TW201229086A - Conductive composition and method for producing conductive coating film - Google Patents

Abstract

Provided is a conductive composition that can produce a conductive coating film having a high conductivity and low corrosiveness. The composition contains a sulfur trioxide complex and a substituted polythiophene of which at least a portion of the thiophene repeating units are substituted at the 3-position and/or the 4-position of the thiophene ring by at least one group selected from the group consisting of: a polyether group having 1-9 repeating units of an oxyalkylene group having 2-4 carbon atoms and of which one terminal is an alkyl group having 1-15 carbon atoms; an alkoxy group having 1-15 carbon atoms; an alkoxyalkyl group having 1-19 carbon atoms; and an alkyl group having 1-15 carbon atoms or said alkyl group of which a hydrogen atom has been substituted with the polyether group. The composition can be used as a conductive composition for a solid electrolyte capacitor.

Description

201229086 DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a conductive composition. More specifically and in detail, the Ming system is composed of a conductive polymer and a chemical structure of (4), a conductive composition, a solid electrolytic electrode using a conductive composition, and a conductive composition. A solid electrolytic capacitor: a method for producing a conductive film formed by a conductive composition. [Prior Art] In recent years, attempts have been made to open a conductive polymer compound which can be guided at a low temperature on a flexible substrate [and are expected to be applied to a conductive functional material, a light-emitting functional material, and a photoelectric conversion functional material. Conventionally, it has been known that a conductive polymer which provides a conductive film is preferably doped with a compound having a acid group (for example, reference materials and 2). In the patent literature, there is a water-dispersible colloidal coating liquid which uses benzene benzene acid as a dopant. However, the coating liquid has a high hydrophilicity, and the conductive coating made of the coating liquid absorbs moisture. The problem is higher, and there is a problem that the strong acidic hydrogen ions generated by the absorption of f are corroded by the metal in contact with the film, etc. The conductivity of the conductive film obtained by using the coating liquid is about (10)^, and is applied to the conductive function. The conductivity required for the material is not sufficient. Further, in Patent Document 2, a method of using a polycondensation polymer compound having a sulfonic acid group as a dopant is proposed, and a film of conductivity of the fern is obtained by performing electrolytic oxidation polymerization. However, the conductivity of the conductive film obtained by using the coating liquid is about (10) S/cm, and the conductivity required for the application of the conductive functional material 3 201229086 is not sufficient. [Patent Document 1] 曰本特开平 7-90060 Bulletin

[Patent Document 2] JP-A-2007-224182 SUMMARY OF THE INVENTION An object of the present invention is to provide a conductive composition capable of producing a conductive film having high corrosivity and high electrical conductivity. The present month is a conductive composition (A) containing a substituted polyporphin (P) and a sulfur dioxide complex, and at least one of the substituted polythiophene (p) porphin repeats A is a thiophene repeating unit & ("), and the 3-position and/or 4-position of the thiophene repeating unit (〇:) is a polyether group (a) represented by the following formula (1) An alkoxy group having 1 to 15 carbon atoms (b), an alkoxyalkyl group having 2 to 19 carbon atoms (c)', and an alkyl group having 1 to 15 carbon atoms or a hydrogen atom of the alkyl group via the above polyether Substituting at least i groups of the group consisting of the substituted alkyl group (d).

OR2

In the formula CD, OR1 represents an alkyl group having 2 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 15 carbon atoms, and is an integer of i to 9. Since the conductive composition of the present invention is small in corrosion resistance, it can be applied to a metal which is liable to cause corrosion, and since the conductive film is highly conductive, it can be expected to be applied to various conductive functional materials. [Embodiment] The conductive composition (A) of the present invention contains a substituted polythiophene (p: and a sulfur trioxide complex as a dopant, and the above-mentioned substituted polybenzazole (7) is sold in a unit weight. At least part of the porphin repeat unit ("), the porphin repeats the 3rd position of the (o) oxime ring and the 4th position of the above-mentioned poly-bonding group (1), the above-mentioned methoxy group (1), the above-mentioned oxygen burning Substituting the base (c) or the above-mentioned alkyl group (4) (also referred to as "the pheno repeat unit (α)" in the specification). As shown in the above formula (1), the above-mentioned poly (a) has a repeating unit composed of a carbon number of 2 to 4 = an oxygen-extended base, and the repeating unit number is from 〜9, and the single-end is a polyether group having an alkoxy group having a carbon number of -15 to 15 carbon atoms. Examples of the oxyalkylene group include an oxyethyl group, an oxypropyl group, and an oxybutyl group. The alkoxy group having a carbon number of 1 to 15 at the terminal may, for example, be a methoxy group, an ethoxy group or a propoxy group. 4 propoxy, n-, iso-, second or third butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, ten Alkoxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, etc. The above alkoxy group (b) may be exemplified by the above polyether group (a). The same alkoxy group having 1 to 15 carbon atoms. The above-mentioned decylalkyl group (c)' may be an alkyl group having 1 to 4 carbon atoms which is substituted by an alkoxy group having a carbon number of 15 to 15. Carbon number 1 to 15 The alkoxy group may, for example, be the same as those exemplified in the above-mentioned polyfluorenyl group (a), and an alkyl group having 1 to 4 carbon atoms, and examples thereof include a mercapto group, an ethyl group, a normal or an isopropyl group, and a positive or a 2. XOR, third-party, 201229086, etc. The alkyl group (d) possessed by the repeating unit (α) may be a linear or branched alkyl group having a carbon number of j 15 , for example, methyl, or Isopropyl, normal, isomeric, second or third butyl, n- or isodecyl, cyclopentyl, n- or isohexyl, cyclohexyl, n- or heptyl, n- or isooctyl-ethylhexyl, Ortho- or isoindolyl, n- or iso-decyl, n- or iso- undecyl, n- or isododecyl, Ortho- or tridecyl, Ortho- or X-tetradecyl The base (4)' may also be a hydrogen atom of the above-mentioned alkyl group The above polyether-based (a)-substituted alkyl group. The thiophene repeating unit (α) of the substituted polythiophene (P) J in the present invention is more excellent in terms of conductivity. N is a repeating early (αΐ), a general formula (3), a seven nr^, a repeating unit represented by the following formula (2), or a repeating unit represented by the following formula (4) Repeated order indicated only (3 6 201229086

