TW201111428A - Conductive composition - Google Patents

Abstract

Disclosed is a conductive composition which contains a solvent, a p-conjugated conductive polymer that is doped with a dopant and dissolved in the solvent, and a phenolic compound that has an LD 50 of 500 mg/kg or more and is represented by formula (X) (wherein R1 represents a group having a function of donating electrons to the benzene ring in formula (X)). In the conductive composition, the weight ratio of the phenolic compound to the p-conjugated conductive polymer (phenolic compound (kg)/p-conjugated conductive polymer (kg)) is 0.01-10.0.

Description

201111428 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an electrically conductive composition. [Prior Art] As the conductive polymer, polyaniline or the like is a well-known material. In addition to its electrical properties, polyaniline has an advantage that it can be relatively easily synthesized from inexpensive aniline and exhibits excellent stability to air or the like in a state in which conductivity is exhibited. As a method for producing polyaniline, a method of performing electrolytic oxidative polymerization of aniline or an aniline derivative or a method of performing chemical oxidative polymerization is known. In the electrolytic oxidation polymerization, Patent Document 1 or Patent Document 2 describes a method of polymerizing aniline on an electrode. A film excellent in electrical characteristics and the like can be obtained by electrolytic oxidation polymerization. However, in general, compared with chemical oxidative polymerization, it is expensive to manufacture, is not suitable for mass production, and it is also difficult to obtain a molded body of a complicated shape. On the other hand, in order to obtain a conductive polymer of an aniline or an aniline derivative by chemical oxidative polymerization, it is usually necessary to add a doping to a polyaniline in a non-conductive basic state (so-called emeraldine base state). Protonation by doping agent. However, since the polyaniline in a non-conductive basic state is hardly soluble in most of the organic solvent, it is not suitable for industrial production. Further, the conductive polyaniline (so-called emeraldine base state) formed after protonation is substantially insoluble and infusible, and it is difficult to easily produce a conductive composite material and a molded body thereof. Under such circumstances, there are several proposals for the addition of polyaniline which improves the non-conductive alkali state to 149505.doc 201111428 =, = doped conductive polyaniline for organic solvents. For example, Non-Patent Document 1 describes organic solvent properties such as __acid, camphorsulfonic acid (CSA h-'mound and abundance; ae 咖 aeid). . The protonic acid is used as a dopant. The electrical properties of the present invention are excellent. For example, a method in which a sulfonated sulfonic acid is used as a dopant and a polyaniline in a f-test state is dissolved in a mica is described. In Document 2, for example, a method is described in which a non-conductive alkali state is used as a dopant in a special solvent (fan-type strong acid) of 2,2-dichloroethane. Polyaniline is used as a dopant, for example, as described in Patent Document 2, using 2,2-monoacetic acid as a solvent and sulfosuccinic acid as a dopant. Doping of the non-conducting test state. j Φ is reported in Patent Document 5: it is substantially not mixed with water. The two-phase polymerization system of the cold agent and water _, by using an anionic surfactant as a The dopant ' can easily obtain the doped polyaniline. *, and, and the electrical properties such as the electrical conductivity of the molded article of the conductive polyaniline obtained by the methods are not necessarily excellent. Patent Document 1: Patent Document 1: Japanese Patent Laid-Open No. Hei. No. 62-230825 No. I49505.doc 201111428 Patent Document 2: Japanese Patent Laid-Open No. Hei 62-149724 Patent Document No. 3: Japanese Patent Laid-Open No. Hei 7-703 No. Document 4: Japanese Patent Laid-Open Publication No. 2003-183389 Patent Document 5: International Publication W005/052058 Non-Patent Document Non-Patent Document 1: Synthetic metals, 48, 1992, 91-97 Non-Patent Document 2: J. Phys.: Condens. Matter, 10, 1998, 8293-8303 [Invention] In view of the above circumstances, an object of the present invention is to provide a conductive composition capable of forming a conductive molded body having a high electrical conductivity. According to the present invention, the following conductive composition and the like are provided. The solvent includes a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and a phenol having an LD50 of 500 [mg/kg] or more and represented by the following formula (X). Sex compound: [Chemical 1]

OH

(X) (wherein h is a group having a function of providing an electron to the benzene ring in the formula (X)); a weight ratio of the above phenolic compound to the above π-conjugated conductive polymer 149505.doc 201111428 (phenol The compound [kg]/兀 conjugated conductive polymer 叱]) is 〇〇1 to 1〇〇. 2. A conductive composition 'at least using the following (4) to (4) as a raw material: (a) a solvent; (8) dissolved in the above (4) by (4) (4) to (4) a conductive polymer; LD50 is 500 [mg/kg] or more and is composed of the following formula (8): [Chemical 2]

OH

Ri (X) R1 is a group having a function of providing an electron to the benzene ring in the formula (X); a heavy compound of the compound (4) and the above π-conjugated conductive polymer (b) [kg] /7t total light conductivity is divided into ι.ιη~1〇〇. 3 two kinds of conductive compositions' comprising: a solvent, a π-conjugated conductive high-doping agent doped with a dopant, and a compound represented by the following formula (2) : [Chemical 3]

