Composition for molding conductive article

Abstract

The present invention provides a composition for molding a conductive article having high conductivity. Provided is a composition for molding a conductive article, the composition containing a polythiophene compound represented by general formula (A), ammonia, and an amine compound. Also provided is a method for molding a conductive article using said composition. In general formula (A), L is an alkylene or the like. Each of M1 and M2 independently represents an alkyl group or a hydrogen atom. R1A is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or a group represented by formula (15). L1, M1c and M2c are the same as L, M1 and M2, respectively.

Description

Composition for molding conductive articles

[0001] The present invention relates to a composition for molding an electrically conductive article using a polythiophene compound, and a method for producing the electrically conductive article.

[0002] As a polythiophene resin having electrical conductivity, a polythiophene compound having a phosphorus-based structural unit is disclosed in Patent Document 1. However, in fields where various electrically conductive articles are used, even higher electrical conductivity is sometimes preferred, and the development of a material having even higher electrical conductivity has been desired.

[0003] International Publication No. WO2022 / 260007

[0004] An object of the present invention is to provide a composition for molding a conductive article having high electrical conductivity and a method for producing the conductive article.

[0005] As a result of extensive research, the present inventors have found that the above object can be achieved by using a composition containing a specific base when molding a polythiophene compound, and have thus completed the present invention.

[0006] That is, the present invention provides the following compositions, etc.

[0007] (Item 1) A composition used for molding a conductive article, comprising a polythiophene compound, an amine compound, and ammonia, wherein the polythiophene compound is represented by the following general formula (A): wherein L is a structural unit represented by formula (21): where R ５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and n １ is 0 or 1, and n ２ are independently integers from 1 to 6, and n ３ is independently 0 or 1, and n ４is an integer of 0 to 12, and the left end of formula (21) is bonded to a carbon atom in the dioxane ring in formula (A); １ and M ２ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, １Ａ is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or a group represented by formula (15), Here, L １ is expressed by the formula (22): where R １５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R １６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and m １ is 0 or 1, and m ２ are independently integers from 1 to 6, and m ３ are independently 0 or 1, and m ４ is an integer of 0 to 12, and the left end of formula (22) is bonded to a carbon atom in the dioxane ring in formula (A); １ｃ and M ２ｃ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, the amine compound is composed of a nitrogen atom, a carbon atom, and a hydrogen atom, and the conductive article is not a member used in a capacitor.

[0008] (Item 2) The composition according to item 1, further comprising a solvent.

[0009] (Item 3) The composition according to item 1 or 2 (in one embodiment, the composition according to item 1) above, wherein the amine compound has a linear or branched alkyl group having 1 to 4 carbon atoms.

[0010] (Item 4) The composition according to any one of Items 1 to 3 (in one embodiment, the composition according to Item 1) above, wherein the amine compound has 1 to 3 nitrogen atoms.

[0011] (Item 5) The composition according to any one of Items 1 to 4 (in one embodiment, the composition according to Item 1) above, wherein the amine compound is selected from monoalkylamines, dialkylamines, and trialkylamines, and the alkyl group in the amine compound is a linear or branched alkyl group having 1 to 4 carbon atoms.

[0012] (Item 6) The composition according to any one of items 1 to 5 (in one embodiment, the composition according to item 1) above, wherein the amine compound is selected from monomethylamine, dimethylamine, and trimethylamine.

[0013] (Item 7) The composition according to any one of Items 1 to 6 (in one embodiment, the composition according to Item 1), wherein the molar ratio of the amine compound is 1 mol % to 99 mol % of the total amount of the amine compound and ammonia contained in the composition.

[0014] (Item 8) The composition according to item 2, wherein the solvent is water.

[0015] (Item 9) R in the polythiophene compound １Ａ 9. The composition according to any one of items 1 to 8 (in one embodiment, the composition according to item 1), wherein is hydrogen.

[0016] (Item 10) M in the polythiophene compound １ and M ２ The composition according to any one of items 1 to 9 (in one embodiment, the composition according to item 9), wherein is hydrogen.

[0017] (Item 11) n in the polythiophene compound １ is 0, and n ２ is 1, and n ３ is 0, and n ４ The composition according to any one of items 1 to 10 (in one embodiment, the composition according to item 9) above, wherein

[0018] (Item 12) A conductive article formed using the composition according to any one of items 1 to 11 above, which is not used as a component of a capacitor.

[0019] (Item 13) A conductive article formed using the composition according to any one of items 1 to 11, the conductive article being in the form of a film, provided that the conductive article is not used as a component of a capacitor.

[0020] (Item 14) A method for producing a conductive article, comprising the steps of preparing the composition according to any one of items 1 to 11 above and molding the composition to obtain a conductive article, with the proviso that the conductive article is not a component used in a capacitor.

[0021] (Item 15) The method according to item 14, further comprising a step of polymerizing a monomer corresponding to the polythiophene compound contained in the composition to obtain the polythiophene compound, wherein the step of obtaining the polythiophene compound is carried out before the step of preparing the composition.

[0022] By molding a polythiophene compound using the composition of the present invention, a conductive article having high conductivity can be obtained.

[0023] The present invention will be described in detail below.

[0024] The composition of the present invention contains a polythiophene compound, an amine compound, and ammonia, and further contains a solvent as needed.

[0025] As the polythiophene compound, for example, the polythiophene compound described in Patent Document 1 can be used.

[0026] [Polythiophene Compound] The polythiophene compound is represented by, for example, general formula (12): -(A) ｑ - (12) where each A is independently a thiophene monomer residue. q is the degree of polymerization and is an arbitrary positive integer. Specifically, it can be, for example, 3 or more, 6 or more, or 10 or more, and can be 2,000 or less, 1,000 or less, 800 or less, or 400 or less.

[0027] When the structure of a polythiophene compound is described as a general formula, both terminals are generally omitted, and therefore, in this specification, both terminals are also omitted as a general rule when describing the structure of a polythiophene compound. However, for example, if both terminal groups are intentionally written in the above general formula (12), the following general formula (12A) is obtained.

[0028] E １ -(A) ｑ -E ２ (12A) where E １ and E ２ are terminal groups. Usually, one is a polymerization initiation terminal and the other is a polymerization termination terminal.

[0029] The polythiophene compound is preferably a homopolymer. However, if desired, the polythiophene compound may be a copolymer. The copolymer may be a block copolymer or a random copolymer.

[0030] In this specification, a unit constituting the repeating structure of a polymer is referred to as a structural unit. That is, in the polymer of the above general formula (12A), "A" is a structural unit, and the polymer is composed of the structural unit and the terminal group. In other words, the portion of the polymer other than the polymerization initiation end and polymerization termination end is composed of the structural unit. Therefore, in this specification, the statement "the polythiophene compound does not contain any structural unit other than the general formula (A)" means that the portion other than the terminal group is composed only of the structural unit of the general formula (A). The polythiophene compound in the present invention contains a structural unit represented by the following general formula (A):

[0031]

[0032] In the general formula (A), L is a group represented by the formula (21): It is expressed as:

[0033] Here, R ５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0034] n １ is 0 or 1, preferably 0. ２ are independently an integer of 1 to 6, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. ３ is independently 0 or 1, preferably 0. ３ If is 0, then n ４ is preferably 1 or 2, and n ４ It is more preferable that n is 1. ４ is an integer of 0 to 12, preferably 0 to 6, more preferably 1 or 2, and even more preferably 1. ２ and ４ The product of these is the total number of carbon atoms between the dioxane ring and the phosphorus. (Number of carbon atoms between the dioxane ring and the phosphorus) = n ２ ×n ４ The number of carbon atoms between the dioxane ring and the phosphorus is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, particularly preferably 1 to 3, and in one embodiment, 1 or 2.

[0035] The left end of formula (21) is bonded to the carbon atom in the dioxane ring in formula (A), and the right end of formula (21) is bonded to the phosphorus atom in formula (A).

[0036] In one embodiment, R ５ and R ６ is a hydrogen atom, and n １ is 0, and n ３ is 0, and n ４ is 1. That is, in this embodiment, L is -(CH ２ ) ｎ２ -, where n ２ are independently 0 to 12. ２is preferably 0 to 4, more preferably 0 to 2. It is particularly preferably 1.

[0037] M １ and M ２ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom. １ and M ２ At least one of M is a hydrogen atom, and more preferably １ and M ２ are both hydrogen atoms.

[0038] In general formula (A), R １Ａ is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or a group represented by formula (15), preferably an alkyl group or a hydrogen atom, more preferably a hydrogen atom. Here, L １ is expressed by the formula (22): It is expressed as:

[0039] Here, R １５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0040] R １６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0041] m １ is 0 or 1, preferably 0.

[0042] m ２ are independently an integer of 1 to 6, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0043] m ３ is independently 0 or 1, preferably 0. ３ If is 0, then m ４ is preferably 1 or 2, and m４ It is more preferable that the value of .times. ...