The OR3 in the above formula (2) and the oxime R6 in the formula (3) each independently represent an oxyethyl group or an oxypropyl group. From the viewpoint of conductivity, an oxyethyl group is preferred. R4, R7 and R8 in the above formulae (2) to (4) each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms (for example, fluorenyl group, n- or isopropyl group, ortho- and di- , second or third butyl, n- or isopentyl, cyclopentyl, n- or iso-hexyl, cyclohexyl, n- or isoheptyl, n- or iso-octyl, 2-ethylhexyl, n- or isodecyl , or n-isodecyl, n- or iso- undecyl and n- or iso-dodecyl). When η is 1 or more, 'as r4, it is preferably a linear or branched alkyl group having a carbon number of 1 to 6 from the viewpoint of conductivity 7 201229086. More preferably, the carbon number is 1 to 4 a direct bond or a branched base. In the case where η is 0, R4' is preferably a linear or branched alkyl group having a carbon number of 3 to 12, more preferably a linear or branched chain having a carbon number of 6 to 12, from the viewpoint of conductivity. Alkyl group. When the following m is 1 or more, R7 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms from the viewpoint of conductivity, and more preferably a linear chain having 1 to 4 carbon atoms. Or a branched alkyl group. When m is 0, R7 is preferably a linear or branched alkyl group having a carbon number of 3 to 12, more preferably a linear or branched carbon number of 6 to 12, from the viewpoint of conductivity. Alkyl group. R8 is preferably a linear or branched alkyl group having 3 to 12 carbon atoms from the viewpoint of solvent solubility and conductivity, and more preferably a linear or branched alkyl group having 6 to 12 carbon atoms. R5 in the above formula (3) represents a linear or branched alkyl group having 1 to 4 carbon atoms (for example, 'indenylene group, ethyl group, 1, 2 or 1, 3 group), and 1, 2, 1, 3, 2, 3 - or 1, 4 - butyl), preferably a linear or branched carbon number of 1 to 3 from the viewpoint of solvent solubility and conductivity The alkyl group is more preferably a methylene group or an ethyl group. η and m in the above formula (2) or (3) are each independently an integer of 〇~5. η is preferably from 1 to 5, more preferably from 2 to m, from the viewpoints of solvent solubility and conductivity, and is preferably from 观点 to 4, more preferably from 观点 to 3, from the viewpoint of solvent solubility and conductivity. The substituted polythiophene (P) in the present invention may be composed only of the above thiophene repeat 8 201229086 unit (α ), and may also contain an unsubstituted thiophene repeat unit. In the above-mentioned thiophene repeating unit (α) in the polythiophene (Ρ) substituted by the worker, the weight of the substituted polythiophene (ρ) is preferably from the viewpoint of the recombination property. It is 5 〇 to 100% by weight, more preferably 6 〇 to 1 〇〇% by weight, and particularly preferably 70 to 100% by weight. The substituted polythiophene (ρ) in the present month can be synthesized by a known method such as anionic polymerization or oxidative polymerization of a monomer corresponding to each repeating unit. The monomer corresponding to the above thiophene repeating unit (α) may, for example, be a 3-position and/or a 4-position of the thiophene ring via the above polyether group (a), the above alkoxy group (b), or the above alkoxyalkyl group ( c) or a porphin or the like in which the above alkyl group (d) is substituted and the 2nd and 5th positions are substituted with a halogen atom. The monomer corresponding to the unsubstituted thiophene repeating unit may, for example, be thiophene. The content of the substituted polythiophene (p) in the conductive composition (A) is preferably from 观点, 1 to 20% by weight based on the weight of the conductive derivative (A) from the viewpoint of the solubility. More preferably, it is 1〇~6 〇 weight. When the content of the substituted polythiophene (P) is too large, aggregates are formed and the coatability is deteriorated, which is not preferable. Further, when the content of the substituted polythiophene (p) is too small It is difficult to form a uniform conductive film, and thus it is not preferable. The regioregularity (RR) of the substituted polythiophene (p) in the present invention is usually 50% or more, and it is preferably 80 in terms of conductivity. % or more, more preferably 90% or more. The definition of the stereoregularity (RR) in the present invention will be described below. The type of the bond of the substituted polythiophene (P) is as shown in the following formula 9 201229086 ΗΤ - HT key (B 1 ), ΤΤ - HT key (B2), ΗΤ - HH key (B3), TT - HH key (B4). In addition, HT is head-to-tail and TT is tail. The tail and the head are the abbreviation of head to head.

