Composition for shaping conductive articles

Abstract

The present invention provides a composition for molding a conductive article having high conductivity. The present invention provides a composition for molding a conductive article comprising a polythiophene compound represented by general formula (A), ammonia, and an amine compound. A method of forming an electrically conductive article using the composition is also provided. In general formula (A), L represents an alkylene group or the like. M1 and M2 are each independently an alkyl group or a hydrogen atom. R1A represents 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

TECHNICAL FIELD

[0001] The present application relates to a composition for molding an electroconductive article using a polythiophene compound and a method for manufacturing an electroconductive article. BACKGROUND

[0002] As a polythiophene resin having electroconductivity, Patent Literature 1 discloses a polythiophene compound having a phosphorus-based structural unit. However, in the field of using various electroconductive articles, in some cases, higher electroconductivity is considered to be preferable, and development of a material having higher electroconductivity is desired.

[0003] [Related Art Documents] [Patent Literature] [Patent Literature 1] International Publication WO2022 / 260007 SUMMARY [Problems to be Solved by the Invention] The present application relates to a composition for molding an electroconductive article using a polythiophene compound and a method for manufacturing an electroconductive article.

[0004] [Means of Solving the Problems] As a result of diligent research, the present inventors found that the above problems can be solved by using a composition containing a specific base at the time of molding a polythiophene compound, thereby completing the present application.

[0005] Specifically, the present application provides the following composition, etc.

[0006] (Item 1) A composition for molding an electroconductive article, wherein the composition contains a polythiophene compound, an amine compound, and ammonia, The polythiophene compound contains a structural unit represented by the following general formula (A): [Chemical Formula 1] wherein, L is represented by formula (21): [Chemical Formula 21]

[0007] wherein R 5 is independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R 6 is independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, n 1 is 0 or 1, n 2 is independently an integer of 1 to 6, n 3 is independently 0 or 1, n 4 is an integer of 0 to 12, the left end of formula (21) is bonded to a carbon atom in the dioxane ring of formula (A), M 1 and M 2 each independently is an alkyl group having a carbon number of 1 to 15 or a hydrogen atom, R 1A is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or a group represented by formula (15): [Chemical Formula 15]

[0008] wherein L 1 is represented by formula (22): [Chemical Formula 22]

[0009] wherein R 15 independently is a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 5, R 16 independently is a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 5, m 1 is 0 or 1, m 2 independently is an integer of 1 to 6, m 3 independently is 0 or 1, m 4 is an integer of 0 to 12, the left end of formula (22) is bonded to a carbon atom in the dioxane ring in formula (A), M 1c and M 2c each independently is an alkyl group having a carbon number of 1 to 15 or a hydrogen atom, the amine compound consists of a nitrogen atom, a carbon atom, and a hydrogen atom, provided that the conductive article is not a component used in a capacitor.

[0010] (Item 2) The composition according to Item 1, further comprising a solvent.

[0011] (Item 3) The composition according to Item 1 or Item 2 (in one embodiment, the composition of Item 1), wherein the amine compound has a linear or branched alkyl group having a carbon number of 1 to 4.

[0012] (Item 4) The composition according to any one of Items 1 to 3 (in one embodiment, the composition of Item 1), wherein the amine compound has 1 to 3 nitrogen atoms.

[0013] (Item 5) The composition according to any one of items 1 to 4 (in one embodiment, the composition of item 1), wherein the amine compound is selected from the group consisting of monoalkylamine, dialkylamine, and trialkylamine, wherein the alkyl group in the amine compound is a linear or branched alkyl group having 1 to 4 carbon atoms.

[0014] (Item 6) The composition according to any one of items 1 to 5 (in one embodiment, the composition of item 1), wherein the amine compound is selected from the group consisting of monomethylamine, dimethylamine, and trimethylamine.

[0015] (Item 7) The composition according to any one of items 1 to 6 (in one embodiment, the composition of item 1), wherein the molar ratio of the amine compound is 1 mol% to 99 mol% with respect to the total amount of the amine compound and ammonia contained in the composition.

[0016] (Item 8) The composition according to item 2, wherein the solvent is water.

[0017] (Item 9) The composition according to any one of items 1 to 8 (in one embodiment, the composition of item 1), wherein R 1A in the polythiophene compound is hydrogen.

[0018] (Item 10) The composition according to any one of items 1 to 9 (in one embodiment, the composition of item 9), wherein M 1 and M 2 in the polythiophene compound are hydrogen.

[0019] (Item 11) The composition according to any one of items 1 to 10 (in one embodiment, the composition of item 9), wherein, in the polythiophene compound, n 1 is 0, n 2 is 1, n 3 is 0, and n 4 is 1.

[0020] (Item 12) An electroconductive article shaped using the composition according to any one of items 1 to 11, which is not used as a component in a capacitor.

[0021] (Item 13) An electroconductive article shaped using the composition according to any one of items 1 to 11, wherein the electroconductive article is in the form of a film, provided that the electroconductive article is not used as a component in a capacitor.

[0022] (Item 14) A method for producing an electroconductive article, which comprises a step of preparing the composition described in any one of items 1 to 11 and a step of molding the composition to obtain an electroconductive article, provided that the electroconductive article is not a component used in a capacitor.

[0023] (Item 15) The method described in 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 performed before the step of preparing the composition.

[0024] [Effects of the Invention] If the composition of the present application is used and the polythiophene compound is molded, an electroconductive article having high electroconductivity is obtained. DETAILED DESCRIPTION

[0025] The present application is described in detail below.

[0026] The composition of the present application contains a polythiophene compound, an amine compound, and ammonia, and, if necessary, a solvent.

[0027] As the polythiophene compound, for example, the polythiophene compound described in Patent Literature 1 can be used.

[0028] [Polythiophene Compound] The polythiophene compound is represented by general formula (12), for example: - (A) q - (12) wherein each of A is independently a thiophene monomer residue. q is a degree of polymerization, which is an arbitrary positive integer. Specifically, q can be 3 or more, 6 or more, or 10 or more, for example, and q can be 2000 or less, 1000 or less, 800 or less, or 400 or less.

[0029] It should be noted that, in the case where the structure of the polythiophene compound is described as a general formula, its both ends are usually omitted. Therefore, in the present specification, when the structure of the polythiophene compound is described, both ends are omitted in principle. However, if both ends of the above-described general formula (12) are described, the following general formula (12A) will be obtained, for example: E 1 - (A) q -E 2 (12A) wherein each of E 1 and E 2 is an end group. Usually, one is a polymerization starting end and the other is a polymerization termination end.

[0030] The polythiophene compound is preferably a homopolymer. However, depending on the requirements, the polythiophene compound can be a copolymer. The copolymer can be a block copolymer or a random copolymer.

[0031] It should be noted that, in this specification, the units constituting the repeating structure of the polymer are referred to as structural units. Specifically, "A" is the structural unit in the polymer of the above general formula (12A). The polymer consists of structural units and end groups. In other words, the portion of the polymer other than the polymerization initiation and termination ends is composed of structural units. Therefore, in this specification, the description that "the polythiophene compound does not contain structural units other than those of general formula (A)" means that the portion other than the end groups is composed only of structural units of general formula (A).

[0032] The polythiophene compound of the present invention comprises a structural unit represented by the following general formula (A): [Chemical Formula 1]

[0033] In general formula (A), L is represented by formula (21): [Chemical Formula 21]

[0034] In this regard, R 5 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0035] R 6 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0036] n 1 It can be 0 or 1, preferably 0.

[0037] n 2 Independently, it is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 2, and even more preferably 1.

[0038] n 3 It can be 0 or 1 independently, preferably 0. If n 3 If n is 0, then n 4 Preferably 1 or 2, and n 4 A more preferred value is 1.

[0039] n 4 It is an integer from 0 to 12, preferably from 0 to 6, more preferably 1 or 2, and even more preferably 1.

[0040] n 2 and n 4The product will be the total number of carbon atoms between the dioxane ring and phosphorus.

[0041] (Number of carbon atoms between the dioxane ring and phosphorus) = n 2 × n 4 The number of carbon atoms between the dioxane ring and phosphorus is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, and particularly preferably 1 to 3. In one embodiment, the number of carbon atoms is 1 or 2.

[0042] The left end of formula (21) is bonded to the carbon atom in the dioxane ring of formula (A), and the right end of formula (21) is bonded to the phosphorus atom in formula (A).

[0043] In one implementation, R 5 and R 6 It is a hydrogen atom, n 1 It is 0, n 3 It is 0, and n 4 It is 1. In other words, in this implementation, L is -(CH2). n2 -, where n 2 Independently, it is 0 to 12. 2 Preferably 0 to 4, more preferably 0 to 2. 2 The preferred value is 1.

[0044] M 1 and M 2 Each is independently an alkyl group or a hydrogen atom having 1 to 15 carbon atoms. In a preferred embodiment, M 1 and M 2 At least one of them is a hydrogen atom. More preferably, M 1 and M 2 They are all hydrogen atoms.