[0044] m ４ is an integer of 0 to 12, preferably 0 to 6, more preferably 1 or 2, and even more preferably 1.

[0045] m ２ and m ４ The product of these is the total number of carbon atoms between the dioxane ring and the phosphorus. (Number of carbon atoms between the dioxane ring and the phosphorus) = m ２ ×m ４

[0046] The number of carbon atoms between the dioxane ring and the phosphorus is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, particularly preferably 1 to 3, and in one embodiment, 1 or 2.

[0047] In addition, the number of carbon atoms between the dioxane ring and phosphorus in L and L １ The total number of carbon atoms between the dioxane ring and the phosphorus in the formula (I) is preferably 1 to 16, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 4, and in one embodiment, 1 or 2.

[0048] The left end of formula (22) is bonded to the carbon atom in the dioxane ring in formula (A), and the right end of formula (22) is bonded to the phosphorus atom in formula (15).

[0049] In one embodiment, R 1５ and R 1６ is a hydrogen atom, and m １ is 0, and m ３ is 0, and m ４ is 1. That is, in this embodiment, L １ is -(CH ２ ) ｍ２ -, where m ２ are independently 0 to 12. １ｃ and M ２ｃ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom.

[0050] In this specification, the phosphoric acid or phosphonic acid moiety refers to a moiety having a structure of a phosphoric acid group or a derivative thereof (e.g., a salt or an ester), or a phosphonic acid group or a derivative thereof (e.g., a salt or an ester). For example, a phosphoric acid group or a phosphonic acid group may be provided with M of the general formula (A): １ and M ２ or a phosphate group or a phosphonate group, １ｃ and M ２ｃ The site to which is bound is also referred to herein as a phosphate or phosphonate site.

[0051] In general formula (A), R １Ａ The alkyl groups in the formula (I) may each independently be linear, branched, or cyclic. A cyclic alkyl group may consist solely of a cyclic structure, or may have a structure in which a linear alkyl group is further bonded to a cyclic structure. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.

[0052] R １Ａ The alkoxy groups in the formula (I) may each independently be linear, branched, or cyclic. The cyclic alkoxy group may consist solely of a cyclic structure, or may have a structure in which a chain alkyl group and / or a chain alkoxy group is further bonded to the cyclic structure. The number of carbon atoms in the alkoxy group is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, and a pentadecyloxy group.

[0053] R １ＡThe acyl groups in the formula (I) may each independently be linear, branched, or cyclic. The cyclic acyl group may consist of only a cyclic structure, or may have a structure in which a chain alkyl group and / or a chain acyl group is further bonded to the cyclic structure. The number of carbon atoms in the acyl is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, and a pentadecanoyl group.

[0054] In one preferred embodiment, R １Ａ is a hydrogen atom.

[0055] M １ and M ２ may be the same or different from each other. In one preferred embodiment, M １ and M ２ are the same. １ｃ and M ２ｃ may be the same or different from each other. In one preferred embodiment, M １ｃ and M ２ｃ are identical.

[0056] In the above general formula (A), M １ and M ２ and M １ｃ and M ２ｃ The alkyl group in may be either linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. In a more preferred embodiment, the alkyl group has 2 carbon atoms. When the number of carbon atoms in the alkyl group is within the preferred range, a polythiophene compound with good conductivity can be obtained. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl groups.

[0057] In the above general formula (A), M １ and M ２ may all be alkyl groups, but from the viewpoint of electrical conductivity, it is preferable that at least one of them is a hydrogen atom, and it is more preferable that two of them are hydrogen atoms. １ｃ and M ２ｃ may all be alkyl groups, but from the viewpoint of electrical conductivity, it is preferable that at least one of them is a hydrogen atom, and it is more preferable that two of them are hydrogen atoms.

[0058] Specific examples of the structural unit of the general formula (A) include the following formulae (9), (10), (11) and (13).

[0059] In one embodiment, the structural units of the polythiophene compound used in the composition of the present invention may be composed solely of structural units of the general formula (A). In one embodiment, the polythiophene compound used in the composition of the present invention is substantially free of structural units other than structural units of the general formula (A). When the structural units of the polymer are composed solely of structural units of the general formula (A), the advantageous properties can be fully exhibited.

[0060] In another embodiment, the polythiophene compound used in the composition of the present invention may contain structural units other than the structural unit of general formula (A) above, as long as the effects of the present invention are not impaired.

[0061] However, if the content of structural units other than those of general formula (A) is too high, the advantages of the present invention will be impaired, so it is preferable that the content of structural units other than those of general formula (A) is not too high. The content of structural units other than those of general formula (A) is preferably 40 mol% or less of the total structural units in the polythiophene compound, more preferably 30 mol% or less, even more preferably 20 mol% or less, still more preferably 10 mol% or less, particularly preferably 5 mol% or less, particularly preferably 3 mol% or less, and most preferably 1 mol% or less. Furthermore, it can be 0.1 mol% or less, and it can also be 0.01 mol% or less.

[0062] A self-doping conductive polythiophene compound must have a hydrogen ion-donating phosphoric or phosphonic acid moiety. A hydrogen ion-donating phosphoric or phosphonic acid moiety refers to a phosphoric or phosphonic acid moiety having at least one —P—OH group. The number of phosphorus-containing thiophene monomer residues containing a hydrogen ion-donating phosphoric or phosphonic acid moiety in the polythiophene compound used in the composition of the present invention can be selected as desired. The proportion of phosphorus-containing thiophene monomer residues containing a hydrogen ion-donating phosphoric or phosphonic acid moiety can be selected from, for example, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more, based on the total number of phosphorus-containing thiophene monomer residues present in the polythiophene compound (100%). Alternatively, it may be set to 100%. Furthermore, if it is desired to control the content of hydrogen ion donating groups (—P—OH) for some reason, the composition can be designed to suppress the number of hydrogen ion donating phosphoric acid or phosphonic acid moieties. In such cases, the proportion of phosphorus-containing thiophene monomer residues containing hydrogen ion donating phosphoric acid or phosphonic acid moieties can be designed to be 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, or 70% or less, where the total number of phosphorus-containing thiophene monomer residues present in the polythiophene compound used in the composition of the present invention is taken as 100%.

[0063] The ratio of hydrogen ion donating phosphoric or phosphonic acid moieties to the total number of phosphoric or phosphonic acid moieties can also be designed as desired. The ratio of hydrogen ion donating phosphoric or phosphonic acid moieties can be selected from, for example, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more, assuming that the total number of phosphoric or phosphonic acid moieties present in the polythiophene compound used in the composition of the present invention is 100%. Alternatively, it may be set to 100%. Furthermore, if it is desired to control the content of hydrogen ion donating groups for some reason, the number of hydrogen ion donating phosphoric or phosphonic acid moieties can also be designed to be suppressed. In such cases, the proportion of hydrogen ion-donating phosphoric or phosphonic acid sites can be designed to be 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, or 70% or less, where the total number of phosphoric or phosphonic acid sites present in the polythiophene compound used in the composition of the present invention is taken as 100%.

[0064] The ratio of the above-mentioned hydrogen ion donating phosphoric or phosphonic acid moieties can be controlled, for example, by adjusting the type and amount of the thiophene compound used in producing the polythiophene compound.

[0065] The polythiophene compound used in the composition of the present invention can be produced by the method described below.

[0066] (Molecular Weight) The molecular weight of the polythiophene compound used in the composition of the present invention is not particularly limited. The weight-average molecular weight of the polythiophene compound used in the composition of the present invention is preferably 1,000 or more, more preferably 2,000 or more. The weight-average molecular weight of the polythiophene compound used in the composition of the present invention is preferably 500,000 or less, more preferably 200,000 or less, and even more preferably 100,000 or less.

[0067] The polythiophene compound used in the composition of the present invention preferably has a phosphoric acid or phosphonic acid moiety [—OP(O)(OH) ２or -P(O)(OH) ２ ], and monomer residues having a phosphoric acid or phosphonic acid monoalkyl ester structural moiety [—OP(O)(OH)(OR) or —P(O)(OH)(OR), where R is an alkyl group having 1 to 15 carbon atoms]. The phosphoric acid or phosphonic acid structural moiety and the phosphoric acid or phosphonic acid monoalkyl ester structural moiety are capable of doping the thiophene rings in the main chain of the polythiophene compound with hydrogen ions released from the hydrogen ion donating group (—P—OH).

[0068] In one embodiment of the present invention, a polythiophene compound having a specific absorbance ratio can be used. High conductivity can be achieved by a polythiophene compound having a specific absorbance ratio. Specifically, in the polythiophene compound used in the composition of the present invention, the absorbance (A) of the compound at a wavelength of 2000 nm measured using a spectrophotometer is ２０００ ) and the absorbance (A ４０７ ) from the calculation formula (A ２０００ / A ４０７ ) is 1 or more. The absorbance ratio is preferably 1.5 or more, more preferably 2 or more, even more preferably 2.5 or more, and particularly preferably 3 or more. If necessary, the absorbance ratio may be 3.5 or more, 4 or more, or even 4.5 or more. There is no particular upper limit to the absorbance ratio. However, if necessary, the upper limit of the absorbance ratio may be set to, for example, 10 or less, 8 or less, or 6 or less. The method described in Patent Document 1 can be used as a method for measuring absorbance.

