared. This aqueous solution was prepared so that the concentration of PEDOT was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-7)
In an aqueous solution containing 40 mM βCD / Ad / PSSNa (2,2) (second polymer compound) represented by the formula (3-1) obtained in Production Example 3, EDOT and TDCA Was dissolved so that the total concentration of was 40 mM. The molar ratio of EDOT to TDCA was 98: 2. Ammonium persulfate was added thereto to a concentration of 80 mM, and the mixture was stirred at room temperature (25 ° C.) for 24 hours. As a result, a first polymer compound was generated, and a conductive polymer containing the first polymer compound and the second polymer compound was obtained.

Next, an aqueous solution of the conductive polymer was prepared so that the concentration of the second polymer compound was 90 mM, and a suspension was obtained by irradiating ultrasonic waves as needed. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-8)
ΒCD / Ad / PSSNa (2,2) (second polymer compound) represented by the formula (3-1) obtained in Production Example 3 and the polymer represented by the formula (4-2). A certain βCD / Ad / PEDOT (2,2) (first polymer compound) is mixed so that the molar ratio of the SSNa monomer unit and the EDOT monomer unit is 0.5: 1. The aqueous solution was prepared. This aqueous solution was prepared so that the concentration of βCD / Ad / PEDOT (2,2) was 90 mM. Then, if necessary, ultrasonic waves were applied to obtain a suspension. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

(Example 5-9)
In an aqueous solution containing 40 mM βCD / Ad / PSSNa (2,2) (second polymer compound) represented by the formula (3-1) obtained in Production Example 3, the EDOT and the formula (2) The total concentration of Thio-βCD represented by 4-1), Thio-Ad represented by the formula (2-1), and TDCA was dissolved so as to be 40 mM. Ammonium persulfate is added thereto to a concentration of 80 mM, and the mixture is stirred at room temperature (25 ° C.) for 24 hours to produce a first polymer compound, and the first polymer compound and the second high molecular compound are produced. A polymer material containing a molecular compound was obtained. The obtained first polymer compound was the same as the above formula (5-3) and was designated as PEDOT (y, y, z). Y, y, z in parentheses in PEDOT (y, y, z) indicate the molar ratio of the polymerizable monomer having a host group, the polymerizable monomer having a guest group, and the anchor-containing monomer unit in this order. Here, y = 2, y = 2, z = 5, that is, PEDOT (2,2,5).

Next, an aqueous solution containing the first polymer compound and the second polymer compound is prepared so that the concentration of PEDOT (2, 2, 5) is 90 mM, and if necessary, ultrasonic waves are applied to the suspension. A turbid liquid was obtained. The obtained suspension was applied to a substrate S surface-treated in advance, and a film of a conductive polymer having a thickness of about 100 μm was formed on the substrate S. The substrate S is a stainless steel substrate, and atmospheric pressure plasma treatment with a nitrogen / hydrogen mixed gas was performed in advance before applying the suspension. From the XPS analysis after this treatment, the abundance ratio of nitrogen atoms and oxygen atoms is higher than that before the plasma treatment, suggesting that hydroxyl groups and amino groups are formed on the surface of the substrate S by the plasma treatment. Was done.

In Table 2, the conductivity, self-repairing rate and adhesion of Examples 5-1 to 5-9 were measured. The conductivity and self-repairing rate were measured by the same method as in Example 1-1 and the like.

The adhesion was evaluated by a scratch test. A diamond with a radius of curvature of 15 μm is attached to the tip of the indenter, and the pressure sensed by the vertical pressure sensor is measured at an excitation amplitude of 100 μm, a scratch speed of 10 μm / S, and a load application speed of 300 mN / min. The peeling energy between the surface and the substrate was defined as "adhesion force". For the measurement, "CSR-5000" manufactured by Resca was used.

(Example 6-1)
Examples except that βCD / Ad / PEDOT (2,2), which is a polymer represented by the formula (4-2), was changed to βCD / Ad / PEDOT (5,5) as the first polymer compound. A film of the conductive polymer was formed on the substrate S in the same manner as in 5-2.

(Example 6-2)
A conductive polymer film was used as a substrate in the same manner as in Example 5-3 except that PEDOT (5, 5, 5) was produced instead of PEDOT (2, 2, 5) as the first polymer compound. Formed on S.

(Example 6-3)
AAm-βCD / PSSNa (2,0) represented by the formula (1-1) obtained in Production Example 1 was added to AAm-βCD / PSSNa (5,0) (second polymer compound) in PEDOT. A conductive polymer film was placed on the substrate S in the same manner as in Example 5-4 except that (0,2,0) was changed to PEDOT (0,5,0) (first polymer compound). Formed in.

(Example 6-4)
AAm-βCD / PSSNa (2,0) represented by the formula (1-1) obtained in Production Example 1 was changed to AAm-βCD / PSSNa (5,0) (second polymer compound). In the same manner as in Example 5-5, except that PEDOT (0,5,5) (first polymer compound) was produced instead of PEDOT (0,2,5). A film of a conductive polymer was formed on the substrate S.

(Example 6-5)
The βCD / Ad / PSSNa (2,2) represented by the formula (3-1) obtained in Production Example 3 was changed to βCD / Ad / PSSNa (5,5) (second polymer compound). A film of the conductive polymer was formed on the substrate S in the same manner as in Example 5-6 except for the above.

(Example 6-6)
The βCD / Ad / PSSNa (2,2) represented by the formula (3-1) obtained in Production Example 3 was changed to βCD / Ad / PSSNa (5,5) (second polymer compound). Further, the conductive polymer film was formed on the substrate S in the same manner as in Example 5-7 except that the first polymer compound was produced so that the molar ratio of EDOT and TDCA was 95: 5. Formed on top.