149505.doc (2) 201111428 (wherein R2 is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group having a carbon number of 1 to 20); the above phenolic compound is the same as the above The weight ratio of the yoke-based conductive polymer (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 〇〇丨 丨〇〇 丨〇〇. 4. A conductive composition comprising at least the following (a) to (c) as a raw material: (a) a solvent; (b) a π-co-electrical conductivity doped with a dopant dissolved in the solvent (c) a compound represented by the following formula (2): [Chemical 4]

(wherein R 2 is a condensed group having a carbon number of 1 to 20, a dilute group, a cyclodecyl group, an aryl group, an alkyl group or an aryl group); and the above phenolic compound (c) is electrically conductive with the above π The weight ratio of the polymer (b) (phenolic compound [kg] / 7c total conductive polymer [kg]) is 0.01 to 10.0. 5. The conductive composition of 3 or 4 wherein the phenolic compound (c) has an LD50 of 500 [mg/kg] or more. 6. The conductive composition according to any one of 1 to 5, wherein the doped ruthenium-based conductive polymer is a protonated substituted or unsubstituted polyaniline, protonated Substituted or unsubstituted polypyrrole, or substituted or unsubstituted poly(pf) 149505.doc 201111428. The singer is the one who is in charge. 7. The conductive composition according to any one of 1 to 6, wherein the dopant of the π-co-ductive conductive polymer is an organic acid. 8. The conductive composition according to any one of 1 to 7, wherein the π-conjugated conductive dopant is a succinic acid represented by the following (XX): M (03SCH) (CH2C〇〇Ri2)c〇〇Rl3)m (χχ) (In the formula (XX), Μ is a hydrogen atom, an organic radical or an inorganic radical, m is a valence of ruthenium, and R and R are each independently a hydrocarbon group or The group represented by _(R 4〇)r_Rl5 is a fluorenyl group or a fluorenylene group 'R" is a hydrogen atom, a hydrocarbon group or a group which is represented by a group, and R 6 is a hydrocarbon group, and three R 丨 6 may be the same Also, r is an integer of 1 or more ;). 9. The conductive composition according to any one of 1 to 8, wherein the weight ratio of the phenolic compound to the solvent (phenolic compound [kg] / solvent [kg]) is 0.0004 or more and 0. 7 5 or less. A conductive laminate comprising: a substrate; and a conductive layer produced from the conductive composition according to any one of 1 to 9, which is laminated on the substrate. 11. The conductive laminate according to 10, wherein the substrate is a resin film. A conductive article obtained by subjecting a conductive laminate such as 10 or 11 to molding. A hair cultivator which is produced by using the conductive composition according to any one of 1 to 9. 149505.doc -8 · 201111428 14. A conductive film which is formed by molding a compound such as 1 to 9. Conductive group of the item 15. A conductive film which is formed by molding any of 丨 to 9. - Conductive Combination of Items - A conductive article obtained by mixing a composition of ruthenium to ruthenium 9 and a substrate. Any one of the conductive groups 17. The conductive composition and the π-conjugated conductive high-concentration phenolic compound represented by the following formula (1): [Chemical 5] ΟΗ

OR (wherein, R is an alkylaryl group or an aralkyl group having 1 to 2 carbon atoms); an alkenyl group, a cycloalkyl group, an aryl group, an alkyl group, and the above-mentioned sulfonium compound (4), a conductive polymer The weight ratio (phenolic compound / π conjugated conductive polymer) is 〇〇 1 〇〇; the π conjugated conductive polymer Α knife is substituted or unsubstituted in the protonation of horse meal Aniline; the above-mentioned π-conjugated conductive polymer is a sputum-stained product which is doped with an organic sulfonic acid. According to the present invention, an electroconductive composition capable of forming a conductive molded body having a high electrical conductivity from 曰丄 * $ can be obtained. [Embodiment] 149505.doc 201111428 The first conductive composition of the present invention comprises a solvent, a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and 5 〇 0 [mg /kg] or more, and a phenolic compound represented by the following formula (χ). The weight ratio of the phenolic compound to the ruthenium conjugated conductive polymer (phenolic compound [kgj/π conjugated conductive polymer [kg]) is 〇 〇 1 to 1 〇 〇 :