[0069] [Thiophene Compound] A phosphorus-containing thiophene compound is used as a monomer for producing the polythiophene compound used in the composition of the present invention.

[0070] [Phosphorus-containing thiophene compound] The phosphorus-containing thiophene compound is a compound represented by the following general formula (Am).

[0071]

[0072] In the general formula (Am), L represents a group represented by formula (21): where R ５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and n １ is 0 or 1, and n ２ are independently integers from 1 to 6, and n ３ is independently 0 or 1, and n ４ is an integer of 0 to 12, and the left end of formula (21) is bonded to a carbon atom in the dioxane ring in formula (Am).

[0073] In one embodiment, L is —(CH ２ ) ｎ -, where n is 0 to 12. M １ and M ２ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom.

[0074] R １Ａ is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or a group represented by formula (15).

[0075] L １ is expressed by the formula (22): where R １５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R １６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and m １ is 0 or 1, and m ２ are independently integers from 1 to 6, and m ３ are independently 0 or 1, and m ４ is an integer of 0 to 12, and the left end of formula (22) is bonded to a carbon atom in the dioxane ring in formula (Am).

[0076] Here, M １ｃ and M ２ｃare each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom.

[0077] The above M １ and M ２ and M １ｃ and M ２ｃ The alkyl group in may be either a linear alkyl group or a branched alkyl group. It preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. It most preferably has 2 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl groups. Within the above range, the oxidative polymerization reaction proceeds smoothly, which may make it easier to obtain the polythiophene compound used in the composition of the present invention.

[0078] In one embodiment, M １ and M ２ is a hydrogen atom. １ and M ２ When is a hydrogen atom, there is an advantage that a polythiophene compound containing a diacid form can be easily produced. In general, diacid forms of polythiophenes have better electrical conductivity than dialkyl forms and monoacid forms, so it is advantageous that a polythiophene compound containing a diacid form can be easily produced.

[0079] In one embodiment, M １ｃ and M ２ｃ is a hydrogen atom. １ｃ and M ２ｃ When is a hydrogen atom, there is an advantage that the polythiophene compound containing the diacid form can be easily produced.

[0080] M １ and M ２ may be the same or different from each other. In one preferred embodiment, M １ and M ２ are the same. １ｃ and M２ｃ may be the same or different from each other. In one preferred embodiment, M １ｃ and M ２ｃ are identical.

[0081] M １ and M ２ When both are alkyl, a polythiophene compound having good electrical conductivity may be obtained by oxidatively polymerizing a monomer mixture containing the thiophene compound and hydrolyzing the resulting compound.

[0082] Similarly, M １ｃ and M ２ｃ When both of them are alkyl, a polythiophene compound having good electrical conductivity may be obtained by oxidatively polymerizing a monomer mixture containing the thiophene compound and hydrolyzing the resulting compound.

[0083] R １Ａ The alkyl group in may be linear, branched, or cyclic. A cyclic alkyl group may consist of only a cyclic structure, or may have a structure in which a linear alkyl group is further bonded to the cyclic structure. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.

[0084] R １ＡThe alkoxy group in may be linear, branched, or cyclic. The cyclic alkoxy group may consist of only a cyclic structure, or may have a structure in which a chain alkyl group and / or a chain alkoxy group is further bonded to the cyclic structure. The number of carbon atoms in the alkoxy group is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, and a pentadecyloxy group.

[0085] R １Ａ The acyl group in may be linear, branched, or cyclic. A cyclic acyl group may consist of only a cyclic structure, or may have a structure in which a chain alkyl group and / or a chain acyl group is further bonded to the cyclic structure. The number of carbon atoms in the acyl is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, and a pentadecanoyl group.

[0086] In one preferred embodiment, R １Ａ is an alkyl group or a hydrogen atom, more preferably a hydrogen atom.

[0087] Specific examples of the general formula (Am) include the following formulae (5), (9B), (10B) and (11C).

[0088] [Method of producing phosphorus-containing thiophene compound] The phosphorus-containing thiophene compound used in the present invention is a compound represented by the formula R １ＡWhen is a hydrogen atom, it can be produced, for example, by the following method: In particular, in consideration of yield and operability, it is preferable to produce it by the following first and second steps.

[0089] (First Step) In the first step, a compound represented by the following general formula (3) is obtained by a known method.

[0090]

[0091] In formula (3), L is represented by formula (21): where R ５ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and n １ is 0 or 1, and n ２ are independently integers from 1 to 6, and n ３ is independently 0 or 1, and n ４ is an integer of 0 to 12, and the left end of formula (21) is bonded to the carbon atom of the dioxane ring in formula (3).

[0092] In one embodiment, L is —(CH ２ ) ｎ Here, n is 0 to 12. n is preferably 0 to 4, more preferably 0 to 2, and particularly preferably 1. X １ is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of availability of raw materials and operability, a chlorine atom or a bromine atom is preferred.

[0093] Specifically, for example, in the method described in JP-A-2014-74007, in the above formula (3), L is -(CH ２ ) ｎ - can be obtained.

[0094] In addition, in the embodiment where n=1, that is, the compound represented by the following general formula (3A), it can be obtained by a method of heating 3-halogenated-1,2-propanediol and 3,4-dimethoxythiophene in the presence of an acidic catalyst.

[0095]

[0096] Examples of the acid catalyst include sulfuric acid, paratoluenesulfonic acid monohydrate, and methanesulfonic acid, with paratoluenesulfonic acid monohydrate being preferred.

[0097] In the above formula (3), L is -(CH ２ ) ｎ Compounds other than - can also be obtained by the same method as above.

[0098] (Reaction Temperature) The heating is carried out to promote the reaction, and there is no particular limitation on the heating temperature as long as the reaction proceeds at an appropriate rate, but the heating temperature is preferably 60° C. or higher, more preferably 70° C. or higher, and particularly preferably 80° C. or higher. The heating temperature is preferably 200° C. or lower, more preferably 150° C. or lower, and particularly preferably 120° C. or lower.

[0099] (Reaction time) The heating time is not particularly limited, but a time sufficient for the starting materials to react under each condition should be appropriately selected. As long as the reaction proceeds sufficiently, differences in reaction time do not significantly affect the effects of the present invention. For example, 1 hour or more is preferred, and 3 hours or more is more preferred. 2 days or less is preferred, and 1 day (24 hours) or less is more preferred.

[0100] (Solvent) In the first step, a solvent may be used, if necessary. The solvent is not particularly limited as long as it is non-reactive in the oxidative polymerization reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; aliphatic hydrocarbons such as n-hexane, cyclohexane, n-octane, and n-decane; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, and o-dichlorobenzene; and ethers such as tetrahydrofuran, diethyl ether, t-butyl methyl ether, dimethoxyethane, dioxane, and diethylene glycol dimethyl ether. Xylene, toluene, and diethylene glycol dimethyl ether are preferred, and xylene and toluene are more preferred.

[0101] (Purification) The product obtained in the first step may be used in the second step without post-treatment such as purification. If necessary, the product obtained in the first step may be purified by a known method and the resulting purified product may be used in the second step.

[0102] (Second Step) In the second step, the compound represented by the general formula (3) is reacted with a tris(trialkylsilyl)phosphite or a trialkylphosphite to form a compound represented by the general formula (3) containing X １ is substituted with a bis(trialkylsilyl) phosphonate moiety or a diester phosphonate moiety. When synthesizing a thiophene containing a phosphonic acid moiety, i.e., a diacid, a method using a tris(trialkylsilyl)phosphite is preferred in terms of reaction efficiency, etc.

[0103] Tris(trialkylsilyl)phosphites are represented by the following general formula (11A): Here, M ３ａ , M ４ａ and M ５ａ are each independently trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, or triisopropylsilyl, preferably trimethylsilyl or triethylsilyl, and more preferably trimethylsilyl. ３ａ , M４ａ and M ５ａ may be independently selected, but are preferably the same. Specific examples include tris(trimethylsilyl)phosphite and tris(triethylsilyl)phosphite.

[0104] For example, by heating a mixture of the compound represented by the above general formula (3) and tris(trialkylsilyl)phosphite, a Michaelis-Arbuzov rearrangement reaction occurs, and a compound represented by the general formula (2A) is obtained as the rearrangement product. In the formula, M ３ａ and M ４ａ are each independently trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, or triisopropylsilyl. These are generally used as protecting groups for hydroxyl groups, and can be deprotected by a known method to obtain a compound of the following general formula (2C).