[0045] In general formula (A), R 1A It is a hydrogen atom, alkyl, alkoxy, acyl or a group represented by formula (15), preferably an alkyl or hydrogen atom, and even more preferably a hydrogen atom.

[0046] [Chemical Formula 15]

[0047] In the formula, L 1 Equation (22) represents: [Chemical Formula 22]

[0048] In the formula, R 15 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0049] R 16 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0050] m 1 It can be 0 or 1, preferably 0.

[0051] m 2 Independently, it is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 2, and even more preferably 1.

[0052] m 3 Independently 0 or 1, preferably 0. If m 3 If m is 0, then 4 Preferably 1 or 2, more preferably m 4 The value is 1.

[0053] m 4 It is an integer from 0 to 12, preferably from 0 to 6, more preferably 1 or 2, and even more preferably 1.

[0054] m 2 and m 4 The product is the total number of carbon atoms between the dioxane ring and phosphorus.

[0055] (Number of carbon atoms between the dioxane ring and phosphorus) = m 2 × m 4 The number of carbon atoms between the dioxane ring and 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.

[0056] In addition, the number of carbon atoms between the dioxane ring and phosphorus in L is related to the number of carbon atoms in L. 1 The total number of carbon atoms between the dioxane ring and phosphorus 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.

[0057] The left end of formula (22) is bonded to the carbon atom in the dioxane ring of formula (A), and the right end of formula (22) is bonded to the phosphorus atom in formula (15).

[0058] In one implementation, R 15 and R 16 It is a hydrogen atom, m 1 It is 0, m 3 It is 0, and m 4 It is 1. In other words, in this implementation, L 1 For -(CH2) m2 -, where m 2Independently defined as 0 to 12. M 1c and M 2c Each is independently an alkyl group or a hydrogen atom having 1 to 15 carbon atoms.

[0059] It should be noted that, in this specification, the phosphoric acid or phosphonic acid portion refers to the portion having a structure having a phosphate group or a derivative thereof (e.g., a salt or ester) or a phosphonic acid group or a derivative thereof (e.g., a salt or ester). For example, in this specification, M of general formula (A) 1 and M 2 The portion bound to a phosphate group or a phosphonic acid group, M of general formula (15) 1c and M 2c The portion that is bonded to a phosphate group or a phosphonic acid group is also called the phosphate or phosphonic acid moiety.

[0060] In general formula (A), R 1A The alkyl groups can be independently straight-chain, branched, or cyclic. Cyclic alkyl groups can consist solely of a cyclic structure or have a structure in which chain alkyl groups are further bonded to a cyclic structure. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.

[0061] R 1A The alkoxy groups in the alkoxy group can be independently straight-chain, branched, or cyclic. Cyclic alkoxy groups can consist solely of a cyclic structure, or they can have a structure in which chain alkyl groups and / or chain alkoxy groups are 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 methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, and pentadecyloxy.

[0062] R 1A The acyl groups can be independently linear, branched, or cyclic. Cyclic acyl groups can consist solely of a cyclic structure, or they can have a structure with chain alkyl groups and / or chain acyl groups further bonded to the cyclic structure. The number of carbon atoms in the acyl group is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include acetyl, propionyl, butyryl, valeryl, hexanoyl, heptayl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecayl, tetradecanoyl, pentadecanoyl, etc.

[0063] In a preferred embodiment, R 1A It is a hydrogen atom.

[0064] M 1and M 2 They can be the same as or different from each other. In a preferred embodiment, M 1 and M 2 Same. M 1c and M 2c They can be the same as or different from each other. In a preferred embodiment, M 1c and M 2c They are the same.

[0065] In the above general formula (A), M 1 M 2 M 1c and M 2c The alkyl group can be straight-chain or branched, and the number of carbon atoms is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 5. In a further preferred embodiment, the alkyl group has 2 carbon atoms. If the number of carbon atoms in the alkyl group is within the preferred range, a polythiophene compound with excellent electrical conductivity is obtained. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.

[0066] In the above general formula (A), M 1 and M 2 Both can be alkyl groups, but from a conductivity perspective, it is preferable that at least one is a hydrogen atom. More preferably, both are hydrogen atoms. Additionally, M... 1c and M 2c Both can be alkyl groups, but from the perspective of conductivity, it is preferred that at least one is a hydrogen atom. More preferably, both are hydrogen atoms.

[0067] Specific examples of the structural units of the above general formula (A) include the following formulas (9), (10), (11), (13), etc.

[0068] [Chemical Formula 9]

[0069] [Chemical Formula 10]

[0070] [Chemical Formula 11]

[0071] [Chemical Formula 13]

[0072] In one embodiment, the structural units of the polythiophene compound used in the composition of the present invention may consist only of the structural units of the above-described general formula (A). In one embodiment, the polythiophene compound used in the composition of the present invention substantially does not contain structural units other than those of the above-described general formula (A). If the structural units of the polymer consist only of the structural units of the above-described general formula (A), advantageous properties can be exhibited at a high level.

[0073] In other embodiments, the polythiophene compound used in the composition of the present invention may include structural units other than those of the above general formula (A) without impairing the effects of the present invention.

[0074] However, if the content of structural units other than general formula (A) is too high, the advantages of the present invention will be compromised. Therefore, the content of structural units other than general formula (A) is preferably not too high. The content of structural units other than general formula (A) relative to all structural units in the polythiophene compound is preferably 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, further preferably 10 mol% or less, particularly preferably 5 mol% or less, especially preferably 3 mol% or less, and most preferably 1 mol% or less. Additionally, the content of structural units other than general formula (A) may also be 0.1 mol% or less, or even 0.01 mol% or less.

[0075] Conductive polythiophene compounds with self-doping properties require a phosphoric acid or phosphonic acid moiety that provides hydrogen ions. The phosphoric acid or phosphonic acid moiety that provides hydrogen ions refers to a phosphoric acid or phosphonic acid moiety containing at least one -P-OH group. The number of phosphorus-containing thiophene monomer residues containing the phosphoric acid or phosphonic acid moiety that provides hydrogen ions in the polythiophene compound used in the compositions of the present invention can be selected as any number. When the total number of phosphorus-containing thiophene monomer residues present in the polythiophene compound is 100%, the proportion of phosphorus-containing thiophene monomer residues containing the phosphoric acid or phosphonic acid moiety that provides hydrogen ions can be selected, 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. Alternatively, the proportion can be 100%. Furthermore, when it is necessary to control the content of the hydrogen-providing group (-P-OH) for some reason, the design can be implemented to control the number of the phosphoric acid or phosphonic acid moiety that provides hydrogen ions. In this case, when the total number of phosphorus-containing thiophene monomer residues in the polythiophene compound present in the composition of the present invention is 100%, the proportion of phosphorus-containing thiophene monomer residues containing the phosphoric acid or phosphonic acid moiety that provides hydrogen ions can be designed to be, for example, 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, or 70% or less.

[0076] Furthermore, the ratio of the phosphoric acid or phosphonic acid portion providing hydrogen ions to the total number of phosphoric acid or phosphonic acid portions can be designed to be any ratio. When the total number of phosphoric acid or phosphonic acid portions in the polythiophene compound used in the compositions of the present invention is 100%, the ratio of the phosphoric acid or phosphonic acid portion providing hydrogen ions 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. Alternatively, the ratio can be 100%. Furthermore, when it is necessary to control the content of hydrogen-ion-providing groups for some reason, the design can be implemented to control the amount of phosphoric acid or phosphonic acid portions providing hydrogen ions. In this case, when the total number of phosphoric acid or phosphonic acid portions in the polythiophene compound present in the compositions of the present invention is 100%, the ratio of the phosphoric acid or phosphonic acid portion providing hydrogen ions can be designed to, for example, 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, or 70% or less.

[0077] The proportion of the phosphoric acid or phosphonic acid portion that provides hydrogen ions can be controlled, for example, by adjusting the type and amount of the thiophene compound used to prepare the polythiophene compound.

[0078] The polythiophene compound used in the compositions of this invention can be prepared using the following methods.

[0079] (Molecular weight) The molecular weight of the polythiophene compound used in the compositions of the present invention is not particularly limited. The weight-average molecular weight of the polythiophene compound used in the compositions of the present invention is preferably 1,000 or greater, more preferably 2,000 or greater. The weight-average molecular weight of the polythiophene compound used in the compositions of the present invention is preferably 500,000 or less, more preferably 200,000 or less, and even more preferably 100,000 or less.

[0080] The polythiophene compound used in the compositions of the present invention preferably comprises monomer residues having a phosphoric acid or phosphonic acid structural moiety [-OP(O)(OH)2 or -P(O)(OH)2], or a monoalkyl phosphate or monoalkyl phosphonic acid structural moiety [-OP(O)(OH)(OR) or -P(O)(OH)(OR), wherein R is an alkyl group having 1 to 15 carbon atoms]. The phosphoric acid or phosphonic acid structural moiety or the monoalkyl phosphate or monoalkyl phosphonic acid structural moiety can dope the thiophene ring of the polythiophene compound backbone by hydrogen ions released from their hydrogen-donating groups (-P-OH).