(In the formula, Ri is a group having a function of supplying electrons to a benzene ring in the formula (X). In the invention, the doped π-conjugated conductive polymer is dissolved in the composition in the composition. Solvent: Here, the term "dissolution" means that the ruthenium-based conductivity is uniformly dissolved in a solvent in a molecular unit, whereby when the conductive composition is dried, a grain-free boundary and uniformity can be obtained. A film of a yoke-based conductive polymer. The so-called LD50 is a median lethal dose, and when half of the rats are administered to a large mouse (orally ingested), half of the rats are killed during the test. , means the amount of death in 5% of the rats administered, relative to the amount of body weight (mg/kg). In contrast, the graph of the dose-mortality is plotted based on the data of the animal experiment. The amount equivalent to the mortality rate of 5〇〇/0 (LD5〇) can be obtained. The above refers to the LD50 disclosed in the product safety data sheet of Tokyo Chemical Industry Co., Ltd., for the product of Tokyo Chemical Industry Co., Ltd. 149505.doc 201111428 Full Data Sheet The phenolic compound has an LD50 of 500 [mg/kg] or more, and an LD50 of, for example, 30,000 [mg/kg] or less. The base having a function of supplying electrons has a substance having a function of supplying electrons. A group which functions to supply electrons to the benzene ring in the formula (X) to increase the electron density in the benzene ring, and examples thereof include a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group. An alkoxy group such as an oxy group, an ethoxy group or a propoxy group, or an aryloxy group such as a phenoxy group. The phenolic compound represented by the formula (X) has an LD50 of 500 [mg/kg] or more. LD50 is a value of 500 [mg / kg] or more and its LD50 value, for example, 3-methoxyphenol has an LD50 value of 597, 4-methoxyphenol has an LD50 value of 1600, and a third amyl phenol. The value of LD50 is 1830, and the value of LD50 of 3-phenoxy phenol is 5,000. The second conductive composition of the present invention is produced by using at least the following (a) to (c) as raw materials. The weight ratio of the phenolic compound (c) to the following τι conjugated conductive polymer (b) (the compound [kg]/7i total conductive polymer [kg]) is 0.01-10. .0 : (a) a solvent; (b) a π-conjugated conductive polymer doped with a dopant dissolved in the solvent; (c) LD50 of 500 [mg/kg] or more, and a phenolic compound represented by the formula (X): [Chemical 7] 149505.doc -11 - (X> 201111428

(wherein R! is a group having a function of providing an electron to the benzene ring in the formula (X)). The third conductive composition of the present invention comprises a solvent, a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and a phenolic compound represented by the following formula (2). The weight ratio of the above-mentioned ruthenium compound to the above π-conjugated conductive polymer (phenolic compound [kg] / 7t conjugated conductive polymer [kg]) is 〇 〇 1 to 1 〇 〇 : [Chem. 8]

(2) Aryl group, alkane (wherein, Rs is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, a aryl group or an aryl group). The fourth conductive composition of the present invention is produced by using at least the following (a) to (c) as raw materials. The weight ratio of the following aged compound (4) to the following 4-electroconductive polymer (8) (phenolic compound [kg] / 7t conjugated lightning-conducting molecule [kg]) is 0.01-10.0: (a) solvent Highly conductive (b) a conjugated conjugate system doped with a dopant dissolved in the above solvent 149505.doc 12 201111428; (c) a phenolic compound represented by the following formula (2): ]

XOR2 (wherein R2 is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or a aryl group) having a carbon number of 20. The LD50 of the compound (c) in the above-mentioned third and fourth conductive compositions is preferably 5 〇〇 [mg/kg] or more. The LD50 is, for example, 30,000 [mg/kg] or less. The fifth conductive composition of the present invention is characterized by comprising a phenolic compound represented by the following formula (1) and a π-conjugated conductive polymer. The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound/π-conjugated conductive polymer) is 〇.〇1 to 1〇〇, and the ruthenium-conjugated conductive polymer For the protonated substituted or unsubstituted polyaniline, the above ruthenium conjugated conductive polymer is doped with an organic sulfonic acid: [Chemical 10]

(1) (wherein R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a decyl group, an aryl group, or a aryl group 149505.doc 201111428 aryl or aralkyl group). By using the above phenolic compound, a conductive composition having a high electrical conductivity can be obtained. X, the above compounds are non-toxic and odorless. Therefore, it is different from m-cresol or the like. The above phenolic compound can be suitably used for industrial production of a conductive composition. With respect to the rule of the above formula (1) and the formula (7), examples of the alkyl group having a carbon number U0 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a third butyl group. As the base group, those having an unsaturated bond in the molecule of the above-mentioned alkyl group may be mentioned. Examples of the cycloalkyl group include cyclopentane and cyclohexane. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkylaryl group and the aralkyl group include a group obtained by combining the above alkyl group and an aryl group. Among the such groups, 'preferably methyl or ethyl. In the formula (X), the substitution position of _〇 in the formula (1) and the _〇 in the formula (2) is preferably a meta position or a para position. Thereby, the steric hindrance of the hydroxy group can be reduced to obtain a composition having higher conductivity. The first to fifth conductive compositions are preferably a weight ratio of the above-mentioned test compound to the above-mentioned refrigerant (the compound (kg)/solvent is preferably (10) or more and 0.75 or less. More preferably, Q. 45 or less. The conjugated system contained in the third to fifth conductive compositions of the invention is electrically conductive: the molecule 'preferably has a weight average molecular weight of 】, and more preferably 疋 1,000 to 1, 〇〇 149,〇〇〇. 149505.doc 14 201111428 Specific examples of the upper and the common-type conductive polymer include substituted polyaniline, poly-, poly-porphin, poly-p-phenylene, poly-p-acetylene And such derivatives, etc. : A total of a group of electrically conductive polymers is doped with a dopant as an electron accepting substance such as a Brilliant acid or a Lewis acid. Here, the 'degree of doping' is mixed. The doping ratio is usually defined by (the number of moles of dopant molecules in the conductive polymer) / (monomer unit of the conductive polymer). When the conductive polymer is a polyaniline composite, the doping ratio a of the dopant is 'this case' It refers to a dopant which is doped with respect to two molecules of nitrogen. It is preferable that the conductivity is at the earliest in the vicinity of the value and the value, and the nitrogen and the atom are contained in the marriage and the conductive polymer. In the case of (=), it is preferred that the composition of the present invention satisfies the formula 2.2$S1/N1S〇.7...(xxx) = rubbing by the above-mentioned dopant contained in the composition ^ The total number of moles of the sulfur atom of the total light-producing molecule is 总计 is the total of the number of moles of the conjugated conductive high-nitrogen atom which is doped by the above-mentioned dopant of the composition I 3 . The 兀 兀 导电 导电 由 由 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Here, the molded body can be obtained by the following method: "5 〇〇g of an electric polymer such as a light-based or doped sputum by a dopant" is dissolved in bismuth benzene, and is cracked. Conductivity 冽疋 solution. As shown in Figure 149505.doc 201111428 1 by the formation of indium tin oxide on the surface (IT〇, indium_