[0105] For example, deprotection occurs by allowing a basic aqueous solution such as an aqueous solution of sodium carbonate, potassium carbonate, or ammonia to act on the compound of the above general formula (2A). The compound of the general formula (2C) can also be obtained by hydrolyzing the compound of the general formula (2B) described below by a known method, but can be obtained relatively easily by the method using the tris(trialkylsilyl)phosphite.

[0106] The trialkyl phosphite is represented by the following general formula (11B).

[0107]

[0108] Here, M ３ｂ , M ４ｂ and M ５ｂ are each independently an alkyl group having 1 to 15 carbon atoms. Preferably, the number of carbon atoms is 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 5. In a more preferred embodiment, the alkyl group has 2 carbon atoms. M ３ｂ and M ４ｂ respectively represent M in general formula (Am). １ and M ２In the compound of general formula (Am), the desired M １ and M ２ Depending on M ３ｂ and M ４ｂ is selected. ３ｂ and M ４ｂ may be the same or different. ５ｂ is the desired M in the compound of general formula (Am). １ and M ２ may be independently selected from M ５ｂ M ３ｂ or M ４ｂ In one preferred embodiment, M ３ｂ , M ４ｂ and M ５ｂ are the same. Specific examples include trimethyl phosphite and triethyl phosphite.

[0109] For example, by heating a mixture of the compound represented by the above general formula (3) and a trialkyl phosphite, a Michaelis-Arbuzov rearrangement reaction occurs, and a compound represented by the general formula (2B) is obtained as the rearrangement product.

[0110]

[0111] In the formula, M ３ｂ and M ４ｂ are each independently alkyl having 1 to 15 carbon atoms.

[0112] The mixing ratio (molar ratio) of the compound represented by general formula (3) and the trialkyl phosphite or tris(trialkylsilyl) phosphite is not particularly limited. However, from the viewpoint of yield and the like, the mixing ratio (molar ratio) of the compound represented by general formula (3) and the trialkyl phosphite or tris(trialkylsilyl) phosphite is preferably 0.8 moles or more, and more preferably 1 mole or more, of trialkyl phosphite per mole of the compound represented by general formula (3). Furthermore, the mixing ratio of trialkyl phosphite or tris(trialkylsilyl) phosphite per mole of the compound represented by general formula (3) is preferably 10 moles or less, more preferably 5 moles or less, and particularly preferably 3 moles or less.

[0113] (Reaction temperature) The heating is carried out to promote the reaction, and there is no particular limitation on the temperature during the reaction as long as the reaction proceeds at an appropriate rate, but the temperature is preferably 100° C. or higher, more preferably 110° C. or higher, and particularly preferably 120° C. or higher. The temperature is also preferably 220° C. or lower, more preferably 200° C. or lower, and particularly preferably 160° C. or lower.

[0114] (Reaction Time) There is no particular limitation on the heating time. A time sufficient for the reaction materials to react under the conditions such as temperature may be appropriately selected. As long as the reaction proceeds sufficiently, differences in reaction time do not significantly affect the effects of the present invention. The reaction time is preferably 6 hours or more, more preferably 12 hours or more. The reaction time is also preferably 3 days or less, more preferably 2 days or less.

[0115] (Solvent) In the second step, a solvent may be used if necessary. There are no particular limitations on the solvent, as long as it is a liquid that is non-reactive in the second step and can dissolve or disperse the reaction materials. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; aliphatic hydrocarbons such as n-hexane, cyclohexane, n-octane, and n-decane; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, and o-dichlorobenzene; and ethers such as tetrahydrofuran, diethyl ether, t-butyl methyl ether, dimethoxyethane, dioxane, and diethylene glycol dimethyl ether. Preferred solvents are toluene, xylene, and diethylene glycol dimethyl ether, and more preferably xylene and toluene.

[0116] (Hydrolysis) The compound of general formula (2B) obtained by the above reaction may be subjected to hydrolysis or ion exchange, if necessary.

[0117] For example, the compound of general formula (2B) obtained by the above reaction may be subjected to hydrolysis as needed. After the compound of general formula (2B) is subjected to hydrolysis, ion exchange may be further performed. By subjecting the compound of general formula (2B) to hydrolysis, M in general formula (2B) may be obtained. ３ｂ and M ４ｂ Further, by carrying out ion exchange, it is possible to obtain a compound in which M is a hydrogen atom or an alkali metal. ３ｂ and M ４ｂ can be converted to the desired type.

[0118] As the hydrolysis method, various known methods can be used, and the methods and conditions described below for the hydrolysis of polythiophene compounds can also be used.

[0119] As the ion exchange method, various known methods can be used, and the methods and conditions described below for ion exchange of phosphorus-containing thiophene copolymers can also be used.

[0120] (Purification) The product obtained in the second step may be used in the polymerization step as a phosphorus-containing thiophene compound without post-treatment such as purification, or may be subjected to post-treatment such as purification by a known method.

[0121] (R １Ａ is other than a hydrogen atom) The phosphorus-containing thiophene compound is １Ａ When is other than a hydrogen atom, the compound can be produced by a method basically similar to the above method.

[0122] R １Ａ When is a group of formula (15), the phosphorus-containing thiophene compound can be produced, for example, by the following method.

[0123] (First Step) In the first step, a diol of general formula (17A) is reacted with a 3,4-dialkoxythiophene of general formula (18) to obtain an intermediate of general formula (19A) according to the following reaction. Here, R ３ and R ４ is an alkyl group (e.g., a methyl group).

[0124] For example, L and L １ Ga-(CH ２ )-, 1,4-dihalogenated-2,3-butanediol is used as the compound of formula (17A) instead of the 3-halogenated-1,2-propanediol.

[0125] L and L in formula (19A) １ Ga-(CH ２ Compounds other than )- can also be obtained by the same method as above.

[0126] (Step 2) The intermediate of general formula (19A) obtained in Step 1 is reacted with a compound of general formula (11A) by the above-mentioned method, followed by deprotection, or the intermediate of general formula (19A) is reacted with a compound of general formula (11B) by the above-mentioned method, to obtain a phosphorus-containing thiophene compound of general formula (Am). Here, R １Ａ is a group represented by the following general formula (15). The mixing ratio of the intermediate to the phosphite is preferably 1.6 moles or more, more preferably 2 moles or more, of phosphite per mole of intermediate, and is preferably 20 moles or less, more preferably 10 moles or less, and particularly preferably 6 moles or less, of phosphite per mole of intermediate.

[0127] R １Ａ When is a hydrogen atom, an alkyl group, an alkoxy group, or an acyl group, the phosphorus-containing thiophene compound can be produced, for example, by the following method.

[0128] (First Step) In the first step, a diol of general formula (17B) is reacted with a 3,4-dialkoxythiophene of general formula (18) according to the following reaction to obtain an intermediate of general formula (19B).

[0129] (Second Step) The intermediate of general formula (19B) obtained in the first step is reacted with a compound of general formula (11A) by the above-mentioned method, followed by deprotection, or the intermediate of general formula (19B) is reacted with a compound of general formula (11B) by the above-mentioned method, to obtain a phosphorus-containing thiophene compound of general formula (Am). Here, R １Ａ is a hydrogen atom, an alkyl group, an alkoxy group, or an acyl group.

[0130] [Method for producing polythiophene compound] The polythiophene compound used in the composition of the present invention can be obtained by oxidatively polymerizing the above-mentioned phosphorus-containing thiophene compound using an appropriate oxidizing agent, followed by an appropriate purification step. As the oxidative polymerization method, any conventionally known method for polymerizing thiophene compounds can be used. In consideration of the yield and operability, it is preferable to produce the compound under the conditions described below.

[0131] In this specification, "oxidative polymerization" refers to a reaction in which a thiophene monomer compound or a thiophene monomer mixture is polymerized using an oxidizing agent to synthesize a polythiophene compound. Here, "oxidation" refers to the abstraction of hydrogen atoms at the 2- and 5-positions from a thiophene monomer compound during this polymerization reaction. In this specification, "oxidizing agent" refers to a reagent that triggers such an oxidation reaction. The oxidative polymerization reaction of thiophene monomers is described, for example, in Patent Document 1. Regarding the term "oxidative polymerization," the Chemical Dictionary defines it as "a process in which a compound having a hydrocarbon residue containing a double bond gradually polymerizes upon exposure to oxygen. The most prominent example is the drying of oils and fats." However, because the polymerization of thiophene monomers does not generally use oxygen in the air as an oxidizing agent, the term "oxidative polymerization" in this specification has a slightly different meaning from that used in the Chemical Dictionary.

[0132] (Monomer) A polythiophene compound containing a structural unit of the general formula (A) can be obtained by carrying out oxidative polymerization using the phosphorus-containing thiophene compound of the general formula (Am) as a polymerization monomer.

[0133] When carrying out the oxidative polymerization, the oxidative polymerization may be carried out using only one type of thiophene compound represented by the general formula (Am), or two or more types of thiophene compounds represented by the general formula (Am).