[0081] In one embodiment of the present invention, a polythiophene compound having a specific absorbance ratio can be used. High conductivity is achieved by using a polythiophene compound with a specific absorbance ratio. Specifically, in the polythiophene compound used in the compositions of the present invention, the absorbance (AL) of the compound at a wavelength of 2000 nm, as measured using a spectrophotometer, is... 2000 ) and the absorbance of the compound at a wavelength of 407 nm (A 407 ), through calculation formula (A) 2000 / A 407 The calculated absorbance ratio is 1 or higher. The absorbance ratio is preferably 1.5 or higher, more preferably 2 or higher, even more preferably 2.5 or higher, and particularly preferably 3 or higher. Depending on the requirements, the absorbance ratio can be 3.5 or higher, 4 or higher, or 4.5 or higher. There is no upper limit to the absorbance ratio. However, depending on the requirements, the upper limit of the absorbance ratio can be set, for example, to 10 or lower, or 8 or lower, or 6 or lower. The method described in Patent Document 1 can be used as the method for measuring absorbance.

[0082] [Thiophene compound] The polythiophene compound used in the compositions of this invention is prepared using a phosphorus-containing thiophene compound as a monomer.

[0083] [Phosphorus-containing thiophene compounds] Phosphorus-containing thiophene compounds are compounds represented by the following general formula (Am): [Chemical Formula 2A]

[0084] In the above general formula (Am), L is represented by formula (21): [Chemical Formula 21]

[0085] Where R 5 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, R 6 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, n 1 n is either 0 or 1. 2 n is an independent integer from 1 to 6. 3 n is independently 0 or 1. 4 The left end of formula (21) is bonded to the carbon atom in the dioxane ring of formula (Am) and is an integer from 0 to 12.

[0086] In one implementation, L is -(CH2). n -, where n is between 0 and 12.

[0087] M 1 and M2 Each is independently an alkyl group or a hydrogen atom having 1 to 15 carbon atoms.

[0088] R 1A It is a hydrogen atom, alkyl, alkoxy, acyl, or a group represented by formula (15): [Chemical Formula 15]

[0089] L 1 Equation (22) represents: [Chemical Formula 22]

[0090] Where R 15 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, R 16 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m 1 m is 0 or 1 2 m is an independent integer from 1 to 6. 3 Independently 0 or 1, m 4 The left end of formula (22) is bonded to the carbon atom in the dioxane ring of formula (Am) and is an integer from 0 to 12.

[0091] In this regard, M 1c and M 2c Each is independently an alkyl group or a hydrogen atom having 1 to 15 carbon atoms.

[0092] The above M 1 M 2 M 1c and M 2c The alkyl group can be a straight-chain alkyl group or a branched alkyl group. The number of carbon atoms is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 5. The most preferred number of carbon atoms is 2. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc. Within the above range, the oxidative polymerization reaction can proceed smoothly, thereby facilitating the obtaining of polythiophene compounds used in the compositions of the present invention.

[0093] In one implementation, M 1 and M 2 It is a hydrogen atom. If M 1 and M 2 The presence of hydrogen atoms offers an advantage in preparing polythiophene compounds containing diacid forms. In polythiophene, the diacid form typically exhibits higher conductivity than the dialkyl and monoacid forms. Therefore, it is advantageous to readily prepare polythiophene compounds containing diacid forms.

[0094] Furthermore, in one implementation, M 1c and M 2c It is a hydrogen atom. If M 1c and M 2c If it is a hydrogen atom, it has the advantage of being conducive to the preparation of polythiophene compounds containing diacid forms.

[0095] M 1 and M 2 They can be the same as or different from each other. In a preferred embodiment, M 1 and M 2 Same. M 1c and M 2c They can also be the same as or different from each other. In a preferred embodiment, M 1c and M 2c same.

[0096] If M 1 and M 2 Since they are all alkyl groups, a polythiophene compound with excellent conductivity can be obtained by hydrolyzing a compound obtained by oxidative polymerization of a monomer mixture containing the above-mentioned thiophene compound.

[0097] Similarly, if M 1c and M 2c Since they are all alkyl groups, a polythiophene compound with excellent conductivity can be obtained by hydrolyzing a compound obtained by oxidative polymerization of a monomer mixture containing the above-mentioned thiophene compound.

[0098] R 1A The alkyl group can be straight-chain, branched, or cyclic. Cyclic alkyl groups can consist solely of a cyclic structure, or they can have a structure in which a chain alkyl group is further bonded to a cyclic structure. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.

[0099] R 1A The alkoxy group can be straight-chain, branched, or cyclic. Cyclic alkoxy groups can consist solely of a cyclic structure, or they can have a structure with chain alkyl groups and / or chain alkoxy groups 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 methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, and pentadecyloxy.

[0100] R1A The acyl group can be straight-chain, branched, or cyclic. Cyclic acyl groups can consist solely of a cyclic structure, or they can have a structure with chain alkyl groups and / or chain acyl groups further bonded to the cyclic structure. The number of carbon atoms in the acyl group is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include acetyl, propionyl, butyryl, valeryl, hexanoyl, heptayl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecayl, tetradecanoyl, pentadecanoyl, etc.

[0101] In a preferred embodiment, R 1A It is an alkyl group or a hydrogen atom, and more preferably a hydrogen atom.

[0102] Specific examples of the above general formula (Am) include the following formulas (5), (9B), (10B), (11C), etc.

[0103] [Chemical Formula 5]

[0104] [Chemical Formula 9B]

[0105] [Chemical Formula 10B]

[0106] [Chemical formula 11c]

[0107] [Methods for preparing phosphorus-containing thiophene compounds] The phosphorus-containing thiophene compound used in this invention is in R 1A In the case of hydrogen atoms, the compound can be prepared, for example, by the method described below. In particular, from the perspective of yield and operability, it is preferred to prepare the compound by the following first and second steps.

[0108] (Step 1) In step 1, a compound represented by the following general formula (3) is obtained by a known method.

[0109] [Chemical Formula 3]

[0110] In equation (3), L is represented by equation (21): [Chemical Formula 21]

[0111] Where R 5 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, R 6Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, n 1 n is either 0 or 1. 2 n is an independent integer from 1 to 6. 3 n is independently 0 or 1. 4 The left end of equation (21) is bonded to the carbon atom in the dioxane ring in equation (3), and is an integer from 0 to 12.

[0112] In one implementation, L is -(CH2). n - where n is 0 to 12. n is preferably 0 to 4, more preferably 0 to 2, and particularly preferably 1. X 1 The atoms are halogen atoms such as fluorine, chlorine, bromine, or iodine. Considering the availability and operability of the raw materials, chlorine or bromine atoms are preferred.

[0113] Specifically, in equation (3) above, L is -(CH2). n Compounds of - can be obtained, for example, by the method described in Japanese Patent Application Publication No. 2014-74007.

[0114] In addition, in the embodiment where n=1, the compound represented by the following general formula (3A) can be obtained by heating 3-halo-1,2-propanediol and 3,4-dimethoxythiophene in the presence of an acidic catalyst.

[0115] [Chemical Formula 3A]

[0116] Examples of the aforementioned acidic catalysts include sulfuric acid, p-toluenesulfonic acid monohydrate, and methanesulfonic acid. The preferred acidic catalyst is p-toluenesulfonic acid monohydrate.

[0117] In equation (3) above, L is not -(CH2). n Compounds of - can also be obtained by methods similar to those described above.

[0118] (Reaction temperature) The heating described above is performed to allow the reaction to proceed. There are no particular limitations on the heating temperature, as long as the reaction proceeds at an appropriate rate, but 60°C or higher is preferred, more preferably 70°C or higher, and particularly preferably 80°C or higher. The temperature is preferably 200°C or lower, more preferably 150°C or lower, and particularly preferably 120°C or lower.

[0119] (Reaction time) There is no particular limitation on the heating time described above. Under each condition, a sufficient reaction time for the starting materials can be appropriately selected. If the reaction proceeds sufficiently, the difference in reaction time will not significantly affect the effect of the invention. For example, the reaction time is preferably 1 hour or more, more preferably 3 hours or more. The reaction time is preferably 2 days or less, more preferably 1 day (24 hours) or less.

[0120] (solvent) In step 1, a solvent can be used as needed. There are no particular limitations on the solvent, as long as it is non-reactive in the oxidative polymerization reaction. Examples 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; ether solvents such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, dimethoxyethane, dioxane, and diethylene glycol dimethyl ether; and so on. Xylene, toluene, or diethylene glycol dimethyl ether is preferred as the solvent, and xylene or toluene is more preferred.

[0121] (purification) The product obtained in step 1 can be used in step 2 without further purification or other post-processing. Alternatively, if necessary, in step 2, a purified product obtained by purifying the product obtained in step 1 using known methods can also be used.