Tin Oxide) The upper surface of the glass substrate 1 of the electrode 2 was coated with a conductivity measuring solution of 1 μm. Specifically, the coating is carried out by a spin coating method. Here, the coating by the spin coating method was carried out under a nitrogen atmosphere. Further, the spin coating method was carried out by dropping the solution for measuring conductivity to the glass substrate, and the glass substrate was rotated for 15 seconds. Further, the glass substrate rotation speed of the spin coating method was 5 rpm, and then the glass substrate was dried to form a π-conjugated polymer film. Here, the drying is carried out under a nitrogen atmosphere. Also, the drying time was 5 minutes. Further, the drying temperature was 80. (The molding system herein refers to a molded body of a π-conjugated conductive polymer formed on a glass substrate. Further, the conductivity can be obtained, for example, by drying the π-conjugated polymer film. Then, as shown in FIG. 2, the portion of the terminal of the π-co-rolling polymer film 3 covering the ruthenium electrode is 'cut off' in a nitrogen atmosphere to make the terminal of the ιτο electrode exposed to the surface. The terminal of the electrode of the exposed surface is used. The conductivity is measured by a four-terminal method using a resistivity meter manufactured by Mitsubishi Chemical Corporation. In the present invention, the doped π-co-roller conductive polymer is preferably replaced by protonation or not. Any of the substituted polyaniline, the protonated substituted or unsubstituted polypyrrole, or the protonated substituted or unsubstituted ★thiophene, particularly preferably substituted by protonation Or unsubstituted polyaniline. When the π-conjugated conductive polymer is polyaniline, the polyaniline 149505.doc • 16 · 201111428 The weight average molecular weight is preferably 20,000 or more, more preferably a 疋5 Hey, hey 00 If the weight average molecular weight of the polyaniline is less than 20,000, the strength or elongation of the conductive article obtained from the composition is lowered. Further, the molecular weight distribution is, for example, 1.5 to 10_0 or less. In other words, it is preferable that the molecular weight distribution is small, but in terms of the solvent, the seat and the formability in the solvent, there is also a case where the molecular weight distribution is good. The above molecular weight and molecular weight distribution of S can be borrowed. The measurement is carried out by gel permeation chromatography (GPC 'Gel Permeation Chromatography). Examples of the substituent of the substituted polyaniline include a linear or branched hydrocarbon group such as a methylene group, a hexyl group or an octyl group, and a methoxy group. A oxyl group such as a oxyoxy group such as a oxyoxy group or a carbonyl group such as a carbonyl group such as a fluorene group, etc. - The dopant which is suitably used in the present invention is an organic sulfonic acid, as long as it has an acidity of eight to make the conjugated conjugate conductive. When a carrier is produced by a polymer, it is used in a particularly limited manner. Examples of the catalyst include a sulfonic acid such as methanesulfonic acid and B-acid, and H-benzoic acid and isopropyl group. Aromatic acid such as naphthine Or the acid (4). It may also be a salt of such i (sodiumated gas, etc.). These dopants are known to control the conductivity of the conjugated conductive polymer by changing its structure. Solubility in a solvent (Japanese Patent No. 3384566). In the present invention, the most suitable dopant can be selected according to the required characteristics of various uses. One car is good, and the above-mentioned redundant conjugated conductive polymer is used. The succinic acid-based doping represented by (η): 149505.doc 201111428 M(03SCH(CH2C00R12)C00R13)m (XX) (In the formula (XX), 'M is a hydrogen atom, an organic radical or an inorganic radical, The valence of 'R】2 and R" are independently a hydrocarbon group or a group represented by _(Ri4〇)r_R!5, R14 is a hydrocarbon group or a alkylene group, and Ri5 is a hydrogen atom, a hydrocarbon group or represented by R163Si- Further, Ri6 is a hydrocarbon group, and three may be the same or different, and r is an integer of 1 or more. In the conductive composition of the present invention, the weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound/π-conjugated conductive polymer) is 0.01 to 10.0, that is, 0.01 or more, 1〇. 〇The following. When the shape of the phenolic compound is not reached, there is a case where the effect obtained by adding a phenolic compound is not sufficiently exhibited. Further, if it exceeds 10.0, the strength of the film obtained from the composition may be lowered. If it is within this range, the composition ratio can be arbitrarily set according to the required characteristics of various uses, and from the viewpoint of balance between conductivity and film strength, it is preferably 〇. 5 to 5.0. In the conductive composition of the present invention, the weight ratio of the feed compound to the π-co-light conductive polymer is, for example, 2.5 or more and 5.