r in the chemical formula of the above four bonding forms independently represents the above polyether group (a), the above alkoxy group (b), the above alkoxyalkyl group (c) or the above alkyl group (d). The stereoregularity (RR) of the substituted polythiophene (P) in the present invention is defined by the ratio (%) of the HT-HT bond (B 1 ) in the substituted polythiophene (P)' Calculated by the following mathematical formula (1). Stereo regularity (RR) = BlxlOO/ ( B1 + B2 + B3 + B4) ( 1 ) where B1 represents the number of HT-HT bonds, B2 represents the number of TT-HT bonds, and B3 represents HT-HH bonds The number, B4 represents the number of TT - HH keys. Specifically, since the protons possessed by these bonds represent their respective chemical shifts (δ) by nuclear magnetic resonance ("H ~ NMR"), they can be calculated from the integral values of the spikes in the chemical shifts corresponding to the four kinds of bonds. In the case of the polythio 10 201229086 phenanthrene derivative having the repeating unit (α 3 ) represented by the general formula (3), specifically, it is represented by a ΗΤ-HT bond (Bl): δ -6.98, ΤΤ-ΗΤ bond (Β2) : δ = 7.00, ΗΤ— ΗΗ key (Β3): δ = 7.02, ΤΤ- ΗΗ key (Β4): δ = 7·05. Therefore, the integral values S1, S2, S3, and S4 of the spikes in the chemical shifts specific to (Β1), (Β2), (Β3), and ((4) are calculated according to the peaks in the characteristic chemical shift of (B1). The ratio (%) of the integral value S1 to the sum of the integral values is used to calculate the stereoregularity (RR) using the following mathematical formula (2). Stereoregularity (rr ) = s 1 X 100/ ( s 1 + S2 + S3 + S4 ) ( 2 ) Furthermore, the above-mentioned NMR measurement was performed using a measuring machine: AVANcE iii4〇o type digital NMR [Bruker Bi〇 Made by Spin Co., Ltd., under the conditions of Yubei J疋/Valley. Deuterochloroform (Deuter〇chi〇r〇f〇rm) and measuring temperature: °C. The substituted polythiophene (p) of the conductive polymer acts as a dopant for the sulfur trioxide complex supply electron' together with the dopant to form a charge transfer errone 4 charge transfer complex as a carrier for electrons Conductivity is exhibited, and the higher the concentration of the sulfur oxide complex, the better, but if the concentration is too high, the conductivity is lowered. The amount of sulfur trioxide complex used is preferably 5 to 3 wt%, more preferably (7) to heavy emulsifying sulfur complex, in comparison with the substituted phenanthrene (P). Compound. Secret, & 'Sulphur dioxide complex, can be cited as oxygen thiodithioxane complex, trioxane _., IL-oxypentanol complex, sulfur trioxide-methyl ether complex, sulfur trioxide Ethyl "into IT ether sigma, sulphur dioxide diethyl ether chelate, etc.; guanamine - three gas servant MA u at wrong one stone,, · · complex, can be cited sulfur trioxide N, N - 2201229086 Methylformamide complex, etc.; - sulfur dioxide complex, which can be exemplified as ϋH complex, sulfur trioxide, — — — 氧 、 、 、, 三 三 Ν 3 °, Sulfur dioxide dimethyl sulphide sulphide complex, can be listed as a 7-amino complex, etc.: sulfur test - sulphur ethyl sulfonium sulphur _ complex: = thiol dimethyl sulphate, trioxo sulphur oxide Ethyl sulfide complex and the like. From the viewpoint of bismuth, it is preferably guanamine-sulphur trioxide:: amine-sulphur dioxide complex, sulphur oxide in decylamine-sulfur trioxide complex, Ν-dimethylformamide The compound is more preferably sulfur trioxide in the amine-sulfur trioxide complex. "Compound. The conductive composition (Α) of the present invention contains a sulfur trioxide complex as a dopant, and further contains other dopants and organic solvents insofar as the effects of the present invention are not impaired. Examples of the octane dopant include inorganic acids (sulfuric acid and nitric acid, etc.), functional ions (moth, desert chlorine, etc.), auto-ionic ions (tetrafluoro-acid and peroxyacid), and ruthenium compounds [ Gas phthalic acid, tetra-p-benzoquinone, p-benzoquinone, quinone dioxime, di-dioxanyl hydrazine (DDQ,

Dichlorodicyanoquinone), p-toluquinone, alkyl-substituted organic sulfonic acid ions (mercapto sulfonic acid, dodecyl sulfonic acid, etc.) for naphthoquinone, anthracene, gas, and p-toluquinone , a cyclic sulfonic acid ion (camphorsulfonate ion, etc.), a substituted or unsubstituted benzene or a dibasic acid ion (benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid) And benzenedisulfonic acid, etc., a ketone-substituted ionic or unsubstituted ionic (2-naphthalenesulfonic acid and 1,7-naphthalene diacid, etc.) of a naphthoic acid having 1 to 4 acid groups. , acid ionic, sulfonium sulfonate, alkyl substituted or unsubstituted benzene sulfonate ion (alkane 12 201229086 bis benzene sulfonic acid and biphenyl disulfonic acid, etc.) and substituted or not Substituted aromatic polymer sulfonic acid ions (polystyrenesulfonic acid, naphthalenesulfonic acid formaldehyde condensate, etc.). The amount of the other dopant to be used is preferably from 〇1 to 1100% by weight, more preferably from 10 to 600% by weight, based on the substituted polythiophene (P). The conductive composition (A) of the present invention may further contain an organic solvent as described above. After the conductive composition (A) is applied onto a substrate, the organic solvent may be removed by heat treatment as needed. . As an organic solvent, in order to obtain a uniform solution free of precipitates,