[0134] However, if the amount of monomers other than those of general formula (Am) is too large, the advantages of the present invention will be impaired, so it is preferable that the amount of monomers other than those of general formula (Am) is not too large. The amount of monomers other than those of general formula (Am) is preferably 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, still more preferably 10 mol% or less, particularly preferably 5 mol% or less, particularly preferably 3 mol% or less, and most preferably 1 mol% or less of the total monomers used in the polymerization reaction.

[0135] (Oxidizing Agent) The oxidative polymerization reaction in the present invention is carried out in the presence of an oxidizing agent. As the oxidizing agent, an oxidizing agent generally used in the oxidative polymerization reaction of a thiophene compound can be used. Specific examples include ammonium persulfate, ferric chloride, ferric paratoluenesulfonate, ferric sulfate, and ferric nitrate.

[0136] An oxidizing agent containing an iron atom can be preferably used, more preferably ferric chloride, ferric paratoluenesulfonate, ferric sulfate, and ferric nitrate.

[0137] Two or more of the above oxidizing agents may be used in combination. When two or more oxidizing agents are used in combination, it is preferable to use an oxidizing agent containing iron atoms as one of the oxidizing agents. Specifically, a preferred combination when used in combination is a combination of ferric sulfate and ammonium persulfate.

[0138] The amount of the oxidizing agent used is not particularly limited as long as the oxidative polymerization reaction proceeds smoothly. It is preferably 1 equivalent or more, more preferably 2 equivalents or more, and particularly preferably 3 equivalents or more, relative to the monomer used in the oxidative polymerization reaction. It is also preferably 100 equivalents or less, more preferably 60 equivalents or less, and particularly preferably 20 equivalents or less.

[0139] If the amount used is within the above range, the reaction proceeds smoothly.

[0140] Since oxygen in air does not usually serve as an oxidizing agent for the polymerization of thiophene monomers, even when the polymerization reaction is carried out in the presence of air, the oxygen in air is usually not included in the amount of the oxidizing agent used in the polymerization reaction. That is, although the term "oxidative polymerization" is sometimes used to mean a polymerization reaction using oxygen present in air as an oxidizing agent, the polymerization reaction in the present invention is different from such a polymerization reaction.

[0141] (Solvent) In the polymerization reaction of the present invention, a solvent may be used, if necessary.

[0142] The solvent is not particularly limited as long as it is a liquid that can dissolve or disperse the reaction materials. Specific examples of the solvent include water, aqueous ammonia, aqueous solutions of hydrochloric acid, etc., alcohols such as methanol, ethanol, 1-propanol, and 2-propanol, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and 2-butanone, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, acetonitrile, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran. Preferred are water, aqueous ammonia, hydrochloric acid, methanol, ethanol, dimethylformamide, dimethyl sulfoxide, acetonitrile, acetone, tetrahydrofuran, and toluene, and more preferred are water, methanol, acetonitrile, dimethylformamide, and dimethyl sulfoxide.

[0143] The solvents may be used singly or in combination of two or more, preferably in the form of a mixed solvent of two or more.

[0144] (Reaction Temperature) The reaction temperature during polymerization is not particularly limited. It is preferably −20° C. or higher, more preferably −15° C. or higher, and particularly preferably −10° C. or higher. It is also preferably 80° C. or lower, more preferably 60° C. or lower, and particularly preferably 40° C. or lower.

[0145] (Reaction Time) The reaction time for polymerization in the present invention may be appropriately selected so long as it is sufficient for the reaction to proceed under the respective conditions. As long as the reaction proceeds sufficiently, differences in reaction time do not significantly affect the effects of the present invention.

[0146] The reaction time is preferably 1 hour or more, more preferably 3 hours or more, even more preferably 6 hours or more, even more preferably 9 hours or more, particularly preferably 12 hours or more, and can be set to 15 hours or more, 18 hours or more, 21 hours or more, or 24 hours or more as needed. Also, it is preferably 7 days or less, more preferably 5 days or less, even more preferably 3 days or less, even more preferably 2 days or less, particularly preferably 36 hours or less, and can be set to 30 hours or less, 28 hours or less, or 26 hours or less as needed.

[0147] (Hydrolysis) The polythiophene compound obtained by the polymerization reaction may be subjected to hydrolysis, if necessary. By performing hydrolysis, the ester bond of the phosphoric acid or phosphonic acid alkyl ester moiety in the polythiophene compound is decomposed to form a phosphoric acid or phosphonic acid structure moiety [—OP(O)(OH) ２ or -P(O)(OH) ２ ], a monoalkyl phosphate or phosphonate structure moiety [—OP(O)(OH)(OR) or —P(O)(OH)(OR), where R is an alkyl group having 1 to 15 carbon atoms], or a monohydrogen phosphate or phosphonate structure moiety [—OP(O)(OH)(OM ６ ) or -P(O)(OH)(OM ６ ), where M ６ is an alkali metal, alkaline earth metal, or ammonium group.

[0148] For example, hydrolysis can be carried out by a method such as treatment with a strong acid or a strong alkali. For example, hydrolysis can be carried out by a method such as heating in an acidic aqueous solution or an alkaline aqueous solution. Examples of strong acids include protonic acids such as hydrochloric acid and sulfuric acid, and Lewis acids such as trimethylsilyl bromide. Examples of strong alkalis include potassium hydroxide and sodium hydroxide. Here, when a Lewis acid is used, a method such as reacting with the Lewis acid and then reacting with water can be preferably used. Considering the stability of the polythiophene compound skeleton, treatment with an alkali is preferred.

[0149] When heating is performed during hydrolysis, the temperature is not particularly limited. It is preferably 30°C or higher, more preferably 50°C or higher. It is also preferably 100°C or lower, more preferably 90°C or lower.

[0150] The time for hydrolysis is not particularly limited, but is preferably 1 hour or more, more preferably 6 hours or more, and is preferably 4 days or less, more preferably 2 days or less.

[0151] The polythiophene compound obtained by hydrolysis may further be subjected to ion exchange as necessary to adjust the amount of hydrogen ion-donating phosphoric acid or phosphonic acid structural moieties.

[0152] (Purification) The polythiophene compound obtained by the polymerization reaction is subjected to an appropriate purification procedure. Any known method for purifying polythiophene compounds can be used as the purification procedure. For example, procedures such as centrifugation, filtration, dehydration, drying, washing, ultrafiltration, and dialysis can be performed. The number and type of purification procedures are not particularly limited. The purification procedure may be completed by performing one type of purification procedure only once, but two or more purification procedures may be performed as necessary. For example, the purification procedure may be performed three or more times, four or more times, or five or more times. Here, one type of purification procedure may be repeated two or more times, or multiple types of purification procedures may be combined to perform two or more purification procedures in total. There is no particular upper limit to the number of purification procedures, but it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. If the number of procedures is too large, the entire production process will require a long time, reducing production efficiency.

[0153] In a preferred embodiment of the present invention, purification is performed using a chelate compound. Purification using a chelate compound results in a resin with high conductivity. In this specification, a chelate compound refers to a compound having multiple ligands. As a purification method using a chelate compound, any method that can bring a polythiophene compound into contact with a chelate compound can be used. A method that can bring a polythiophene compound into contact with a chelate compound in a liquid is preferred. In one embodiment, a polythiophene compound can be purified by adding a solvent and a chelate compound to the polythiophene compound and stirring the mixture. A preferred solvent is water. The temperature at which purification is performed is not particularly limited. It may be room temperature or a heated temperature. A temperature at which a mixture containing a polythiophene compound and a chelate compound can remain liquid during purification is preferred.

[0154] Any conventionally known chelate compound can be used as the chelate compound. Preferably, it is a chelate compound containing a phosphorus atom and an oxygen atom. More preferably, it is a chelate compound containing a plurality (for example, two) of phosphonic acid structural moieties (-P(=O)(OH) ２) is a compound having the formula (I). For example, bisphosphonates can be used. A particularly preferred example is etidronic acid.

[0155] (Ion Exchange) The polythiophene compound obtained by the polymerization reaction may be subjected to ion exchange, if necessary, to adjust the amount of dope. The ion exchange can be carried out using an acidic aqueous solution or an ion exchange resin.

[0156] That is, when the amount of hydrogen ion donating groups of phosphoric acid or phosphonic acid, monoalkyl phosphoric acid or phosphonic acid, or monohydrogen phosphoric acid or phosphonic acid in the polythiophene compound obtained by polymerization is less than the desired amount in the entire polymer, the doping effect can be increased by ion-exchanging the metal ions or ammonium ions bonded to the phosphoric acid or phosphonic acid with hydrogen ions.

[0157] Conversely, when the amount of hydrogen ion donating groups of phosphoric acid or phosphonic acid, monoalkyl phosphoric acid or phosphonic acid, or monohydrogen phosphoric acid or phosphonic acid in the polythiophene compound obtained by polymerization is greater than the desired amount for the entire polymer, the doping effect can be reduced by ion-exchanging the hydrogen ions of the phosphoric acid or phosphonic acid, monoalkyl phosphoric acid or phosphonic acid, or monohydrogen phosphoric acid or phosphonic acid with other ions (e.g., alkali metal ions, ammonium ions, etc.).