〇 or less, and 2 or more and 4.0 or less. Further, the composition of the present invention contains a solvent in addition to the above phenolic compound and the conjugated conjugated conductive ruthenium molecule. The solvent may be an inorganic solvent or an organic solvent, and an organic solvent may be used, for example, a coating for forming a conductive film, or the like. The organic solvent may be a water-insoluble organic solvent in which it is not mixed with water (water-immiscible organic solvent). "As a water-immiscible organic solvent", for example, a stupid, a stupid 149,505.doc •18·201111428 J, a second, a hydrocarbon solvent such as tetralin, methylene chloride, chloroform, tetrachlorinated b = ethyl bromide, A chloroform-containing solvent such as tetrachloroethane or the like, and a vinegar such as ethyl acetate or the like is chilled. Among these solvents, the solubility of the doped i-form amine is preferably ethyl acetate.疋甲本-甲本, 气仿,三氯乙炫 and as a water-soluble organic solvent, examples include: alcohols, _, methyl ethyl ketone and the like, n soils, 虱 喃, 呤a polar ether such as an alkane, an aprotic polar solvent such as N-methylpyrrolidone, etc. In an organic solvent, it is preferably a mass ratio of 99 to 5 〇:1 to 5 Å using a water-non-tailing organic solvent and A mixed organic solvent of a water-soluble organic solvent, whereby the gel or the like can be prevented from being formed when the composition of the present invention is stored. {The water-immiscible organic solvent in combination with the organic solvent can be used with low polarity = Machine solvent. For example, toluene or chloroform is preferred. Further, as a water-soluble organic solvent for mixed organic agents A highly polar organic solvent can be used. For example, methanol, ethanol, isopropanol, 2-methoxyethanol, 2-ethoxyethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like are preferred. Hydrogen: B. The ratio of the π-conjugated conductive polymer in the organic solvent depends on the type of the organic solvent, and is usually 900 g/L or less, preferably 〇〇1 to 3 〇〇g/L or less. If the content of the conjugated conductive polymer is too large, the solution state cannot be maintained, and it is difficult to perform the operation for molding the molded body, and the uniformity of the molded body and the molded body, thereby causing electrical properties of the molded body or On the other hand, if the content of the π-conjugated conductive high score 149505.doc 201111428 is too small, it is only possible to form a film by the method of the next method. It is difficult to manufacture a conductive film of a uniform sentence. For example, the composition of the present invention is, for example, 1 weight μ 壬. / 里里/〇u, 15 weight. / 〇 or more, 45 weights / 〇 、 ! ! ! ! ! ! 3 3 3 3 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 、 、 In addition to these components, the effect of the present invention is not impaired (4). The composition of the present invention may contain other resins, inorganic materializing agents, etc. 』 Other resins such as adhesive substrates or plastics The compounding agent, a matrix substrate, and the like are added, and specific examples thereof include, for example, polyolefin such as polyethylene oxide or polypropylene, chlorinated polyolefin, polystyrene, polyester, polyamine, and polycondensation. Aldehyde, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyoxyalkylene, polyacrylic acid, polyacrylic acid vinegar, methacrylate, polyvinyl alcohol, etc. Preferably, gasification polymerization An olefin may be used in place of a resin to form a thermosetting resin precursor such as an epoxy resin, an amino phthalate resin or a phenol resin, or may be used together with a resin. The inorganic material is added to improve strength, surface hardness, dimensional stability, and other mechanical properties, and examples thereof include silica, titania, and alumina. The hardening agent is added to increase the strength, such as surface hardness, dimensional stability, and other mechanical properties. Specific examples thereof include a thermosetting agent such as a resin, and an acrylate monomer. A light-curing agent or the like which is formed by a photopolymerizable initiator. 149505.doc 201111428 j匕j is added to the mechanical property 4 such as tensile strength or bending strength, and specific examples thereof include, for example, a specific example. : phthalic acid g| class or phosphates, etc. The composition of the present invention can be produced by a known method, for example, by the method disclosed in WO 05/052058. Conductivity can be obtained from the composition of the present invention. The molded article of the present invention is applied to a substrate having a desired shape such as a glass or a resin film, a sheet #, a non-woven fabric, or the like, and is a (four) agent, whereby the film can be coated with a conductive film. Conductive laminated body (surface conductive article). For example, # is obtained by a known method such as vacuum formation into M or dust forming, and