For the substituted "Phenyl (P) solvent and the good solvent for the dopant, D is used as the good solvent for the substituted "Ph" (p), and the carbon number of 1 to 10, 醯An amine system, an ether system, an aromatic hydrocarbon system, an alcohol system, a ketone system, and a sulfur solvent. The preferred ones are exemplified by gas-like, di-methane, and dimethylformamide-f-based materials. (hereinafter, abbreviated as), '1,3-diox〇lane, 曱 、, methyl ketone, acetone, decyl ketone 7 - butyrolactone, cyclopentanone, cyclohexanone Mixed with _. The methyl group is similar to the above-mentioned good solvent in the solution of the substituted polythiophene polythiophene (Ρ). / 〇, more preferably 5 〇 ~ 98 〇 / good solvent and substituted amount in the solution is preferably alcohol, 2-proprolactone and cyclopentanone, ethanol, 2 - good for dopants The solvent may, for example, be methanol or ethanol hydrazine-fluorenyl. In the case of a slightly biting ketone, THF, or a butyl group, it is preferably a 13 201229086 propanol and r-butyrolactone from the viewpoint of solubility stability. The content of the good solvent in the solution in which the dopant and the dopant are mixed with the dopant is preferably from 0 to 99% by weight in the solution, more preferably 98% by weight/0. @ :>υ~ will be replaced by the poly. When the phenotype is mixed with the dopant, it is preferred to separately prepare a solution of the (4) solution of the substituted polythiophene (7) and a solvent solution of the dopant, and then mix the two. When a conductive film is produced using the conductive composition (4) of the present invention, it is necessary to remove the solvents. In the case of a solvent having a relatively low boiling point, it is naturally dried, dried by heating and drying by air blowing, and the solvent is removed and dried by heat. Preferably, the conductive composition (Α) of the present invention is particularly suitable for a solid electric electrode. In the solid electrolytic capacitor, a porous film is formed by etching a film of a oxidized film, and a conductive polymer is formed on the surface of the solid electrolytic capacitor: a pole (cathode) is formed, and a capacitor is coated with a conductive polymer. The method of dispersing the liquid in the early body or the method of coating the conductive polymer H in a solvent using a dodecyl benzene sulfonate as a dopant: ::: As follows, the production efficiency of TM is U, which cannot effectively increase the capacity of the capacitor, and further causes a decrease in withstand voltage or an increase in leakage current due to doping and corrosion of the electrode. In contrast, the conductive composition of the present invention is completely dissolved in a solvent and has high conductivity. Therefore, the conductive polymer can be effectively impregnated into the porous film by a simple procedure. Capacitor capacity, 201229086 and because the dopant is not acid, there is no corrosion. After the conductive composition (A) of the present invention is applied onto a substrate and then subjected to heat treatment, an electrode for a solid electrolytic capacitor having a high withstand voltage and a small leakage current can be obtained. Examples of the method of applying the conductive composition (A) to the substrate include a spin coating method, a dropping method, a dip coating method, and a method of impregnating the substrate with the conductive composition (A). Further, examples of the substrate include plastic, glass, metal, rubber, ceramics, and paper. From the viewpoint of conductivity, the thickness of the film obtained by drying the conductive composition (A) formed on the surface of the substrate is preferably 〇〇5 to 〇〇"m, more preferably 〇" to 5 〇. In m. If the film is thinner than 〇 & 5 " claws, the conductivity of the filling knife may not be known. Further, when i 〇〇 # m is exceeded, problems such as cracking or peeling are likely to occur at the time of formation. In order to obtain a highly conductive conductive film using the conductive composition (A) of the present invention, the heat treatment temperature is preferably (10) to 19 (rc, more preferably (10) to 17 〇C. It is lower than 1 G (rc^ temperature). In the case of the case, the strength and conductivity of the filling blade may not be obtained. χ, when the temperature is higher than ΐ9〇, the conductivity may deteriorate. The heating time is based on the heating temperature and conductivity. The concentration of the polythiophene (P) in the substance (A) is appropriately selected, and is usually G·5 to 8 hours: “1 to 4 hours. If the heating time is too short, the conductive small composition may be used... The conductivity of the obtained conductive film is insufficient. The conductive bismuth-acid and the conductive composition (A) are excellent in conductivity because of the dopant contained in the conductive composition (A), and can be simply used by the simple 2 15 201229086 cloth. Making a conductive film, so there is ffl. Especially by simple steps