[0122] (Step 2) In step 2, the compound represented by the above general formula (3) is reacted with tri(trialkylsilyl) phosphite or trialkyl phosphite to remove X from the compound represented by general formula (3). 1 The substitution is made with a bis(trialkylsilyl)phosphonate moiety or a phosphonate diester moiety. When synthesizing thiophene containing a phosphonate moiety, i.e., a diacid form, the method of using a tri(trialkylsilyl) phosphite is preferred from the perspective of reaction efficiency.

[0123] Tris(trialkylsilyl) phosphite is represented by the following general formula (11A): [Chemical Formula 11A]

[0124] Where M 3a M 4a and M 5a Each of the following is independently trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, or triisopropylsilyl, preferably trimethylsilyl or triethylsilyl, and more preferably trimethylsilyl. 3a M 4a and M 5aThey can be chosen independently, but the same is preferred. Specific examples include, for example, tris(trimethylsilyl) phosphite, tris(triethylsilyl) phosphite, etc.

[0125] For example, the Michaelis-Arbuzov rearrangement occurs by heating a mixture of the compound represented by the above general formula (3) and trialkylsilyl phosphite. The compound of general formula (2A) is obtained as its rearrangement product.

[0126] [Chemical Formula 2A]

[0127] In the formula, M 3a and M 4a Each of these is independently a trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, or triisopropylsilyl group, which are commonly used as protecting groups for hydroxyl groups. Compounds of the following general formula (2C) can be obtained by deprotection using known methods.

[0128] For example, by reacting an alkaline aqueous solution such as sodium carbonate, potassium carbonate, or ammonia with a compound of the above general formula (2A), deprotection occurs.

[0129] [Chemical formula 2C]

[0130] Although the compound of general formula (2C) above can be obtained by hydrolyzing the compound of general formula (2B) described below using a known method, it can be obtained more readily by using the method described above for trialkylsilyl phosphite.

[0131] Trialkyl phosphites are represented by the following general formula (11B): [Chemical Formula 11B]

[0132] Where M 3b M 4b and M 5b Each alkyl group is independently an alkyl group having 1 to 15 carbon atoms. The number of carbon atoms is preferably 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 with M in the general formula (Am) 1 and M 2 Same. M 3b and M 4b Based on the M of the compound of interest in the general formula (Am) 1 and M 2 Choose. M 3band M 4b They can be the same or different. Although M 5b The M of interest can be independently selected from compounds of general formula (Am). 1 and M 2 However, M is preferred. 5b With M 3b Or M 4b The same as any of them. In a preferred embodiment, M 3b M 4b and M 5b They are the same. Specific examples include, for instance, trimethyl phosphite and triethyl phosphite.

[0133] For example, the Michaelis-Arbuzov rearrangement occurs by heating a mixture of the compound represented by the above general formula (3) and a trialkyl phosphite. The compound of general formula (2B) is obtained as its rearrangement product.

[0134] [Chemical Formula 2B]

[0135] In the formula, M 3b and M 4b Each is an alkyl group having 1 to 15 carbon atoms.

[0136] There are no particular limitations on the mixing ratio (molar ratio) of the compound represented by general formula (3) with trialkyl phosphite or tri(trialkylsilyl) phosphite. However, considering factors such as yield, the mixing ratio (molar ratio) of the compound represented by general formula (3) with trialkyl phosphite or tri(trialkylsilyl) phosphite relative to 1 mole of the compound represented by general formula (3) is preferably 0.8 moles or more, more preferably 1 mole or more of trialkyl phosphite or tri(trialkylsilyl) phosphite. In addition, relative to 1 mole of the compound represented by general formula (3), the trialkyl phosphite or tri(trialkylsilyl) phosphite is preferably 10 moles or less, more preferably 5 moles or less, and particularly preferably 3 moles or less.

[0137] (Reaction temperature) The heating described above is performed to allow the reaction to proceed. There are no particular limitations on the reaction temperature, as long as the reaction proceeds at an appropriate rate. Preferably, the temperature is 100°C or higher, more preferably 110°C or higher, and particularly preferably 120°C or higher. Furthermore, the temperature is preferably 220°C or lower, more preferably 200°C or lower, and particularly preferably 160°C or lower.

[0138] (Reaction time) There is no particular limitation on the heating time described above. A suitable time can be selected to allow the reactants to react under conditions such as temperature. If the reaction proceeds sufficiently, differences in reaction time will not significantly affect the effectiveness of the invention. The reaction time is preferably 6 hours or more, more preferably 12 hours or more. Furthermore, the reaction time is preferably 3 days or less, more preferably 2 days or less.

[0139] (solvent) In step 2, a solvent may be used as needed. There are no particular limitations on the solvent, as long as it is a liquid that is non-reactive in step 2 and can dissolve or disperse the reactants. Examples 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; ether solvents such as tetrahydrofuran, diethyl ether, tert-butylmethyl ether, dimethoxyethane, dioxane, and diethylene glycol dimethyl ether; and so on. Toluene, xylene, or diethylene glycol dimethyl ether is preferred as the solvent, and xylene or toluene is more preferred.

[0140] (hydrolysis) The compounds of general formula (2B) obtained by the above reaction can be hydrolyzed or ion-exchanged as needed.

[0141] For example, the compound of general formula (2B) obtained by the above reaction can be hydrolyzed as needed. The compound of general formula (2B) can be hydrolyzed, followed by additional ion exchange. M in general formula (2B) 3b and M 4b Compounds containing hydrogen atoms, alkali metals, etc., can be obtained by hydrolyzing compounds of general formula (2B). Furthermore, by further ion exchange, M can be obtained... 3b and M 4b The type is converted into the desired type.

[0142] Various well-known methods can be used as hydrolysis methods. Alternatively, the following methods and conditions can be used to hydrolyze polythiophene compounds.

[0143] Various known methods can be used as ion exchange methods. Alternatively, the following methods and conditions for ion exchange of phosphorus-containing thiophene copolymers can be used.

[0144] (purification) The product obtained in step 2 can be used as a phosphorus-containing thiophene compound in the polymerization step without further purification or other post-treatment. Alternatively, it can be purified or subjected to other post-treatment using known methods.

[0145] (R) 1A Preparation method when it is not a hydrogen atom) Even if R 1A Phosphorus-containing thiophene compounds can also be produced using methods that are essentially similar to those described above, even if the atoms are not hydrogen atoms.

[0146] If R 1A If it is a group of formula (15), then the phosphorus-containing thiophene compound can be prepared by, for example, the following methods.

[0147] (Step 1) In step 1, the diol of general formula (17A) is reacted with 3,4-dialkoxythiophene of general formula (18) to give the intermediate shown in general formula (19A) by the following reaction.

[0148] [Chemical Formula 17A]

[0149] In the formula, R 3 and R 4 It is an alkyl group (e.g., methyl).

[0150] For example, if L and L 1 If it is -(CH2)-, then 1,4-dihalo-2,3-butanediol is used instead of the above-mentioned 3-halo-1,2-propanediol as the compound of formula (17A).

[0151] L and L in equation (19A) 1 Compounds that are not -(CH2)- can be obtained by methods similar to those described above.

[0152] (Step 2) The phosphorus-containing thiophene compound of general formula (Am) is obtained by reacting the intermediate of general formula (19A) obtained in step 1 with the compound of general formula (11A) and deprotecting it by using the method described above, or by reacting the intermediate of general formula (19A) with the compound of general formula (11B) by using the method described above.

[0153] [Chemical Formula 2A]

[0154] In the formula, R 1A The group is represented by the following general formula (15).

[0155] [Chemical Formula 16]

[0156] The mixing ratio of the intermediate and the phosphite is preferably 1.6 moles or more of phosphite relative to 1 mole of intermediate, more preferably 2 moles or more. Furthermore, the mixing ratio of phosphite relative to 1 mole of intermediate is preferably 20 moles or less, more preferably 10 moles or less, and particularly preferably 6 moles or less.

[0157] If R 1A If the atom is a hydrogen atom, alkyl group, alkoxy group, or acyl group, then the phosphorus-containing thiophene compound can be prepared by, for example, the following methods.

[0158] (Step 1) In step 1, the diol of general formula (17B) and the 3,4-dialkoxythiophene of general formula (18) are reacted via the following reaction to give the intermediate represented by general formula (19B): [Chemical Formula 17B]

[0159] (Step 2) The phosphorus-containing thiophene compound of general formula (Am) can be obtained by reacting the intermediate of general formula (19B) obtained in step 1 with the compound of general formula (11A) by the above method and then deprotecting it, or by reacting the intermediate of general formula (19B) with the compound of general formula (11B) by the above method.

[0160] [Chemical Formula 2A]

[0161] In the formula, R 1A It can be a hydrogen atom, alkyl, alkoxy, or acyl group.

[0162] [Methods for preparing polythiophene compounds] The polythiophene compound used in the compositions of the present invention is obtained by oxidative polymerization of the aforementioned phosphorus-containing thiophene compound using a suitable oxidant and followed by appropriate purification steps. As the oxidative polymerization method, conventional and well-known methods for polymerizing thiophene compounds can be used. From the perspective of yield and operability, preparation under the conditions described below is preferred.