the conductive laminated body of the present month is cured into a desired shape to obtain conductivity. From the viewpoint of molding, the substrate is preferably a resin thin material. As a method of coating the composition on the substrate, a washing method, a spray method, a dip coating method, a knife method, or a rod coating method may be used. A known general method such as a method, a spin coating method, an electrospinning (eIeCtr) spinning method, a screen printing method, or a gravure printing method. When the coating film is dried, the coating film may be heated depending on the type of the solvent. The heating is carried out at a temperature of 25 Torr below t, preferably at a temperature of 50 to 200 ° C, and further heated under reduced pressure as needed. The heating temperature and the heating time are not particularly limited as long as The material to be used may be appropriately selected. Further, for example, a conductive film can be produced by removing a solvent from the composition of the present invention. When the molded body of the present invention is a film or a film, the 149505.doc 21 S - 201111428 nm~5 The thickness of the 0 μηι range crack is generally 1 mm or less, preferably 1 Å. The thickness of the film in this range is advantageous in that it is not easily produced during film formation. Further, the composition of the present invention may also be The substrate is mixed to form a conductive article. Examples of the substrate include polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamine, polyacetal, and polycarbonate. , thermoplasticity of polyethylene glycol, polyoxyethylene #, polyacrylic acid, acryl vinegar 'polymethacrylate, polyvinyl alcohol, etc., or thermosetting properties such as epoxy resin, phenol resin, urethane resin Further, the composition of the present invention can also be formed into a self-supporting molded body free from a substrate. In the case of forming a self-supporting molded body, it is preferred that a molded article having a desired mechanical strength can be obtained if the composition contains the above other resin. EXAMPLES Production Example 1 [Production of Polyaniline Complex 1] 18 g of hydrazine (sodium diisooctyl sulfosuccinate) was dissolved in decene %, and the solution was poured into 5 〇〇 mL under a nitrogen stream. In a separate flask, 1.8 mL of aniline was further added to the solution. Thereafter, 15 〇 mL of 1 N hydrochloric acid was added to the solution, and the temperature of the solution was cooled to 5 and the internal temperature of the solution reached 5. (: When using a dropping funnel, a solution of dissolving 3.6 g of ammonium persulfate in 5 〇N hydrochloric acid was added dropwise over 2 hours. The internal temperature of the solution was maintained for 18 hours from the start of the dropwise addition. After adding 125 mL of toluene, the reaction temperature is raised to 25 and it is maintained, and the reaction is continued for 149505.doc -22·201111428 for 4 hours. Thereafter, the liquid phase is separated into two phases by standing, and the liquid phase is separated. The side of the toluene phase was washed twice with 50 mL of ion-exchanged water and once with 1 mL of 1 N hydrochloric acid to obtain a polyaniline complex (protonated polyaniline) solution. By # 5 C The paper crosses the insoluble matter contained in the composite solution and recovers the toluene solution of the polyaniline composite. The solution is transferred to an evaporator 'heated in a hot water bath at 60 ° C' and decompressed. Thereby, the volatile component was evaporated and evaporated to obtain a 1.25 g polyaniline composite. Production Example 2 [Production of Polyaniline Complex 2] (1) 3,4-Bis[(2-ethylhexyl)oxycarbonyl] Synthesis of sodium cyclohexanesulfonate under argon flow, and input of 4-cyclohexene-1,2-didecanoic acid di(2-ethylhexyl) 80 g of vinegar (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9 〇〇mL of isopropyl alcohol, and a solution of 42.3 g of water (660 mL) of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The solution was heated to reflux temperature at 80 °. 83. (: stirring for 16 hours. During the period from the start of the reflux until every 1 hour after 1 to 5 hours, then after 2 hours, after 10 hours, adding 2,2,-azo diiso) Nitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 1.66 g. After cooling the reaction solution to room temperature, it was concentrated under reduced pressure. The concentrated residue was dissolved in 1 L of ethyl acetate/hexane mixed solution, and 250 g of silica gel was added for stirring. And the solution was separated by filtration. Further, the mixture was extracted twice with a solution of 1 L of ethyl acetate in hexane, and the filtrate was combined and concentrated under reduced pressure. The solvent was purified by the solvent: ethyl acetate / hexane. The purified product was dried without sodium 149505.doc.23.201111428, and then the solvent was evaporated under reduced pressure to obtain 3,4- Sodium [(2-ethylhexyl)oxycarbonyl]cyclohexanesulfonate (Compound A of the following formula = Na salt) 52.4 g : [Chem. 11]