Therefore, it is useful to make the conductive Η 八 7 7 A A 同 同 同 同 同 含 含 含 含 含 含 含 含 含 含 含 含 含 含 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ [Examples] The present invention will be further described by way of examples and comparative examples, but the present invention is not limited thereto. Hereinafter, parts represent parts by weight. <Manufacturing Example 1>····································································· Synthesis of tetrasyl 11 base): Sodium hydride (which is dispersed in paraffin at a concentration of 6 〇 wt%) 6 〇 Disperse in N,N-didecylamine 5 〇 And 36.9 parts of triethylene glycol monoterpene ether was added dropwise thereto. The reaction solution foamed and became cloudy. After the completion of the foaming, 24 parts of 3-bromothiophene and copper bromide (work) were added to the reaction solution in this order. The reaction solution was heated to i 1 〇〇c and allowed to react for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and 5 parts of a liquefied aqueous solution of lm 〇 1 / L was added thereto, and the mixture was transferred to a separating funnel using 50 parts of ethyl acetate, and then the aqueous layer was separated. Further, the organic layer was washed twice with 30 parts of distilled water, and then ethyl acetate was evaporated to give 3 (1,4,7,10-tetraethoxyundecyl)thiophene. (2) Synthesis of 2'5-two deserts-3-(1,4,7,1〇-tetraoxyundecyl) porphin: The above 3-(1,4,7,1〇-tetraoxide 7 parts of undecyl)thiophene and n-bromosuccinimide (brom〇succinimide) 1〇7 parts were dissolved in thf 16 201229086 parts and reacted at room temperature for 2 hours. 50 parts of ethyl acetate was used and the precipitate was removed with a glass filter, and THF and ethyl acetate were evaporated. The obtained mixture was purified using a silica gel column, whereby 10.5 parts of 2,5-dibromo-3-(1,4,7,10-tetraoxaundecyl)thiophene was obtained. (3) Synthesis of poly[3-(1,4,7,10-tetraoxyundecyl)thiophene]: The above 2,5-dibromo-3-(1,4,7,10-four After dissolving 8.1 parts of oxygen undecyl)thiophene in 150 parts of thF, 21 parts of a 1 mol/L methyl magnesium bromide THF solution was added, and the mixture was reacted at 75 Torr for 30 minutes. To the reaction solution, 0.1 part of [1,3-bis(diphenylphosphino)propane]-dicarburized nickel (II) was added, and further reacted at 75 ° C for 5 hours. After the reaction solution was left to cool to room temperature, 20 parts of sterol was added. After distilling off the solvent, the reaction mixture was transferred to a Soxhlet extractor, and washed with 150 parts of decyl alcohol and 150 parts of hexane. Finally, the residue was extracted with 150 parts of chloroform, and the solvent was evaporated to give a poly[3 - (1,4,7,10-tetraoxy-J-alkyl) ° thiophene] (P - 1 ) 3 _ 1 part. The stereoregularity calculated by the above method using 1H-NMR was 96.3%. &lt;Production Example 2&gt;: Synthesis of poly[3-(1,4,7,10,13,16,19-heptaoxaeicosyl) porphin] (p-2) in a production example In (1), the same experimental operation as in Production Example 1 was carried out except that triethylene glycol monoterpene ether was changed to hexaethylene glycol monoterpene ether (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain a stereoscopic rule. The content was 95.1% of poly[3-(1,4,7,10,13,16,19-heptadecanecosyl)thiophene] 2.9 parts. Further, when triethylene glycol monoterpene ether is changed to hexaethylene glycol monomethyl ether, the molar ratio of the reaction component and the weight of the non-reactive component (solvent, etc.) 17 201229086 ratio and the case of the production example 1 The experimental operation was carried out by adjusting the amount of each raw material in the same manner. &lt;Production Example 3&gt;: Synthesis of poly(3-heptyloxythiophene) (p-3) In (1) of Production Example 1, triethylene glycol monomethyl ether was changed to 1 - heptanol, except The same experimental procedure as in Production Example 1 was carried out, and 2.7 parts of poly(3-heptoxythiophene p-3) having a stereoregularity of 95.4% was obtained. &lt;Production Example 4&gt;: Synthesis of poly{3-(2,5-dioxaheptyl)thiophene} (P-4) (1) 3 -Bromomethyl "Synthesis of phenotype·· 3 - Methyl group Thiophene [manufactured by Tokyo Chemical Industry Co., Ltd.] 5 parts (50.9 mmol), N-bromosinium imine 9.97 parts (56.0 mmol), diphenylmethyl hydrazine peroxide [manufactured by Tokyo Chemical Industry Co., Ltd.] 〇.12 parts (〇5〇mmol) After dissolving in 30 parts of benzene, the temperature was raised to 1 Torr.匚 and react for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and a 1 M aqueous sodium thiosulfate solution was added and transferred to a separating funnel, and then the aqueous layer was separated. Further, the organic layer was washed twice with 30 parts of distilled water, and then benzene was distilled off to obtain 3.32 parts (35.7 mmol). (2) Synthesis of 3-(2,5-dioxyheptyl)thiophene:

3.54 parts (39.3 mm 〇l) of 2 ethoxyethanol was dissolved in THF, and sodium hydride (dispersed in 60% paraffin) was added thereto. The above 3, methyl plug force 6.32 parts (35_7mmol) was dissolved in 15 parts of THF,