(Example 6-7)
The βCD / Ad / PSSNa (2,2) represented by the formula (3-1) obtained in Production Example 3 was changed to βCD / Ad / PSSNa (5,5) (second polymer compound). Also, except that βCD / Ad / PEDOT (2,2), which is a polymer represented by the formula (4-2), is changed to βCD / Ad / PEDOT (5,5) (first polymer compound). Formed a film of a conductive polymer on the substrate S in the same manner as in Example 5-8.

(Example 6-8)
The βCD / Ad / PSSNa (2,2) represented by the formula (3-1) obtained in Production Example 3 was changed to βCD / Ad / PSSNa (5,5) (second polymer compound). , A conductive polymer film was formed on the substrate S in the same manner as in Example 5-9, except that PEDOT (5, 5, 5) was generated instead of PEDOT (2, 2, 5). Formed in.

In Table 3, the resistance value, self-repair rate and adhesion of Examples 6-1 to 6-8 were measured. The self-repair rate and the adhesion were measured by the same method as in Example 5-1 and the like.

The resistance value was measured using a "digital multimeter CDM-11D" manufactured by CUSTOM. The measurement sample (conductive polymer film) had a film thickness of 3 to 5 μm, a width of 1.5 mm, and a length of 8 mm.

As shown in Tables 2 and 3, a comparison between Examples 5-6 and 5-7, a comparison between Examples 5-8 and 5-9, Examples 6-5 and 6- From the comparison with 6 and the comparison between Examples 6-7 and 6-8, by introducing the anchor-containing monomer unit into the conductive polymer, the conductive polymer has higher adhesion to the substrate S. It was found that the film was formed in. This result can be said to support that the conductive polymer is covalently bonded to the substrate S to form a film.

As shown in FIG. 2, a functional group (acid anhydride moiety) capable of forming a covalent bond in the anchor-containing monomer unit of the first polymer compound and a functional group (hydroxyl group or amino group) on the surface of the substrate S. ) And react to form a covalent bond. In the covalent bond state as shown in FIG. 2, the acid anhydride moiety in the anchor-containing monomer unit is ring-opened and changed to a carboxy group and an ester (or amide).

Claims (12)

It is formed of a conductive polymer containing a first polymer compound and a second polymer compound as constituent components, and the conductive polymer has polymer chains hosting host groups and guest groups. Form guest interactions,
The host group is a group obtained by removing one hydrogen atom or a hydroxyl group from α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin.
The guest group is one group selected from the group consisting of a linear hydrocarbon group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, a heteroaryl group and an organic metal complex.
The conductive polymer has a monomer unit having a styrene sulfonic acid skeleton, a monomer unit having a thiophene skeleton, a monomer unit having an aniline skeleton, a monomer unit having a phenylene vinylene skeleton, and an acetylene skeleton. A self-healing conductive material containing at least one monomeric unit selected from the group consisting of monomeric units. Wherein one of the first polymer compound and the second polymer compound has a monomer unit having the host group, without a monomer unit having an guest group, the other, the It has a monomer unit having a guest group does not have a monomer unit having the host group, self-healing conductive material according to claim 1. Wherein one of the first polymer compound and the second polymer compound, having both of the monomer units having a monomer unit and the guest group having the host group, according to claim 1 Self-healing conductive material. Both the first polymer compound and the second polymer compound has both of the monomer units having a monomer unit and the guest group having the host group, self as claimed in claim 1 Restorative conductive material. The self-healing conductive material according to any one of claims 1 to 3 , which is formed in a film shape. It has one or both of a monomer unit having a host group and a monomer unit having a guest group, and a monomer unit having a thiophene skeleton.
The monomer unit having the host group has the following formula (H1).

(In formula (H1), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
And the following formula (H2)

(In the formula (H2), CD is synonymous with the CD of the formula (H1))
It is at least one monomer unit selected from the group consisting of
The monomer unit having a guest group is represented by the following formula (G1).

(In equation (G1), ^RG indicates a guest group)
And the following formula (G2)

(In equation (G2), ^RG indicates a guest group)
It is at least one monomer unit selected from the group consisting of
The monomer unit having the thiophene skeleton has the following formula (C1).

In Ri monomer units der represented,
The guest group is a straight chain hydrocarbon group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, Ru one group Der selected from the group consisting of heteroaryl groups and organometallic complexes, conductive polymer Compound. The following formula (h1)

(In formula (h1), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
A polymerizable monomer represented by. The following formula (h2)

(In formula (h2), CD represents a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin, and cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin).
A polymerizable monomer represented by. The following formula (g1)

(In formula (g1), ^RG indicates a guest group)
In expressed,
The guest group is a straight chain hydrocarbon group having 1 to 30 carbon atoms (excluding C ₁₈ H _37), a cycloalkyl group, an aryl group, one selected from the group consisting of heteroaryl groups and organometallic complexes groups der of Ru, a polymerizable monomer. The following formula (g2)

(In formula (g2), ^RG indicates a guest group)
In expressed,
The guest group is a straight chain hydrocarbon group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, Ru one group Der selected from the group consisting of heteroaryl groups and organometallic complexes, polymerizable monomer body. The self-healing conductive material according to any one of claims 1 to 4 , which is covalently bonded to the substrate and formed on the substrate. At least one of the first polymer compound and the second polymer compound contains a monomer unit having a functional group capable of forming the covalent bond with the substrate, and the covalent bond can be formed. The self-healing conductive material according to claim 11 , wherein the functional group and the functional group on the surface of the substrate form a covalent bond.

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