[0163] It should be noted that, in this specification, "oxidative polymerization" refers to the reaction in which a thiophene monomer compound or a mixture of thiophene monomers is polymerized using an oxidizing agent to synthesize a polythiophene compound. In this context, "oxidation" refers to the removal of hydrogen atoms at the 2 and 5 positions from the thiophene monomer compound during the polymerization reaction. In this specification, "oxidizing agent" refers to the reagent that induces this oxidation reaction. Oxidative polymerization reactions of thiophene monomers are described, for example, in the aforementioned Patent Document 1, etc. It should be noted that the term oxidative polymerization is described in the Encyclopaedia Chimica as "the process by which a compound having hydrocarbon residues containing double bonds comes into contact with oxygen and gradually polymerizes; the best example is the drying of oils and fats." However, the polymerization of thiophene monomers typically does not use oxygen from the air as an oxidizing agent. Therefore, in this respect, the term "oxidative polymerization" in this specification has a slightly different meaning than that used in the Encyclopaedia Chimica, etc.

[0164] (monomer) Polythiophene compounds containing structural units of the above general formula (A) can be obtained by oxidative polymerization using phosphorus-containing thiophene compounds of the above general formula (Am) as monomers for polymerization.

[0165] It should be noted that, during oxidative polymerization, only one type of thiophene compound of general formula (Am) can be used, or two or more types of thiophene compounds of general formula (Am) can be used.

[0166] However, if the amount of monomers other than those of general formula (Am) is too high, the advantages of the present invention will be compromised. Therefore, the amount of monomers other than those of general formula (Am) is preferably not too high. The amount of monomers other than those of general formula (Am) relative to the total amount of monomers used in the polymerization reaction is preferably 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, even more preferably 10 mol% or less, particularly preferably 5 mol% or less, especially preferably 3 mol% or less, and most preferably 1 mol% or less.

[0167] (Oxidizing agent) The oxidative polymerization reaction in this invention is carried out in the presence of an oxidizing agent. As the oxidizing agent, oxidizing agents commonly used in the oxidative polymerization of thiophene compounds can be used. Specific examples include ammonium persulfate, ferric chloride, ferric p-toluenesulfonate, ferric sulfate, ferric nitrate, etc.

[0168] Oxidizing agents containing iron atoms can be preferred. More preferred examples include ferric chloride, ferric p-toluenesulfonate, ferric sulfate, and ferric nitrate.

[0169] Two or more types of oxidants can be used simultaneously. When two or more types of oxidants are used simultaneously, it is preferable to use an oxidant containing iron atoms as one of the two or more types. Specifically, a preferred combination for use together is a combination of ferric sulfate and ammonium persulfate.

[0170] There is no particular limitation on the amount of oxidant used, as long as the oxidative polymerization reaction proceeds well. The amount is preferably 1 equivalent or more relative to the monomer used in the oxidative polymerization reaction, more preferably 2 equivalents or more, and particularly preferably 3 equivalents or more. Additionally, 100 equivalents or less is preferred, more preferably 60 equivalents or less, and particularly preferably 20 equivalents or less.

[0171] If the dosage is within the above range, the reaction proceeds smoothly.

[0172] It should be noted that oxygen in the air is generally not an oxidant in the polymerization of thiophene monomers. Therefore, even when the polymerization reaction is carried out in the presence of air, the oxygen in the air is generally not included in the amount of oxidant used in the polymerization reaction. In other words, the term "oxidative polymerization" is sometimes used to refer to polymerization reactions that use oxygen present in the air as an oxidant, but the polymerization reaction in this invention is different from such a polymerization reaction.

[0173] (solvent) The polymerization reaction of the present invention can use solvents as needed.

[0174] There are no particular limitations on the solvent, as long as it is a liquid capable of dissolving or dispersing the reactants. Specific examples of solvents include: water; aqueous solutions, such as ammonia, hydrochloric acid, etc.; alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, etc.; aromatic hydrocarbons, such as benzene, toluene, xylene, etc.; ketones, such as acetone, 2-butanone, etc.; halogenated hydrocarbons, such as dichloromethane, chloroform, chlorobenzene, etc.; acetonitrile; dimethylacetamide; dimethylformamide; dimethyl sulfoxide; tetrahydrofuran; etc. The solvent is preferably water, ammonia, hydrochloric acid, methanol, ethanol, dimethylformamide, dimethyl sulfoxide, acetonitrile, acetone, tetrahydrofuran, or toluene, and more preferably water, methanol, acetonitrile, dimethylformamide, or dimethyl sulfoxide.

[0175] The solvents mentioned above can be used alone or in combination of two or more. A mixed solvent, consisting of two or more solvents, is preferred.

[0176] (Reaction temperature) There are no particular limitations on the reaction temperature during polymerization. The temperature is preferably -20°C or higher, more preferably -15°C or higher, and particularly preferably -10°C or higher. The temperature is also preferably 80°C or lower, more preferably 60°C or lower, and particularly preferably 40°C or lower.

[0177] (Reaction time) The polymerization reaction time in this invention can be appropriately selected to allow the reaction to proceed under various conditions. If the reaction proceeds sufficiently, the difference in reaction time will not significantly affect the effectiveness of this invention.

[0178] The reaction time is preferably 1 hour or more, more preferably 3 hours or more, even more preferably 6 hours or more, further preferably 9 hours or more, particularly preferably 12 hours or more, and can be 15 hours or more, 18 hours or more, 21 hours or more, 24 hours or more as needed. Additionally, the reaction time is preferably 7 days or less, more preferably 5 days or less, even more preferably 3 days or less, further preferably 2 days or less, particularly preferably 36 hours or less, and can be 30 hours or less, 28 hours or less, or 26 hours or less as needed.

[0179] (hydrolysis) Polythiophene compounds obtained through polymerization can be hydrolyzed as needed. The phosphate or phosphonic acid moiety [-OP(O)(OH)2 or -P(O)(OH)2], the monoalkyl phosphate or monoalkyl phosphonic acid moiety [-OP(O)(OH)(OR) or -P(O)(OH)(OR) or -P(O)(OH)(OR), where R is an alkyl group having 1 to 15 carbon atoms], or the monohydrogen phosphate or monohydrogen phosphonic acid moiety [-OP(O)(OH)(OM] 6 ) or -P(O)(OH)(OM 6 ), where M 6 [It is an alkali metal, alkaline earth metal or ammonium group] can be obtained by hydrolyzing the ester bonds of the alkyl phosphate or alkyl phosphonate moiety in the polythiophene compound.

[0180] Hydrolysis can be carried out, for example, by treatment with a strong acid or a strong base. For instance, hydrolysis can be performed by heating in an acidic or alkaline aqueous solution. Examples of strong acids include protic acids such as hydrochloric acid and sulfuric acid; Lewis acids such as trimethylsilyl bromide; and so on. Examples of strong bases include potassium hydroxide and sodium hydroxide. In this regard, when using Lewis acids, a method that reacts with the Lewis acid followed by a reaction with water is preferred. From the perspective of the stability of the polythiophene compound backbone, base treatment is preferred.

[0181] When heating is performed during hydrolysis, there are no particular limitations on the temperature. The temperature is preferably 30°C or higher, more preferably 50°C or higher. Additionally, the temperature is preferably 100°C or lower, more preferably 90°C or lower.

[0182] There is no particular limitation on the hydrolysis time. The preferred time is 1 hour or more, more preferably 6 hours or more. Additionally, 4 days or less is preferred, more preferably 2 days or less.

[0183] The polythiophene compounds obtained by hydrolysis can be further subjected to ion exchange as needed to adjust the amount of phosphoric acid or phosphonic acid structural moieties that provide hydrogen ions.

[0184] (purification) The polythiophene compound obtained from the polymerization reaction is subjected to appropriate purification procedures. Any method known as a purification method for polythiophene compounds can be used as a purification procedure. For example, centrifugation, filtration, dehydration, drying, washing, ultrafiltration, or dialysis can be performed. There are no particular limitations on the number and type of purification procedures. While purification can be completed in one operation of one type, two or more purification procedures may be performed as needed. For example, three or more, four or more, or five or more purification procedures may be performed. In this regard, a purification procedure may be repeated two or more times, or multiple purification procedures may be combined to perform a total of two or more purification procedures. There is no particular upper limit to the number of purification procedures, but 20 or fewer is preferred, more preferably 15 or fewer, and even more preferably 10 or fewer. If the number of procedures is too high, the entire preparation process will take a long time, reducing the preparation efficiency.

[0185] In a preferred embodiment of the invention, purification is performed using a chelating compound. Purification using a chelating compound yields a resin with high conductivity. In this specification, a chelating compound refers to a compound having multiple ligands. As a purification method using a chelating compound, any method capable of contacting the polythiophene compound with the chelating compound can be used. A method capable of contacting the polythiophene compound with the chelating compound in a liquid is preferred. In one embodiment, purification of the polythiophene compound can be performed by adding a solvent and a chelating compound to the polythiophene compound and stirring the mixture. Water is a preferred solvent. There are no particular limitations on the temperature at which purification is performed. The temperature can be room temperature or a heated temperature. Preferably, the temperature is such that the mixture containing the polythiophene compound and the chelating compound remains in a liquid state during purification.