Si: Force 2: Raise i ^ and react for 4 hours. After the reaction was completed, the separated aqueous layer was poured into a 3 G portion and transferred to a separatory funnel, and the organic layer was further subjected to two times using 30 parts of distilled water: 18 201229086 After the net, the THF was distilled off and the column was used. The obtained mixture was purified, whereby 5.68 parts of 3-(2,5-dioxaheptyl)thiophene (3〇5 mm〇1) was obtained. (3) Synthesis of 2,5-dibromo-3-(2,5-dioxopentyl)thiophene: 5.68 parts of the above 3-(2,5-dioxoheptyl)thiophene (3〇5mm〇1) And N_edge number ί 白亚亚fe 11.9 wound (67.1 mmol) was dissolved in THF and reacted at room temperature for 2 hours. 50 parts of ethyl acetate was used and the plate was removed with a glass transitioner, taking care of THF and acetic acid. The selected mixture was purified using a gel column to obtain 8.11 parts (23.6 mmol) of 2,5-dibromo-3-(2,5-dioxoheptyl)thiophene. (4) Synthesis of poly{3 -(2,5-dioxaheptyl)thiophene}: 811 parts (23.6 mmol) of the above 2,5-dibromo-3-(2,5-dioxoheptyl)thiophene After dissolving in 30 parts of THF, 25 parts of methyl oxalate THF solution was added, and the mixture was reacted at 75 ° C for 30 minutes. To the reaction solution, 0.13 parts of [^3-bis(*·-base scale) propylidene]--one mouse chemistry (II) was added, and further reacted at 75 ° C for 2 hours. After the reaction solution was left to cool to room temperature, 5 parts of methanol was added. The reaction mixture was transferred to a Soxhlet apparatus, and washed with 150 parts of methanol and 150 parts of hexane. Finally, the residue was extracted with 15 parts of a gas mixture and the solvent was distilled off to obtain 2.85 parts of poly{3 - (2 - 5 -dioxyheptyl)thiophene} (P-4) having a stereoregularity of 94.6%. &lt;Production Example 5&gt;: Synthesis of poly(3--f&quot;dimercaptothiophene) (P-5)

In (3) of Production Example 1, 2,5-dibromo~ 3 - (i,4,7,10-tetraoxyundecyl)thiophene was changed to 2,5-dibromo- 3-12 The alkyl thiophene (manufactured by Aldrich Co., Ltd.) was subjected to the same experimental procedure as in Production Example 1 to obtain a poly(3- 12-yard σ-septene) having a stereoregularity of 96.4% (P 19 201229086 - 5 ) 3.5 Share. &lt;Examples 1 to 1 6 &gt; The substituted polythiophenes (P-1) to (P-5) obtained in Preparation Examples 1 to 5 prepared in Table 1 were prepared, and Table 1 The sulfur trioxide complex compound and the organic solvent are shown, whereby the conductive compositions (A-1) to (A-16) of the present invention are obtained. 20 201229086 【1^】 α-.ν) 5sq1 UJV) 孓8- (τ·ν) (9I-V) 0.1

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Is •2&quot; 〇 〇 -&gt; - 1 066 ο.ζε 62 9Ί&quot; 〇 〇 z&quot; '0 0·66 ι·6κ 〇 〇 0m