[0158] Ion exchange can be carried out after the polymerization of the polythiophene compound. It can be carried out simultaneously with the above-mentioned purification operation, or it can be carried out before or after the purification operation. For example, when purification is carried out by filtration, if a column for filtration is filled with an ion exchange resin, ion exchange can be carried out simultaneously with purification by filtration.

[0159] As the ion exchange method, a conventionally known ion exchange method can be used.

[0160] For example, when an acidic aqueous solution is used, ion exchange can be performed by contacting the polythiophene compound product obtained by polymerization with the acidic aqueous solution. Specifically, ion exchange can be performed by, for example, stirring the polythiophene compound product in the acidic aqueous solution to react the salt portion of the phosphoric acid or phosphonic acid compound present in the polythiophene compound product with the hydrogen ions in the aqueous solution. When increasing the hydrogen ions to enhance the doping effect, it is preferable to use an excess amount of acid relative to the acidic substituents of the polythiophene compound product. The doping effect can be reduced by simply reducing the amount of acid used. In other words, the doping effect can be set as desired by changing the amount of acid used. Furthermore, the time for reacting the polythiophene compound product with the acid can also be set as desired.

[0161] For example, when using an ion exchange resin, ion exchange can be performed by contacting the polythiophene compound product with the ion exchange resin in water. To increase the hydrogen ions to enhance the doping effect, it is preferable to use a strongly acidic cation exchange resin. To decrease the hydrogen ions to reduce the doping effect, it is preferable to use a strongly basic cation exchange resin. Any method can be used to contact the polythiophene compound product with the ion exchange resin. For example, a column may be packed with the ion exchange resin and a solution containing the polythiophene compound product may be passed through it. Alternatively, the ion exchange resin may simply be placed in a container and a solution containing the polythiophene compound product may be placed in the container. Furthermore, when contacting the polythiophene compound product with the ion exchange resin, the efficiency may be improved by shaking the container or stirring the solution. The time for contacting the polythiophene compound product with the ion exchange resin can be set arbitrarily. For example, when a small amount (e.g., one drop) of polythiophene compound product solution is passed through the column, the time is set as the time from when the small amount of solution contacts the top of the ion exchange resin to when it leaves the bottom of the ion exchange resin. For example, when a large amount of polythiophene compound product solution is passed through a column, the time is set as the average of the time from when the initial part of the solution contacts the ion exchange resin at the top until it separates from the bottom of the ion exchange resin and the time from when the final part of the solution contacts the ion exchange resin at the top until it separates from the bottom of the ion exchange resin. When an ion exchange resin and a polythiophene compound product solution are placed in a container, the time is set as the time it takes for the solution and the ion exchange resin to mix in the container.

[0162] The time for performing one operation of ion exchange of the polythiophene compound product (for example, the contact time between the above-mentioned polythiophene compound product and the acidic aqueous solution or the contact time between the ion exchange resin and the polythiophene compound product) is arbitrarily set depending on the desired degree of ion exchange, but is, for example, preferably 5 seconds or more, more preferably 10 seconds or more, even more preferably 1 minute or more, and still more preferably 10 minutes or more. If the contact time is too short, the ion exchange tends to be insufficient. Also, it is preferably 1 day or less, more preferably 12 hours or less, and even more preferably 2 hours or less. If the contact time is too long, the entire production process will require a long time, and production efficiency will decrease.

[0163] The number of times the ion exchange operation is performed is not particularly limited. Ion exchange may be completed by performing only one ion exchange operation on the polythiophene compound product, or the ion exchange operation may be repeated two or more times. Repeating the ion exchange operation two or more times makes it possible to easily obtain a polythiophene compound with a high doping effect. Specifically, it is preferably repeated three or more times, more preferably repeated four or more times, and even more preferably repeated five or more times. The number of times the ion exchange operation is performed is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. If the number of times is too large, the entire production process will require a long time, and production efficiency will decrease.

[0164] When the ion exchange operation is carried out two or more times, the same ion exchange operation may be repeated two or more times, or two or more types of ion exchange operations may be carried out.

[0165] In one preferred embodiment, the ion exchange operation can be combined with the purification operation to form a series of steps. For example, an acidic aqueous solution is added to a polythiophene compound product to perform ion exchange, and then the polythiophene compound product is purified (e.g., by centrifugation) to remove water and other components, thereby obtaining a highly purified polythiophene compound. This allows for the production of a polymer with high doping efficiency and high purity. Furthermore, this series of steps, combining the ion exchange operation with the purification operation, can be performed as a single cycle, and this cycle can be repeated multiple times. For example, an acidic aqueous solution is added to a polythiophene compound product to perform ion exchange, and then the polythiophene compound product is purified (e.g., by centrifugation) to obtain a highly purified polythiophene compound. The polythiophene compound after the first purification is then subjected to a second ion exchange by adding an acidic aqueous solution again, and then a purification step is performed again to obtain a second purified polythiophene compound with even higher purity. By repeating this series of steps, a polymer with extremely high doping efficiency and high purity can be efficiently obtained. That is, a highly purified and electrically conductive polymer can be efficiently obtained. The number of times that the cycle consisting of a series of steps including the ion exchange operation and the purification operation is repeated is not particularly limited. Specifically, it is preferably repeated three or more times, more preferably four or more times, and even more preferably five or more times. It is also preferably 20 or less times, more preferably 15 or less times, and even more preferably 10 or less times. If the number of times is too many, the entire production process will take a long time, and production efficiency will decrease.

[0166] (Amine Compound) The amine compound contained in the composition of the present invention can be an amine compound composed of nitrogen atoms, carbon atoms and hydrogen atoms.The number of nitrogen atoms in the amine compound is preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and particularly preferably 1.The number of carbon atoms in the amine compound is preferably 15 or less, more preferably 12 or less, even more preferably 9 or less, and particularly preferably 6 or less.In addition, a compound having 5 or less carbon atoms may be selected, a compound having 4 or less carbon atoms may be selected, or a compound having 3 or less carbon atoms may be selected.

[0167] The amine compound may be a compound composed of a nitrogen atom and a hydrocarbon group, a compound composed of a nitrogen atom, a hydrogen atom, and a hydrocarbon group, or a compound having a ring structure (heterocyclic structure) composed of a nitrogen atom and a carbon atom. The heterocyclic structure may be an aliphatic ring structure or an aromatic ring structure. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. That is, the amine compound may be an aliphatic amine or an aromatic amine, but is preferably an aliphatic amine.

[0168] The aliphatic amine may be a primary amine, a secondary amine, or a tertiary amine. The number of carbon atoms in the alkyl group of the aliphatic alkylamine is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4; in one embodiment, it is 1 to 2, and in one embodiment, it is 1. Examples of primary amines include monoalkylamines (e.g., monomethylamine, monoethylamine, monopropylamine, and monobutylamine). Examples of secondary amines include dialkylamines (e.g., dimethylamine, diethylamine, dipropylamine, and dibutylamine). Examples of tertiary amines include trialkylamines (e.g., trimethylamine, triethylamine, tripropylamine, and tributylamine). Examples of aromatic amines include aniline, toluidine, and xylidine. Examples of aliphatic compounds having a ring structure composed of nitrogen atoms and carbon atoms include piperidine, pyrrolidine, etc. Examples of aromatic compounds having a ring structure composed of nitrogen atoms and carbon atoms include pyridine, picoline, lutidine, collidine, imidazole, and 4-dimethylaminopyridine.

[0169] The amine compound contained in the composition of the present invention contains at least one of the above-mentioned compounds, and may contain two or more of them.

[0170] (Solvent) The composition of the present invention optionally contains a solvent. The solvent may be an inorganic solvent or an organic solvent. A solvent capable of dissolving an amine compound and ammonia is preferred. In one preferred embodiment, the solvent is water. Since ammonia is a gas at room temperature, dissolving ammonia in a solvent (e.g., water) to prepare an ammonia solution (e.g., an aqueous ammonia solution) facilitates mixing with a polythiophene compound. Furthermore, when a compound that is a gas at room temperature is used as the amine compound, dissolving the compound in a solvent (e.g., water) to prepare an amine compound solution (e.g., an aqueous amine compound solution) facilitates mixing with a polythiophene compound. When a compound that is a liquid at room temperature is used as the amine compound, ammonia may be dissolved in the amine compound before use. When a compound that is a gas at room temperature is used as the amine compound, it is preferable to dissolve the amine compound in a solvent (e.g., water).

[0171] (Preparation of Composition) The composition of the present invention can be prepared by mixing a polythiophene compound, an amine compound, ammonia, and, if necessary, a solvent. The order of mixing is not particularly limited.