[0186] Any conventional and known chelating compound can be used as a chelating compound. The chelating compound is preferably a chelating compound containing phosphorus and oxygen atoms, more preferably a compound having multiple (e.g., two) phosphonic acid moieties (-P(=O)(OH)2). For example, bisphosphonates can be used. Particularly preferred examples include etidronic acid.

[0187] (Ion exchange) Polythiophene compounds obtained through polymerization can optionally undergo ion exchange to adjust the doping level. Ion exchange can be performed using acidic aqueous solutions, ion exchange resins, etc.

[0188] Specifically, when the amount of hydrogen-donating groups in the polythiophene compound obtained by polymerization, such as phosphoric acid or phosphonic acid, monoalkyl phosphate or monoalkyl phosphonic acid, monohydrogen phosphate or monohydrogen phosphonic acid, is less than the required amount for the entire polymer, ion exchange between metal ions or ammonium ions bound to phosphoric acid or phosphonic acid and hydrogen ions can be carried out to improve the doping effect.

[0189] Conversely, when the amount of hydrogen-donating groups in the polythiophene compound obtained by polymerization, such as phosphoric acid or phosphonic acid, monoalkyl phosphate or monoalkyl phosphonic acid or monohydrogen phosphate or monohydrogen phosphonic acid, is greater than the required amount in the polymer as a whole, ion exchange of the hydrogen ions of the phosphoric acid or phosphonic acid, monoalkyl phosphate or monoalkyl phosphonic acid or monohydrogen phosphate or monohydrogen phosphonic acid with other ions (e.g., alkali metal ions, ammonium ions, etc.) can be carried out to reduce the effect of doping.

[0190] Ion exchange can be performed after the polymerization of the polythiophene compound. Ion exchange can be performed simultaneously with the purification operations described above, or it can be performed before or after the purification operations. For example, when purifying by filtration, if the ion exchange resin is already loaded into the column used for filtration, ion exchange can be performed simultaneously with the purification by filtration.

[0191] As an ion exchange method, conventionally known ion exchange methods can be used.

[0192] For example, if an acidic aqueous solution is used, ion exchange can be performed by contacting the polymerized polythiophene compound product with the acidic aqueous solution. Specifically, ion exchange can be performed, for example, by stirring the polythiophene compound product in the acidic aqueous solution and reacting a portion of the phosphate or phosphonate salt present in the polythiophene compound product with hydrogen ions in the aqueous solution. When increasing hydrogen ions to enhance the doping effect, it is preferable to use an acid in excess relative to the acidic substituents of the polythiophene compound product. To reduce the doping effect, the amount of acid used can be reduced. In other words, the doping effect can be set to any level depending on the amount of acid used. Furthermore, the reaction time between the polythiophene compound product and the acid can also be set to any time.

[0193] For example, if an ion exchange resin is used, ion exchange can be performed by contacting the polythiophene compound product with the ion exchange resin in water. When increasing hydrogen ions to improve the doping effect, a strongly acidic cation exchange resin is preferred. When reducing hydrogen ions to decrease the doping effect, a strongly basic cation exchange resin is preferred. Any method can be used to contact the polythiophene compound product with the ion exchange resin. For example, an ion exchange resin column can be filled to allow a solution containing the polythiophene compound product to flow through the column, or the ion exchange resin can simply be placed in a container and the solution containing the polythiophene compound product can be placed in the container. Furthermore, when contacting the polythiophene compound product with the ion exchange resin, the container can be shaken, or the solution can be stirred to improve its efficiency. The contact time between the polythiophene compound product and the ion exchange resin can be set to any time. For example, if a small amount (e.g., a droplet) of the polythiophene compound product solution is allowed to flow into the column, this time is set to the period from when the small amount of solution has contacted the top of the ion exchange resin to when the solution leaves the bottom of the ion exchange resin. For example, if a large amount of polythiophene compound product solution is allowed to flow into the column, the time is set as the average of the time from the first portion of the solution contacting the top of the ion exchange resin to the first portion leaving the bottom of the ion exchange resin and the time from the last portion of the solution contacting the top of the ion exchange resin to the last portion leaving the bottom of the ion exchange resin. Alternatively, when the ion exchange resin and the polythiophene compound product solution are placed in a container, the time is set as the time period for mixing the solution and the ion exchange resin in the container.

[0194] The time used for a single ion exchange operation on the polythiophene compound product (e.g., the contact time between the polythiophene compound product and the aforementioned acidic aqueous solution or the contact time between the ion exchange resin and the polythiophene compound product) is set arbitrarily according to the desired degree of ion exchange. For example, the time is preferably 5 seconds or more, more preferably 10 seconds or more, further preferably 1 minute or more, and even more preferably 10 minutes or more. If the contact time is too short, the ion exchange tends to be insufficient. In addition, it is preferable to have 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 preparation process will take a long time, which will reduce the preparation efficiency.

[0195] There is no particular limitation on the number of ion exchange operations. Although ion exchange can be completed by performing one ion exchange operation on the polythiophene compound product, it can also be repeated two or more times. If repeated two or more times, a polythiophene compound with a high doping effect can be easily obtained. Specifically, it is preferable to repeat 3 or more times, more preferably 4 or more times, and even more preferably 5 or more times. In addition, the number of ion exchange operations is preferably 20 or fewer times, more preferably 15 or fewer times, and even more preferably 10 or fewer times. If the number is too high, the entire preparation process will take a long time, which will reduce the preparation efficiency.

[0196] In addition, when performing two or more ion exchange operations, the same ion exchange operation can be repeated two or more times, or two or more types of ion exchange operations can be performed.

[0197] In a preferred embodiment, the ion exchange operation can be combined with a purification operation as a series of steps. For example, by adding an acidic aqueous solution to the polythiophene compound product for ion exchange, followed by a purification step (e.g., centrifugation) to remove water and the like, and recovering the polythiophene compound with increased purity, a polymer with high doping efficiency and high purity can be obtained. Furthermore, the series of steps combining the ion exchange and purification operations can be a cycle, and this cycle can be repeated multiple times. For example, by repeatedly adding an acidic aqueous solution to the polythiophene compound product for ion exchange, followed by a purification step (e.g., centrifugation) to recover the polythiophene compound with increased purity, adding an acidic aqueous solution again after the first purification for a second ion exchange, and then performing another purification step to recover the polythiophene compound with further increased purity after the second purification, a polymer with very high doping efficiency and high purity can be effectively obtained. In other words, a polymer with high purity and high conductivity can be obtained efficiently. There is no particular limitation on the number of repetitions of the cycle consisting of a series of steps including ion exchange and purification operations. Specifically, the process is preferably repeated 3 or more times, more preferably 4 or more times, and even more preferably 5 or more times. Furthermore, the cycle is preferably repeated 20 times or less, more preferably 15 times or less, and even more preferably 10 times or less. Too many repetitions will result in a long preparation time, reducing efficiency.

[0198] (Amine compounds) As the amine compound included in the composition of the present invention, an amine compound consisting of nitrogen atoms, carbon atoms, and hydrogen atoms can be used. The number of nitrogen atoms in the amine compound is preferably 5 or less, more preferably 3 or less, further 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, further preferably 9 or less, and particularly preferably 6 or less. Furthermore, compounds with 5 or fewer carbon atoms, compounds with 4 or fewer carbon atoms, and compounds with 3 or fewer carbon atoms can also be selected.

[0199] Amine compounds can be compounds composed of nitrogen atoms and hydrocarbon groups, compounds composed of nitrogen atoms, hydrogen atoms, and hydrocarbon groups, and compounds having a ring structure (heterocyclic structure) composed of nitrogen atoms and carbon atoms. Furthermore, the heterocyclic structure can be an aliphatic ring structure or an aromatic ring structure. The hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. That is, amine compounds can be aliphatic amines or aromatic amines. However, aliphatic amines are preferred.

[0200] Aliphatic amines can be primary, secondary, or tertiary amines. The alkyl group in an aliphatic alkylamine preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 4. In one embodiment, the number of carbon atoms is 1 to 2, and in another embodiment, the number of carbon atoms 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, toluene, and xyleneamine. Examples of aliphatic compounds having a ring structure consisting of nitrogen and carbon atoms include piperidine, pyrrolidine, etc. Examples of aromatic compounds having a ring structure consisting of nitrogen and carbon atoms include pyridine, methylpyridine, dimethylpyridine, trimethylpyridine, imidazole, 4-dimethylaminopyridine, etc.

[0201] The compositions of the present invention comprise at least one of the above-described amine compounds, and may also comprise two or more of the above-described amine compounds.