Compound A. (2) Production of Polyamino Amine Complex Using 2.0 g of sodium 34-bis[(2•ethylhexyl)oxycarbonyl]cyclohexanesulfonate synthesized in the above (1) instead of the production example 丨8 giA In the same manner as in Production Example 1, 1.32 g of a polyaniline composite was obtained, except that 〇T, except that the polyaniline complex obtained in Production Example 1 of 〇.1 g was re-dissolved. A solution of 5 parts by weight of rhodium/ruthenium was prepared in toluene. To this was added 〇〇2 § 4_decyloxyphenol (LD50 = 1600 mg/kg), and the mixture was stirred and stirred at room temperature for 3 minutes. This solution was formed into a film by spin coating, and formed on a substrate of IT〇 (indium tin oxide) by spin coating, and the intrinsic conductivity was measured by a four-terminal method. Specifically, about 丨mL of the solution was applied to the upper surface of the glass substrate 形成 on which the ITO electrode 2 was formed on the surface as shown in Fig. 1 . Here, the coating by spin coating is carried out under a nitrogen atmosphere. Further, the glass substrate rotation time after the solution was dropped onto the glass substrate by the spin coating method was set to 15 seconds. Further, the glass substrate rotation speed of the spin coating method was set to 5 〇〇 rpin. 149505.doc -24- 201111428 Thereafter, the glass substrate was dried to form a conductive polyaniline film. Here, the drying is carried out under a nitrogen atmosphere. Also, the drying time was set to 5 minutes. Further, the drying temperature was set to 80 °C. After drying the conductive polyaniline film, as shown in Fig. 3, the terminal of the conductive polyaniline thin layer 4 covering the IT electrode was cut in a nitrogen atmosphere. The file causes the terminals of the 1TO electrode to be exposed to the surface. The intrinsic conductivity was measured using L〇resta-GP (manufactured by Mitsubishi Chemical Corporation; a resistivity meter using a four-terminal method) using the terminal of the electrode on the exposed surface. (Example 2) A film was formed in the same manner as in Example 1 except that the amount of the addition of 4-nonyloxybenzoic acid was changed to 〇, 4 g, and the intrinsic conductivity was measured. (Example 3) A film was formed in the same manner as in Example 1 except that the amount of the addition of 4-methoxy phenol was changed to 〇 〇〇 ^ , and the intrinsic conductivity was measured. (Example 4) A film was formed in the same manner as in Example 1 except that the amount of the 4-methoxy group added was ίοg, and the intrinsic conductivity was measured. Example 5 A film was formed in the same manner as in Example 1 except that 3-methoxyphenol (LD50 = 597 mg/kg) 0.02 g was used instead of 4-methoxybenzene, and the intrinsic conductivity was measured. Example 6 A film was formed in the same manner as in Example 3 except that 3 g of 3-methoxybenzene was used, and the intrinsic conductivity was measured. 149505.doc -25- 201111428 Example 7 In the same manner as in Example 1, except that 3-phenoxyphenol (LD50 = 5000 mg/kg) 〇.2 g was used instead of 4?-methylphenol. Film formation, measurement of intrinsic conductivity. (Example 8) A film was formed in the same manner as in Example 5 except that 0.4 g of 3-phenoxyphenol was used, and the intrinsic conductivity was measured. Example 9 0.1 g of the polyphenylamine complex 2 obtained in Production Example 2 was redissolved in a solution of 5% by weight. To this was added 〇.〇2 g of 4-decyloxybenzene, and the mixture was stirred and stirred at room temperature for 30 minutes. This solution was formed into a film by a spin coating method by spin coating on an ITO (Indium Tin Oxide) substrate, and the intrinsic conductivity was measured by a four-terminal method. Comparative Example 1 A film was formed in the same manner as in Example 1 except that 4-decyloxyphenol was not added, and the intrinsic conductivity was measured. Comparative Example 2 A film was formed in the same manner as in Example 1 except that the amount of the 4-anthracene group was changed to 0.0005 g, and the intrinsic conductivity was measured. Comparative Example 3 A film was formed in the same manner as in Example 1 except that the amount of the 4-methoxy group added was 2.0 g. However, the film itself was significantly brittle and the conductivity could not be measured. Comparative Example 4 149505.doc •26- 201111428 In addition to the addition of 0.4 g of LD50 = 242 mg/kg, instead of 4-nonoxybenzene, a film was formed in the same manner as in Example 1 to determine the inherent Conductivity. The measurement results of the composition and the intrinsic conductivity of the conductive compositions of the above Examples and Comparative Examples are shown in Table 1. [Table 1] Conductive polymer second dopant intrinsic conductivity Compound name addition amount Compound name addition amount Example 1 Polyphenylamine 1 0.1 g 4-decyloxyphenol 0.02 g 48 (S/cm) Example 2 Polyaniline 1 0.1 g 4-methoxyphenol 0.4 g 279 (S/cm) Example 3 Polyaniline 1 ol g 4-decyloxyphenol 0.001 g 3 (S/cm) Example 4 Polyaniline 1 0.1 R 4-methoxyphenol lo g 107 (S/cm) Example 5 Polyaniline 1 ol g 3-methoxyphenol 0.02 g 53 (S/cm) Example 6 Polyaniline 1 ol g 3-methoxyphenol 0.4 g 291 (S/cm) Example 7 Polyaniline 1 ol g 3-Phenoxyphenol 0.02 g 24 (S/cm) Example 8 Polyaniline 1 0.1s 3-Phenoxybenzene 0.4 g 78 (S /cm) Example 9 Polyaniline 2 ol g 4-methoxyphenol 0.02 g 218 (S/cm) Comparative Example 1 Polyaniline 1 ol g No 0.02 (S/cm) Comparative Example 2 Polyaniline 1 ol g 4- Nonyloxyphenol 0.0005 g 0.01 (S/cm) Comparative Example 3 Polyaniline 1 ol g 4-decyloxyphenol 2.0 g No film formation Comparative Example 4 Polyaniline 1 ol g m-decylphenol 0.4 g 240 (S/cm) INDUSTRIAL APPLICABILITY The conductive composition of the present invention is in the field of power electronics and optoelectronics, Used in static and antistatic materials, transparent electrodes and conductive film materials, materials for electroluminescent devices, circuit materials, electromagnetic wave shielding materials, dielectrics and electrolytes for capacitors, polar materials for solar cells and secondary batteries, fuel cells Partition material, etc., or electroplated bottom layer, rust inhibitor, etc. In the above, several embodiments and/or embodiments of the present invention have been described in detail 149505.doc -27-201111428, ''Tian Tian'', but it is easy for the manufacturer to fall within the scope of the novel object and effect of the present invention. The exemplified embodiments and/or embodiments are subject to numerous modifications. Accordingly, many such modifications are intended to be included within the scope of the present invention. The contents of the documents described in this specification are hereby incorporated by reference in their entirety. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a glass-like upper surface of an indium tin oxide (IT0) electrode formed on a surface; an exposed electrode is shown in FIG. 2, and a redundant conjugated polymer film is removed. FIG. 3 is a view showing the upper surface of the glass substrate of the terminal; and FIG. 3 showing the upper surface of the glass substrate from which the terminal of the conductive polyaniline film is removed. [Main component symbol description] Glass substrate ΙΤΟ electrode π total light polymer film Conductive polyaniline film 149505.doc -28-