[0172] When a solvent is used in the composition of the present invention, in one embodiment, a polythiophene compound is mixed with a solvent to form a mixture, an amine compound is dissolved in the solvent to form an amine compound solution, and ammonia is dissolved in the solvent to form an ammonia solution, and then the mixture is mixed with the amine compound solution and the ammonia solution. The order of mixing is not particularly limited, and the ammonia solution may be added to the mixture of the polythiophene compound and the solvent, and then the amine compound solution is added. The amine compound solution may be added to the mixture of the polythiophene compound and the solvent, and then the ammonia solution is added. The amine compound solution and the ammonia solution may be added simultaneously to the mixture of the polythiophene compound and the solvent. Alternatively, a mixed solution of the amine compound solution and the ammonia solution may be prepared in advance, and then the mixed solution may be added to the mixture of the polythiophene compound and the solvent.

[0173] (pH of Composition) When water is used as a solvent in the composition, the pH of the composition is preferably 7 or higher, more preferably 8 or higher, and even more preferably 9 or higher. The pH is preferably 12 or lower, more preferably 11 or lower, and even more preferably 10 or lower. If the pH is too high or too low, it may be difficult to obtain the desired shape during molding.

[0174] (Mixing Ratio) Of the total amount of amine compound and ammonia contained in the composition of the present invention, the molar ratio of the amine compound is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 15 mol% or more, and can be 20 mol% or more if necessary. The molar ratio of the amine compound is preferably 99 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less. The molar ratio of the amine compound can range, for example, from 1 mol% to 99 mol%, and can also be 5 mol% to 99 mol%, 10 mol% to 95 mol%, 15 mol% to 95 mol%, or 20 mol% to 90 mol%. If the ratio of the amine compound is too low or too high, the effect of improving conductivity tends to be reduced.

[0175] (Other Additives) The composition of the present invention may contain other additives as long as the effects of the invention are not impaired. Examples of other additives include additives commonly used in the technical field, such as amine compounds other than those mentioned above, basic compounds such as metal hydroxides, and dopants such as polystyrene sulfonic acid.

[0176] (Method for producing a conductive article) In one aspect, the present invention relates to a method for producing a conductive article. This method includes the steps of preparing the composition and molding the composition. In one embodiment, before the step of preparing the composition, a step of polymerizing a monomer corresponding to the polythiophene compound to obtain the polythiophene compound as a solid polymer is carried out. By carrying out the molding step, the shape of the solid polymer becomes the shape desired for the conductive article. In this specification, the term "monomer corresponding to the polythiophene compound" refers to a monomer in which the relationship between the polythiophene compound and the monomer is such that the polythiophene compound is obtained when the monomer is polymerized.

[0177] (Molding Process) The composition of the present invention is used in a process for molding a conductive article. Any known method for molding a conductive article can be used for the molding process. Since polythiophene compounds obtained by polymerization usually cannot be used as conductive articles in their original form, a method for molding the compound into a desired shape (e.g., a film) is known. The composition of the present invention can be used in such a known molding process. In this specification, the process for processing the polythiophene compound obtained by polymerization into a desired shape is referred to as the molding process. Furthermore, when the desired shape is a film, the process for processing the polythiophene compound obtained by polymerization into a film shape is referred to as the film-forming process. For example, a film can be formed by applying the composition of the present invention to a smooth substrate surface and drying it.

[0178] (Conductive Article) In one aspect, the present invention relates to a conductive article obtained by molding the molding composition. The conductive article obtained by molding the molding composition has high conductivity. It is believed that the high conductivity is due to the synergistic effect of the amine compound and ammonia on the polythiophene compound during molding.

[0179] The molded conductive article may be used as a final product or an intermediate product depending on the purpose. For example, the film obtained by molding may be used as a final product such as an antistatic film. When used as an intermediate product, a further processing step, such as connecting with another component, is carried out to produce a final product.

[0180] (Impossible / Impratically Impractical) In a conductive article obtained by molding the composition of the present invention, it is impossible to measure the presence of both amine compounds or substances derived from amine compounds and ammonia or substances derived from ammonia using conventional analytical techniques. In theory, it may be possible to determine the respective amounts of amine compounds or substances derived from amine compounds and ammonia or substances derived from ammonia in the conductive article by conducting an extremely long analysis using specialized analytical equipment at a cost far exceeding the amount of money typically available for corporate research and development. However, due to the first-to-file system adopted by the Patent Act, applications must be filed quickly, making such an analysis unfeasible. Furthermore, it is impossible for a company to determine the respective amounts of amine compounds or substances derived from amine compounds and ammonia or substances derived from ammonia within the reasonable research and development costs. Therefore, it is impossible or impractical to directly identify the structure of a conductive article obtained by molding the composition of the present invention.

[0181] (Applications) Conductive articles molded using the composition of the present invention can be used in various applications conventionally known for conductive polythiophene compounds. That is, the conductive article may be used in any conductive article manufactured using a conductive polymer. Specific examples of applications of conductive articles include antistatic agents, transparent electrodes, organic thin-film solar cells (e.g., hole transport layers), organic electroluminescent devices, secondary batteries, antistatic agents, solar cells, electrode materials for plastic electrodes, EMI materials, organic ferromagnetic materials, electrochromic materials, and various sensors (e.g., touch sensors). The conductive article may be a component of a capacitor, but in one embodiment, the conductive article is a conductive article other than a component of a capacitor.

[0182] (Antistatic Agent) The conductive article molded using the composition of the present invention can be used as an antistatic agent by employing various known methods in which conventional conductive polythiophene compounds are used as antistatic agents. For example, by applying the composition of the present invention to a substrate and drying it, a conductive film is formed on the substrate, imparting antistatic properties to the surface of the substrate. The substrate can be any solid material for which antistatic properties are desired. Specific examples include polymer films, polymer fibers, and polymer resin molded products.

[0183] As a coating method, any method that has been used to coat a substrate with a conventional polythiophene compound can also be used for the polythiophene compound of the present invention, such as spin coating or dip coating.

[0184] (Solar Cell) In one embodiment, the conductive article formed using the composition of the present invention can be used as a material for a solar cell. The conductive article formed using the composition of the present invention can be used, for example, in the hole transport layer of a solar cell.

[0185] As a method for producing a solar cell, a conventionally known method for producing a solar cell can be used. For example, a method for laminating each layer constituting a solar cell can be used. More specifically, a method including a step of forming a hole transport layer containing a material containing the polythiophene compound of the present invention and a step of forming other layers constituting the solar cell can be used. As a material for forming the hole transport layer, the composition of the present invention may be used and formed into a desired shape (for example, a thin film).

[0186] The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way.

[0187] Production Example 1 (Synthesis of Thiophene Monomer) A thiophene monomer represented by the following formula (5) was obtained by the method described in Example 3, paragraph 0145 of Japanese Patent No. 6912060.

[0188] Polymer Preparation Example A (Synthesis of Polythiophene Compound, Polymer A) A mixed solution containing 0.3 g (1.27 mmol) of the thiophene monomer obtained in Production Example 1, 2.86 g (5.08 mmol) of iron (III) sulfate nonahydrate, and 4.6 ml of dilute sulfuric acid was stirred for 7 hours at 5° C.±5° C. Hydrochloric acid was added to the resulting mixed solution, and the precipitated solid was taken out, washed with acetone, and then dried under reduced pressure to obtain a black-blue solid.

[0189] To the resulting black-blue solid, 12 ml of water and 20 ml of 2 M etidronic acid were added, and the mixture was stirred at room temperature (20°C to 25°C) for 2 hours. The solid was then filtered, washed with acetone, and dried under reduced pressure to obtain 0.26 g of a polythiophene compound represented by the following formula (6). The polymer obtained in this preparation example is hereinafter referred to as "Polymer A." (6)

[0190] Polymer Preparation Example B (Synthesis of Polythiophene Compound, Polymer B) A mixed solution containing 7 g (29.6 mmol) of the thiophene monomer obtained in Production Example 1, 66.7 g (119 mmol) of iron (III) sulfate nonahydrate, and 121 ml of water was stirred for 7 hours at 5° C.±5° C. Hydrochloric acid was added to the resulting mixed solution, and the precipitated solid was collected, washed with acetone, and then dried under reduced pressure to obtain a black-blue solid.

[0191] To the resulting black-blue solid, 280 ml of water and 463 ml of 2 M etidronic acid were added, and the mixture was stirred at room temperature (20°C to 25°C) for 2 hours. The solid was then filtered, washed with acetone, and dried under reduced pressure to obtain 6.0 g of a polythiophene compound. The chemical formula of this polythiophene compound is the same as formula (6) above. The polymer obtained in this preparation example will be referred to as "Polymer B" hereinafter.

[0192] (Example 1) (Preparation of Aqueous Solution) An aqueous ammonia solution containing ammonia and a base-containing aqueous solution containing trimethylamine (TMA) were prepared. These aqueous solutions were added to a mixture of 20 mg of a polythiophene compound (polymer A) and water so that the molar ratio of ammonia to trimethylamine (TMA) was 10:90 and the pH was 9 to 10, thereby preparing a total of 1 ml of aqueous film-forming solution.