[0202] (solvent) If desired, the compositions of the present invention contain a solvent. The solvent can be an inorganic solvent or an organic solvent. Preferably, a solvent capable of dissolving both the amine compound and ammonia is preferred. In a preferred embodiment, the solvent is water. Since ammonia is a gas at room temperature, dissolving it in a solvent (e.g., water) to form an ammonia solution (e.g., an aqueous ammonia solution) and using it facilitates its mixing with the polythiophene compound. Furthermore, when a compound that is a gas at room temperature is also used as an amine compound, dissolving it in a solvent (e.g., water) to form an amine compound solution (e.g., an aqueous amine compound solution) and using it facilitates its mixing with the polythiophene compound. When a compound that is a liquid at room temperature is used as an amine compound, ammonia can be dissolved in the amine compound and the solution used. When a compound that is a gas at room temperature is used as an amine compound, it is preferable to dissolve the amine compound in a solvent (e.g., water) and use the solution.

[0203] (Preparation of the composition) The compositions of the present invention can be prepared by mixing a polythiophene compound, an amine compound, ammonia, and a solvent as desired. There are no particular restrictions on the order of mixing.

[0204] In one embodiment of the invention, when a solvent is used in the composition, 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. The mixture, the amine compound solution, and the ammonia solution are then mixed. The order of mixing is not particularly limited. The ammonia solution can be added to the mixture of the polythiophene compound and the solvent, followed by the amine compound solution. Alternatively, the amine compound solution can be added to the mixture of the polythiophene compound and the solvent, followed by the ammonia solution. Or, the amine compound solution and the ammonia solution can be added simultaneously to the mixture of the polythiophene compound and the solvent. Furthermore, the amine compound solution and the ammonia solution can be pre-mixed to prepare a mixed solution, which is then added to the mixture of the polythiophene compound and the solvent.

[0205] (pH of the composition) If 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. Additionally, the pH is preferably 12 or lower, more preferably 11 or lower, and even more preferably 10 or lower. When the pH is too high or too low, it may be difficult to obtain the desired shape during molding.

[0206] (Mixing ratio) Relative to the total amount of amine compounds and ammonia contained in the composition of the present invention, the molar ratio of the amine compounds is preferably 1 mol% or higher, more preferably 5 mol% or higher, further preferably 10 mol% or higher, particularly preferably 15 mol% or higher, and may also be 20 mol% or higher if desired. Additionally, the molar ratio of the amine compounds is preferably 99 mol% or lower, more preferably 95 mol% or lower, and further preferably 90 mol% or lower. Possible ranges for the molar ratio of the amine compounds include, for example, 1 mol% to 99 mol%, and this range 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 proportion of the amine compounds is too low or too high, the effect of improving conductivity will be reduced.

[0207] (Other additives) The compositions of the present invention may contain other additives without impairing the effects of the invention. Other additives include those commonly used in the art, such as basic compounds, for example amine compounds and metal hydroxides other than those described above, and dopants such as polystyrene sulfonic acid.

[0208] (Method for manufacturing conductive products) In one aspect, the present invention relates to a method for manufacturing a conductive article. The method includes the steps of preparing the above-described composition and molding the composition. In one embodiment, prior to the composition preparation step, a step of polymerizing a monomer corresponding to a polythiophene compound is performed to obtain a polythiophene compound as a solid polymer. By performing the molding step, the solid polymer is shaped into the desired shape of the conductive article. It should be noted that, in this specification, "monomer corresponding to a polythiophene compound" refers to a monomer in which the relationship between the polythiophene compound and the monomer is such that the polymerization of the monomer yields the polythiophene compound.

[0209] (Molding steps) The composition of the present invention is used in the step of molding a conductive article. As a molding step, any known method for molding conductive articles can be used. Specifically, polythiophene compounds obtained by polymerization generally cannot be used as conductive articles in their original shape. Therefore, methods for molding to process into a desired shape (e.g., a film) are known. The composition of the present invention can be used in known molding methods. In this specification, the step of processing a polythiophene compound obtained by polymerization into a desired shape is described as a molding step. Furthermore, the method for cases where the desired shape is a film, i.e., the step of processing the polymerized polythiophene compound into the shape of a film, is described as a film-forming step. For example, a film can be formed by coating the composition of the present invention onto a smooth surface of a substrate and allowing it to dry.

[0210] (Conductive products) In one aspect, the present invention relates to a conductive article obtained by molding the aforementioned composition for molding. The conductive article obtained by molding the aforementioned composition for molding exhibits high conductivity. It is believed that even higher conductivity can be obtained during molding through the synergistic effect of amine compounds and ammonia on polythiophene compounds.

[0211] Depending on the purpose, molded conductive articles can be used as either final products or intermediate products. For example, a film obtained through molding can be used as a final product, such as an antistatic film. When an article is used as an intermediate product, further processing steps, such as attaching it to another component, are then performed to manufacture the final product.

[0212] (Impossible or unrealistic situations) In conductive articles obtained by molding the compositions 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. Theoretically, if a significant amount of specialized analytical equipment were used, far exceeding the typical R&D costs of a company, and the analysis were conducted over an extremely long period, it would be possible to confirm the amount of each of the amine compounds or substances derived from amine compounds and ammonia or substances derived from ammonia present in the conductive articles. However, due to the first-to-file principle of patent law, there is an urgent need to file an application. Therefore, it is impossible to conduct analysis over a very long period. Furthermore, from a common-sense perspective, it is impossible to confirm the amount of each of the amine compounds or substances derived from amine compounds and ammonia or substances derived from ammonia within the budget that a company can afford for R&D. Therefore, for conductive articles obtained by using and molding the compositions of the present invention, there are situations where direct identification of the structure is impossible or impractical.

[0213] (application) Conductive articles formed using the compositions of the present invention can be used in a variety of applications, commonly referred to as applications of conductive polythiophene compounds. That is, conductive articles can be used in any conductive article manufactured using conductive polymers. Specific examples of applications for conductive articles include, for example, antistatic agents, transparent electrodes, organic thin-film solar cells (e.g., hole transport layers), organic EL, secondary batteries, antistatic agents, electrode materials for solar cells, plastic electrodes, EMI materials, organic ferromagnets, electrochromic materials, and various sensors (e.g., touch sensors, etc.). Conductive articles can be components in capacitors, while in one embodiment, conductive articles are conductive articles other than components in capacitors.

[0214] (Antistatic agent) As a method for using conductive articles molded using the compositions of the present invention as antistatic agents, various known methods can be used, in which conventional conductive polythiophene compounds have been used as antistatic agents. For example, the compositions of the present invention are coated onto a substrate and dried, thereby forming a conductive film on the substrate and imparting an antistatic effect to the substrate surface. Examples of substrates include any solid material requiring antistatic properties. Specific examples include, for example, polymer films, polymer fibers, polymer resin molded articles, etc.

[0215] As a coating method for the polythiophene compound of the present invention, any method that uses conventional methods for coating substrates with polythiophene compounds can be used. Specific examples include, for example, spin coating, dip coating, etc.

[0216] (Solar cells) 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, as a hole transport layer in a solar cell.

[0217] As a method for manufacturing solar cells, conventional and known solar cell manufacturing methods can be used. For example, a method of laminating each layer of the solar cell can be used. More specifically, a method including the steps of forming a hole transport layer of a material comprising the polythiophene compound of the present invention, and forming other layers constituting the solar cell, etc., can be used. As the material for forming the hole transport layer, the composition of the present invention can be used, and it can be shaped into the desired shape (e.g., a thin film).

[0218] [Example] The present invention is described below with reference to embodiments, but the present invention is not limited to any of the embodiments.

[0219] Preparation Example 1 (Synthesis of Thiophene Monomer) Using the method described in Example 3 of Japanese Patent Publication No. 6912060, paragraph 0145, a thiophene monomer represented by the following formula (5) was obtained.

[0220] [Chemical Formula 5]

[0221] Polymer Preparation Example A (Synthesis of polythiophene compound, i.e., polymer A) A mixture of 0.3 g (1.27 mmol) of the thiophene monomer obtained in Example 1, 2.86 g (5.08 mmol) of ferric sulfate (III) nonahydrate, and 4.6 ml of dilute sulfuric acid was added and stirred at 5 °C ± 5 °C for 7 hours. Hydrochloric acid was added to the resulting mixture to remove the precipitated solid, which was then washed with acetone and dried under reduced pressure to obtain a dark blue solid.

[0222] 12 ml of water and 20 ml of 2M etidronic acid were added to the obtained dark blue solid. The mixture was stirred at room temperature (20°C to 25°C) for 2 hours. Subsequently, the filtered solid was washed with acetone and dried under reduced pressure to obtain 0.26 g of the polythiophene compound represented by formula (6). The polymer obtained in this preparation example is referred to as "polymer A" below.

[0223] [Chemical Formula 6] (6) Polymer Preparation Example B (Synthesis of polythiophene compound, i.e., polymer B) A mixture of 7 g (29.6 mmol) of the thiophene monomer obtained in Example 1, 66.7 g (119 mmol) of ferric sulfate (III) nonahydrate, and 121 ml of water was added and stirred at 5 °C ± 5 °C for 7 hours. Hydrochloric acid was added to the resulting mixture. The precipitated solid was removed, washed with acetone, and dried under reduced pressure to obtain a dark blue solid.