LI ns 8053 〇 〇 ο-ει 〇 〇 β 5 -- 12 〇 〇 6·ε L-l 6·Ι β 〇 〇 ? 0n

LI •3ε εε- me 〇 〇 - 2

Inch-I -6- 〇〇psz 56.0 9.9s 〇〇ττ Lz 5 !·εο々〇〇1 •6 6-0 ri 〇〇-&gt; - Ll 0- &lt;β 〇〇oe - If 咖 珀»-ΛΙζ·Ν lt?q5w ~&quot;'f ssd/loa3d 珐8^!4»-农ϊίν^Μ--Ι I5ch丨卜呛宇硪6-—2 svlii *钕(ετ/)6* 8 (Ε3/$)φ^* (ΖΗ o'-/J^)1^1^^^ (Λ)Butterfly OOI/GE)85^»5 (φ 蝌1! every |汝尨_*| e 201229086 &lt;Comparative Example 1> Preparation of substituted polythiophene (p-1) 1 oxime, 0. 3 parts of gas phthalic acid and 30.0 parts of 1,3-dioxolane as an organic solvent, thereby obtaining Comparative conductive composition (A'-1). <Comparative Example 2 &gt; Known "PEDOT/PSS" of an aqueous dispersion of polybenzazole (Baytro-P manufactured by HC Starck; 3, 4 - Conductive polymer obtained by polymerizing ethylene dioxetane in a high molecular weight polystyrene sulfonic acid aqueous solution) is directly used as a comparative conductive composition (A·-2) » &lt;Comparative Example 3 &gt; 1.0 part of substituted polythiophene (P-1), 2.7 parts of p-p-benzenesulfonate, 32.3 parts of 1,3-dioxolane as organic solvent, and 8.4 parts of decyl alcohol Thus, a comparative conductive composition was obtained. (A' to 3) The conductive compositions (A-1) to (A_16) of Examples 1 to 16 and the comparative conductive composition (A'-1) were used. (A'-3) A conductive film was produced, and the conductivity was evaluated by the following method. The results are shown in Table 1. [Method for Producing Conductive Film] The conductivity of Examples 1 to 16 was measured using a doctor blade. The composition (A - 丨) ~ (A - 16) and the comparative conductive composition (A, - n~ J , A - 3 ) were applied to a glass substrate to have a rectangular pattern of 3 cm x 7 cm, and dried at room temperature under reduced pressure. After 3 minutes, at 17 η: heating using a hot plate for 60 minutes to obtain a film. [Electrical evaluation method] According to JIS Κ 7 194 "Resistance of a conductive plastic using a resistive method 22 201229086 test method" The surface resistance of the obtained conductive film was measured. Then, the film thickness of the conductive film was measured using a laser microscope (VK-87〇0 manufactured by Keyence Corporation), and the conductivity of the conductive film was calculated from the surface resistance and the film thickness. Conductive composition of ~16 (A-丨)~(A-16) Comparative conductive composition (A.—丨)~(A,_3) 1〇mL was placed in a glass granulator to immerse the ITO-attached glass substrate (icmxicmxO.lmm) in the solution and the glass container Closed. Store at a temperature of 25. After storing and maintaining the tube for 150 hours, remove the glass substrate with IT〇 and wash it with THF. The corrosion state of the surface of the ruthenium-attached glass substrate after washing was observed with a microscope (digital microscope VHX manufactured by Keyence Co., Ltd.), and evaluated according to the following criteria. The results are not shown in Table 1. &lt;Corrosion evaluation criteria&gt; 〇 (No worms were observed) χ (visible corrosion) 々 Table 1 * The conductive composition of the present invention showed no rotification. [Method for Evaluating Capacitor Characteristics] (1) Preparation of a dielectric film on an anode, impregnation as an anode metal (size: 4×3.3 mm): 3 wt% aqueous ammonium adipate solution, used Strange current clamp voltage supply: put the voltage from Q v to (4) under the condition of 0.53mA/see, add: 4. The formation voltage of the voltage is 4 〇 minutes, and the surface of the R surface is etched to form a dielectric film formed by oxidation. After washing with deionized water 23 201229086 for Η), it was dried for 1 minute at lQ5t to prepare an anode composed of an anode metal and a dielectric film. The obtained obtained was impregnated into the above-mentioned (4) aqueous solution, and the electrostatic electricity was measured at _z, and the value of 4.2 &quot; F was set as the theoretical electrostatic capacitance.谷(2) Preparation of electrodes for solid electrolytic capacitors The anode is immersed in the conductive composition (A - < A-16) and (A, ~Ad), and after removal, 'drying at room temperature for % min. Thereby, an electrolyte layer was formed to produce an electrode for a solid electrolytic capacitor. (3) The electrolytic capacitor was fabricated in the above-obtained electrolyte layer ± coated carbon-burning [Varniphite Fu manufactured by Nippon Graphite Co., Ltd.] and dried, and then coated with silver paste [Manufactured by Nippon Graphite Co., Ltd. "EveryGhmME"] and dried to form a cathode. Pull out the lead connection terminals from the silver paste. (4) Measurement and evaluation The electrostatic capacitance of the obtained electrolytic capacitor at 12 Hz and the internal resistance at 100 kHz were measured by an LCR meter, and the presence or absence of leakage and withstand voltage were evaluated according to the following criteria. &lt;Evaluation Criteria for Leakage&gt; When the measurement is performed by the LCR meter, the leakage current is not lowered, the capacitance cannot be measured, and the internal resistance is set to χ, and the leakage current is lowered to measure the capacitance and the internal resistance. The situation is set to 〇. &lt;Evaluation Criteria for Withstand Voltage&gt; Using a DC power supply device [GP0650 to 05R manufactured by Takasago Manufacturing Co., Ltd.], a voltage was applied in a low current mode of 0.2 mA, and the voltage was automatically boosted, and the voltage when the voltage 24 201229086 was lowered was set as the withstand voltage. The solid electrolytic capacitor of the conductive composition can obtain a value close to 4.2 μ F ) with a relatively low internal resistance. On the other hand, in the capacitor used in Comparative Example 1, since the dopant was an acid, the electrode leakage was large and measurement was impossible. In addition, in the case of using the comparative example 2, the present invention was used as a capacitor for the theoretical electrostatic capacitance (the conductive composition inside the conductive composition is corroded, and the conductive composition for the bulk electrolytic capacitor is used as the capacitor, since the conductivity is still The molecule is present in the solution as a dispersion, and the soil is caused inside the void, and the method is filled with a secondary conductive polymer. Therefore, the internal resistance is high, and only about 1/10 of the theoretical electrostatic capacitance is obtained. In Comparative Example 3, the capacity was insufficient and the internal resistance was also large. Further, the withstand voltage was also lower than that of Examples i to i6. As shown in Table 1, the conductive composition of the present invention showed a higher value. Conductivity The conductive composition of the present invention has a low corrosivity, so that it can be coated with a metal which is susceptible to corrosion, and since the conductive film is highly conductive, it can be expected to be applied to various conductive functions. Material, especially as an electrode for solid electrolytic capacitors. [Simplified description of the diagram] Benefit [main component symbol description]

Claims (1)