[0193] (Conductive polymer film formation) A circular frame with a diameter of 1 cm was prepared using polyimide tape on an alkali-free glass substrate. This was used as a test substrate. Using 20 μL of the above-mentioned film-forming aqueous solution, a thin film was formed within the circular frame of this test substrate by a drop-cast method, and the thin film was then heated and dried on a hot plate.

[0194] (Measurement of Electrical Conductivity) The surface resistance was measured by the four-point probe method using a low resistivity meter (LORESTA-GX MCP-T700, manufactured by Nitto Seiko Analytech Co., Ltd.) and the film thickness was measured with a film thickness meter (High-Precision Digimatic Micrometer MDH-25MB, manufactured by Mitutoyo), and the electrical conductivity was calculated using the following formula.

[0195] Electrical conductivity (S / cm)=1 / (surface resistance value (Ω / □)×film thickness (cm)) The results are shown in Table 1.

[0196] Examples 2 to 5 A base-containing aqueous solution was prepared in the same manner as in Example 1, except that the molar ratio of ammonia and trimethylamine (TMA) was changed as shown in Table 1. A film-forming aqueous solution was prepared in the same manner as in Example 1, a thin film was formed, and the conductivity was measured.

[0197] Comparative Example 1 A film-forming aqueous solution was prepared in the same manner as in Example 1, except that a base-containing aqueous solution containing only trimethylamine (TMA) was prepared, a thin film was formed, and the electrical conductivity was measured.

[0198] Comparative Example 2 A film-forming aqueous solution was prepared in the same manner as in Example 1, except that a base-containing aqueous solution containing only ammonia was prepared, a thin film was formed, and the electrical conductivity was measured.

[0199]

[0200] TMA: trimethylamine

[0201] (Considerations on Examples 1 to 5 and Comparative Examples 1 and 2) Since the conductivity of Comparative Example 1, which used only trimethylamine, was 136 S / cm, and the conductivity of Comparative Example 2, which used only ammonia, was 90 S / cm, it is naturally expected that when trimethylamine and ammonia are used in combination, an intermediate conductivity (i.e., 90 to 136 S / cm) should be achieved.

[0202] However, in Examples 1 to 5, in which a mixture of trimethylamine and ammonia was used, a conductivity of 138 to 176 S / cm was measured, which is higher than the expected value of 90 to 136 S / cm, and particularly in Examples 1 to 4, the conductivity was remarkably high at 150 S / cm or more. That is, it was confirmed that in Examples 1 to 5, a high conductivity that could not be expected from common sense was achieved.

[0203] Examples 6 and 7 A base-containing aqueous solution was prepared in the same manner as in Example 1, except that ammonia, monomethylamine (MMA), and dimethylamine (DMA) were used in the molar ratios shown in Table 2. A film-forming aqueous solution was prepared in the same manner as in Example 1, except that this base-containing aqueous solution was used and polymer B was used instead of polymer A, and a thin film was formed and its conductivity was measured.

[0204] Comparative Example 3 A film-forming aqueous solution was prepared in the same manner as in Example 6, except that a base-containing aqueous solution containing only monomethylamine (MMA) was prepared, a thin film was formed, and the electrical conductivity was measured.

[0205] Comparative Example 4 A film-forming aqueous solution was prepared in the same manner as in Example 6, except that a base-containing aqueous solution containing only ammonia was prepared, a thin film was formed, and the electrical conductivity was measured.

[0206] Comparative Example 5 A film-forming aqueous solution was prepared in the same manner as in Example 6, except that a base-containing aqueous solution containing only dimethylamine (DMA) was prepared, a thin film was formed, and the electrical conductivity was measured.

[0207]

[0208] MMA: Monomethylamine DMA: Dimethylamine

[0209] (Discussion on Examples 6 and 7 and Comparative Examples 3 to 5) Since the conductivity of Comparative Example 3, which used only monomethylamine, was 58 S / cm, and the conductivity of Comparative Example 4, which used only ammonia, was 52 S / cm, it is naturally expected that when monomethylamine and ammonia are used in combination, an intermediate conductivity (i.e., 52 to 58 S / cm) should be achieved.

[0210] However, in Example 6, in which a mixture of monomethylamine and ammonia was used, a conductivity of 63 S / cm was measured, which is significantly higher than the expected value of 52 to 58 S / cm. In other words, it was confirmed that Example 6 achieved a significantly higher conductivity than could be expected from common sense.

[0211] Since the conductivity of Comparative Example 5, in which only dimethylamine was used, was 46 S / cm, and the conductivity of Comparative Example 4, in which only ammonia was used, was 52 S / cm, it is naturally expected that when dimethylamine and ammonia are used in combination, an intermediate conductivity (i.e., 46 to 52 S / cm) should be achieved.

[0212] However, in Example 7, in which a mixture of dimethylamine and ammonia was used, a conductivity of 60 S / cm was measured, which is significantly higher than the expected value of 46 to 52 S / cm. In other words, it was confirmed that Example 7 achieved a significantly higher conductivity than could be reasonably expected.

[0213] According to the present invention, a composition for molding an electrically conductive article having excellent electrical conductivity and a method for molding an electrically conductive article are provided. The electrically conductive article molded using the composition of the present invention can be used as a variety of electrically conductive products or components for electrically conductive products. The electrically conductive article can be used in a variety of applications, such as antistatic agents, capacitors, organic electroluminescent devices, secondary batteries, antistatic agents, solar cells, electrode materials for plastic electrodes, EMI materials, organic ferromagnetic materials, electrochromic materials, and various sensors.

[0214] As described above, the present invention has been illustrated using preferred embodiments of the present invention, but the present invention should not be construed as being limited to these embodiments. It is understood that the scope of the present invention should be interpreted only by the claims. It is understood that a person skilled in the art can implement an equivalent scope based on the description of the present invention and common general knowledge from the description of specific preferred embodiments of the present invention. It is understood that the contents of the patents, patent applications, and literature cited in this specification should be incorporated by reference into this specification as if the contents themselves were specifically set forth in this specification.

Claims

1. A composition used for forming a conductive article, comprising a polythiophene compound, an amine compound and ammonia, wherein the polythiophene compound is represented by the following general formula (A): wherein L is a structural unit represented by formula (21): where R ５ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R ６ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; １ is 0 or 1, n ２ is independently an integer from 1 to 6; ３ is independently 0 or 1; n ４ is an integer of 0 to 12, and the left end of formula (21) is bonded to a carbon atom in the dioxane ring in formula (A); １ and M. ２ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom; １Ａ is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or a group represented by formula (15), Here, L １ is expressed by the formula (22): where R １５ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R １６ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; m １ is 0 or 1, m ２ are independently integers from 1 to 6; m ３ is independently 0 or 1; m ４ is an integer of 0 to 12, and the left end of formula (22) is bonded to a carbon atom in the dioxane ring in formula (A); １ｃ and M. ２ｃ are each independently an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, the amine compound is composed of nitrogen atoms, carbon atoms and hydrogen atoms, and the conductive article is not a member used in a capacitor.

2. The composition of claim 1 further comprising a solvent.

3. The composition according to claim 1, wherein the amine compound has a linear or branched alkyl group having 1 to 4 carbon atoms.

4. The composition of claim 1, wherein the amine compound has 1 to 3 nitrogen atoms.

5. The composition according to claim 1, wherein the amine compound is selected from monoalkylamines, dialkylamines and trialkylamines, and the alkyl group in the amine compound is a straight or branched alkyl group having 1 to 4 carbon atoms.

6. The composition of claim 1, wherein the amine compound is selected from monomethylamine, dimethylamine and trimethylamine.

7. The composition according to claim 1, wherein a molar ratio of the amine compound to the total amount of the amine compound and ammonia contained in the composition is 1 mol % to 99 mol %.

8. The composition of claim 2, wherein the solvent is water.

9. R in the polythiophene compound １Ａ The composition of claim 1 , wherein is hydrogen.

10. M in the polythiophene compound １ and M. ２ The composition of claim 9 , wherein is hydrogen.

11. n in the polythiophene compound １ is 0, n ２ is 1, and n ３ is 0, n ４ The composition of claim 9 , wherein:

12. A conductive article molded using the composition according to any one of claims 1 to 11, the conductive article not being used as a component of a capacitor.

13. An electrically conductive article formed using the composition according to any one of claims 1 to 11, the electrically conductive article being in the form of a film, with the proviso that the electrically conductive article is not used as a component of a capacitor.

14. A method for producing an electrically conductive article, comprising the steps of preparing a composition according to any one of claims 1 to 11 and molding the composition to obtain an electrically conductive article, with the proviso that the electrically conductive article is not a component used in a capacitor.

15. The method of claim 14, further comprising the step of polymerizing a monomer corresponding to a polythiophene compound contained in said composition to obtain said polythiophene compound, said step of obtaining said polythiophene compound being carried out prior to the step of preparing said composition.

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