[0224] 280 ml of water and 463 ml of 2M etidronic acid were added to the obtained dark blue solid. The mixture was stirred at room temperature (20°C to 25°C) for 2 hours. The filtered solid was then washed with acetone and dried under reduced pressure to obtain 6.0 g of the polythiophene compound. The chemical formula of this polythiophene compound is the same as that of formula (6) above. The polymer obtained in this preparation example is referred to below as "polymer B".

[0225] (Example 1) (Preparation of aqueous solution) An ammonia solution containing ammonia and an alkaline aqueous solution containing trimethylamine (TMA) were prepared. These aqueous solutions were added to a mixture of 20 mg of polythiophene compound (polymer A) and water, such 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 solution for film formation.

[0226] (Forming a conductive polymer film) A circular frame with a diameter of 1 cm was fabricated on an alkali-free glass substrate using polyimide tape. This was used as the test substrate. A film was prepared within the circular frame on the test substrate by drop casting using 20 μL of the aqueous solution described above for film formation. The film was then heated and dried on a hot plate.

[0227] (Conductivity measurement) The conductivity was calculated using the following formula. The surface resistance was measured using a low resistivity meter (Nittosiko Analytech Co., Ltd., LORESTA-GX MCP-T700) via the 4-point probe method, and the film thickness was measured using a film thickness meter (Mitsutoyo, High-Accuracy Digimatic Micrometer MDH-25MB).

[0228] Electrical conductivity (S / cm) = 1 / (Surface resistivity (Ω / □) × Film thickness (cm)) The results are shown in Table 1.

[0229] (Examples 2 to 5) Except for changing the molar ratio of ammonia to trimethylamine (TMA) as shown in Table 1, an alkaline aqueous solution was prepared similarly to that in Example 1. An aqueous solution for membrane formation was prepared similarly to that in Example 1, the thin film was prepared, and its conductivity was measured.

[0230] (Comparative Example 1) Except for preparing an alkaline aqueous solution containing only trimethylamine (TMA), an aqueous solution for forming the film was prepared similarly to that in Example 1. The thin film was prepared, and its conductivity was measured.

[0231] (Comparative Example 2) Except for preparing an alkaline aqueous solution containing only ammonia, an aqueous solution for forming the film was prepared similarly to that in Example 1. The thin film was prepared, and its conductivity was measured.

[0232] [Table 1]

[0233] TMA: Trimethylamine (Considerations regarding Examples 1 to 5 and Comparative Examples 1 to 2) The conductivity of Comparative Example 1, which uses only trimethylamine, is 136 S / cm, while the conductivity of Comparative Example 2, which uses only ammonia, is 90 S / cm. Therefore, it is naturally expected that if trimethylamine and ammonia are used in combination, a conductivity value between them (i.e., 90 to 136 S / cm) should be obtained.

[0234] However, in Examples 1 to 5, where trimethylamine and ammonia were mixed, the measured conductivity values ​​were 138 to 176 S / cm. These values ​​are higher than the expected values ​​of 90 to 136 S / cm, and particularly in Examples 1 to 4, these values ​​were 150 S / cm or higher, significantly higher. That is, in Examples 1 to 5, it was confirmed that high conductivity levels were achieved that would not have been expected from a common-sense perspective.

[0235] (Examples 6 and 7) The alkaline aqueous solution was prepared similarly to that in Example 1, except that ammonia, monomethylamine (MMA), and dimethylamine (DMA) were used in the molar ratios shown in Table 2. The aqueous solution for film formation was prepared similarly to that in Example 1, except that polymer B was used instead of polymer A. Thin films were prepared, and their conductivity was measured.

[0236] (Comparative Example 3) Except for preparing an alkaline aqueous solution containing only monomethylamine (MMA), an aqueous solution for forming the film was prepared similarly to that in Example 6. Thin films were prepared, and their conductivity was measured.

[0237] (Comparative Example 4) Except for preparing an alkaline aqueous solution containing only ammonia, an aqueous solution for forming the film was prepared similarly to that in Example 6. The thin film was prepared, and its conductivity was measured.

[0238] (Comparative Example 5) Except for preparing an alkaline aqueous solution containing only dimethylamine (DMA), an aqueous solution for forming the film was prepared similarly to that in Example 6. The thin film was prepared, and its conductivity was measured.

[0239] [Table 2]

[0240] MMA: Monomethylamine DMA: Dimethylamine (Considerations regarding Examples 6 to 7 and Comparative Examples 3 to 5) The conductivity of Comparative Example 3, which uses only monomethylamine, is 58 S / cm, and the conductivity of Comparative Example 4, which uses only ammonia, is 52 S / cm. Therefore, it is naturally expected that if monomethylamine and ammonia are used in combination, a conductivity value between them (i.e., 52 to 58 S / cm) should be obtained.

[0241] However, in Example 6, where a mixture of monomethylamine and ammonia was used, a conductivity of 63 S / cm was measured. This value is significantly higher than the expected value of 52 to 58 S / cm. In other words, Example 6 demonstrated a remarkably high conductivity that would not be expected from a common-sense perspective.

[0242] The conductivity of Comparative Example 5, which uses only dimethylamine, is 46 S / cm, while the conductivity of Comparative Example 4, which uses only ammonia, is 52 S / cm. Therefore, it would be natural to expect that if dimethylamine and ammonia are used in combination, a conductivity value between them (i.e., 46 to 52 S / cm) should be obtained.

[0243] However, in Example 7, where dimethylamine and ammonia were used in combination, a conductivity of 60 S / cm was measured. This value is significantly higher than the expected 46 to 52 S / cm. In other words, Example 7 demonstrated a remarkably high conductivity that would not be expected from a common-sense perspective.

[0244] Industrial applicability This invention provides a composition for molding conductive articles with high conductivity and a method for molding conductive articles. Conductive articles molded using the composition of this invention can be used as components of various conductive products. The conductive articles can be applied to a variety of applications, such as antistatic agents, condensers, organic electroluminescent materials (ELs), secondary batteries, capacitors, antistatic agents, solar cells, electrode materials for plastic electrodes, EMI materials, organic ferromagnets, electrochromic materials, and various sensors.

[0245] As described above, the present invention has been illustrated by way of preferred embodiments. However, the invention should not be construed as limited to such embodiments. It should be understood that the scope of the invention should be interpreted solely based on the claims. It should be understood that those skilled in the art can realize equivalent scopes based on the description of the specific preferred embodiments of the invention and common general knowledge. It should be understood that any patents, patent applications, and references cited herein are incorporated herein by reference in the same manner as their contents are specifically described herein.

Claims

1. A composition for molding conductive articles, wherein the composition comprises a polythiophene compound, an amine compound, and ammonia. The polythiophene compound comprises structural units represented by the following general formula (A): [Chemical Formula 1] ,in L is represented by equation (21): [Chemical Formula 21] Where R 5 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, R 6 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, n 1 n is either 0 or 1. 2 n is an independent integer from 1 to 6. 3 n is independently 0 or 1. 4 The integer is between 0 and 12, and the left-hand side of formula (21) is bonded to the carbon atom in the dioxane ring of formula (A). M 1 and M 2 Each is independently an alkyl group or a hydrogen atom having 1 to 15 carbon atoms. R 1A It is a hydrogen atom, alkyl, alkoxy, acyl, or a group represented by formula (15): [Chemical Formula 15] Where L 1 Equation (22) represents: [Chemical Formula 22] Where R 15 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, R 16 Independently, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m 1 m is 0 or 1 2 m is an independent integer from 1 to 6. 3 Independently 0 or 1, m 4 The integer is between 0 and 12, and the left-hand side of formula (22) is bonded to the carbon atom in the dioxane ring of formula (A). M 1c and M 2c Each is independently an alkyl group or a hydrogen atom having 1 to 15 carbon atoms. Amine compounds are composed of nitrogen, carbon, and hydrogen atoms. The condition is that the conductive material is not a component used in a capacitor.

2. The composition according to claim 1, further comprising a solvent.

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

4. The composition according to 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, wherein the alkyl group in the amine compound is a straight-chain or branched alkyl group having 1 to 4 carbon atoms.

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

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

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

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

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

11. The composition according to claim 9, wherein, In the polythiophene compound, n 1 It is 0, n 2 It is 1, n 3 It is 0, and n 4 It is 1.

12. A conductive article formed using the composition of any one of claims 1 to 11, wherein the conductive article is not used as a component in a capacitor.

13. A conductive article formed using the composition of any one of claims 1 to 11, wherein the conductive article is in the form of a film, provided that the conductive article is not used as a component in a capacitor.

14. A method for manufacturing a conductive article, comprising the steps of preparing a composition according to any one of claims 1 to 11 and molding the composition to obtain a conductive article, wherein the 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 the polythiophene compound contained in the composition to obtain the polythiophene compound, wherein the step of obtaining the polythiophene compound is performed prior to the step of preparing the composition.

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