201229086 VII. Patent application scope: 1. A conductive composition (A) containing substituted polythiophene (P) and sulfur trioxide complex, wherein the substituted polythiophene (p) is in a repeating unit of thiophene At least a portion is a thiophene repeating unit (α), and the thiophene repeating unit (α) is at the 3-position and/or 4-position of the thiophene ring selected from the group consisting of polyether groups (a) represented by the following formula (1), and carbon number Alkoxy group (b) of 1 to 15 , alkoxyalkyl group (c) having 2 to 19 carbon atoms, and an alkyl group having 1 to 15 carbon atoms or a hydrogen atom of the alkyl group via the above polyether group (&amp; Substituting at least one of the groups consisting of the substituted alkyl group (d), -U〇R1-J__〇r2 (1) [wherein, OR1 represents an alkylene group having a carbon number of 2 to 4, and R2 represents a carbon number. 1 to 15 of the alkyl group, k is an integer of 1 to 9]. 2. The conductive composition according to item i of the whistle patent, wherein the thiophene repeating unit is a repeating unit (Η) represented by the formula (7), a repeating unit (α2) represented by the formula (7) or a formula (4) Repetitive units indicated (α 3 ), 26 201229086 [wherein, OR3 and OR6 are each independently (indicating that an oxy-ethyl or oxy-propyl group R, R7 and R8 each independently represent a straight or branched alkyl group having a carbon number of i to 12] R5 represents a carbon number The linear or branched extension base, ^ and πι are each independently an integer of 〇~5.] J is a conductive composition of the cloth, wherein the early (α 1) system (2) OR3 is a thiol-extended ethyl group, and the square material is a linear or branched alkyl group having a carbon number of 3 to 12, and is a straight or branched chain having a carbon number of 1 to 6. The alkyl group is reset in the early position (α 2 ) is Fu + h, ei ^ , ^ wherein R in the formula (3) is an alkyl group of a straight gold branch having a carbon number of 1 to 3, and a fluorene R6 alkoxy group is an ethyl group. When m is 0, 27 201229086 is a direct bond or a bond of a bond of 3 to 12, and in the case of 1 or more, R7 is a linear or branched alkyl group having 1 to 6 carbon atoms; The unit (wherein r8 in the formula (4) is a direct bond or a branched alkyl group having a carbon number of 3 to 12. 4. The conductive composition according to any one of claims 1 to 3, Wherein the porphin repeat in the substituted polyporphin (ρ) The content of the (a) is 50 to 100% by weight in the substituted polythiophene (ρ). 5. The conductive composition according to any one of the above items, wherein the The stereoregularity defined by the percentage of the head-to-tail-to-tail bond in the substituted polythiophene (p) is 9〇% or more. 6· The conductive composition of the fourth aspect of the patent application, wherein The ratio of the head-to-tail-to-tail bond in the substituted (iv) phene (7) is more than 90%. For example, the conductive composition of the central item of items i to 3 of the patent application range, The sulfur trioxide complex is selected from the group consisting of sulfur trioxide n, n-dimethylmethanamine complex, sulfur trioxide, specific bite complex and sulfur trioxide triethylamine complex. At least one sulfur trioxide complex. 8. The conductive composition of claim 4, wherein the sulfur complex is selected from the group consisting of: rg pore-gasification &amp; N, N-dimethyl Basementamide mismatch: medium: Li bite complex and sulfur trioxide triethylamine complex formed in the group to ^ 1 kind of sulfur dioxide 9. The conductive composition of the chemical composition of claim 5 is selected from the group consisting of trioxoporous, sulfur trioxide (tetra) complex; oxime; dimethyl amide In the erroneous group, the sulphur trioxide is sulphuric acid sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphur sulphide At least one sulfur trioxide complex in the group consisting of sulfur trioxide, N,N-diindenyl, decylamine, sulfur trioxide W complex, and sulfur trioxide triethylamine complex. The conductive composition of any one of claims 1 to 3, wherein the content of the sulfur trioxide complex based on the weight of the substituted polythiophene (p) is 5 to 300% by weight. . 12. The conductive composition of claim 4, wherein the content of the sulfur trioxide complex based on the weight of the substituted polyfluorene- _ &amp; 5 to 300% by weight. 13. The electrically conductive composition of claim 5, wherein the substituted composition is based on the substituted composition. The content of the sulfur trioxide complex of the weight of the phenotype (P) is 5 to 300% by weight. 14. The conductive composition of claim 6, wherein the content of the sulfur trioxide complex based on the weight of the substituted polysphene (P) is from 5 to 300% by weight. The conductive composition according to claim 7, wherein the content of the sulfur trioxide complex based on the weight of the substituted polyporphin (P) is 5 to 300% by weight. The electroconductive composition of the eighth item, wherein the content of the sulfur trioxide complex of the basis weight is 16. 5 to 300% by weight of the substituted polythiophene (P) as claimed in the patent application. 17. The conductive composition of the substituted polypyrrole (p) 9 according to the patent application, wherein the content of the sulfur oxide complex of one of the monomers 29 201229086 is 5 to 300% by weight. The conductive composition according to the first aspect of the invention, wherein the content of the sulfur trioxide complex based on the weight of the substituted polyporphin (P) is 5 to 300% by weight. . 19. An electrode for a solid electrolytic capacitor, which is obtained by using the conductive composition according to any one of claims 1 to 3. 20. A solid electrolytic capacitor obtained by using the conductive composition according to any one of claims 1 to 3. A method for producing a conductive film, comprising the step of applying a conductive composition according to any one of claims 1 to 3 to a substrate, followed by heat treatment. 30