Claims (1)

201111428 VII. Patent application scope: 1. A conductive composition comprising: a solvent, a π-coaxial conductive polymer which is dissolved in the solvent and mixed by a dopant, and an LD50 of 500 [mg/ a phenolic compound represented by the following formula (8): [Chemical Formula 1] OH 0.01 to 10.0. The weight ratio of the above-mentioned ruthenium compound to the above π-co-(tetra) conductive polymer (age compound; 2. a total of conductive polymer. 2. Material: - a conductive composition, at least The following (4) to (4) are used as the original (a) solvent; = the conductive sol-gel having a phenolic (c) LD50 of 500 [mg/kg] or more, which is miscible in the above solvent. By the following formula (force compound:. [Chemical 2] 149505.doc 201111428 OH The electropolymer [kg] of the conductive polymer (b) is a weight ratio of the phenolic compound (c) to the above π-conjugated system (phenolic compound [kgj/?t conjugated system] 〇1 to 10.0. 3. A conductive composition comprising: a solvent, a choline-based light-conductive conductivity doped with a dopant in the above solvent, and a formula (2) The phenolic compound shown: [Chemical 3] OH Γ^-OR, ^ (2) (wherein R 2 is an alkyl group having 1 to 20 carbon atoms alkenyl, cycloalkyl, aryl, aryl or The aralkyl group; the weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg]/7i conjugated conductive polymer [kg]) is 〇.〇1 to 10.0 〇 4- a conductive composition which uses at least the following (a) to (c) as a raw material: 149505.doc 201111428 (a) a solvent; (b) a dopant doped in the above solvent by a dopant The yoke system is also a molecule; (c) a phenolic compound represented by the following formula (2): [Chemical 4] OH OR2 (2) (wherein & is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aromatic group having a carbon number of 20); the above phenolic compound (c) is altogether with the above π The weight ratio of the conductive polymer (the phenolic compound [kg] / : t conjugated conductive polymer [to 0.01 to 10.0 〇 5. The conductive composition of claim 3 or 4, wherein the above The LD50 of the test compound (4) is 500 [mg/kg] or more. 6. The conductive composition according to any one of claims 1 to 4, wherein the above-mentioned π-group-based conductive polymer is a proton Any of the substituted or unsubstituted polyphenylamines, protonated substituted or unsubstituted poly-half' or protonated substituted or unsubstituted poly(tetra). The entangled composition, wherein the dopant of the ruthenium conjugated conductive polymer is an organic sulfonic acid, as in any one of claims 1 to 4.至中中—The 暮 暮 暮 知 & & & & 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 149 Succinic acid: M(03SCH(CH2CO〇R12)c〇〇Rl3)m (χχ) (In the formula (XX), Μ is a hydrogen atom, an organic radical or an inorganic radical, m is the valence of ruthenium, R and R is independently a hydrocarbon group or a group represented by _(Rl4〇)r_Rl5, R14 is a hydrocarbon group or a alkylene group, and Rls is a hydrogen atom, a hydrocarbon group or a group represented by R, Si-, and is a hydrocarbon group, 3] 6 may be the same or different, and r is an integer of 1 or more. 9. 10. 11. 12. 13. 14. The conductive composition according to any one of claims 1 to 4, wherein the phenolic compound is The weight ratio of the solvent (the phenolic compound to / solvent [^^]) is 0.0004 or more and 0.75 or less. A conductive laminated body comprising: a substrate; and the method of any one of claims 1 to 9 The conductive layer produced by the conductive composition is laminated on the substrate. The conductive laminate according to claim U, wherein the substrate is a resin film. A conductive article obtained by molding the conductive laminate of claim (7) or ". A capacitor produced by using the conductive composition of any one of claims 1 to 9. A conductive film obtained by molding the conductive composition of any one of the items of Item No. 9. 149505.doc 201111428 1 5. Kind of m roll, composition addition: green film: it is formed by forming the conductivity σ of any one of claims 1 to 9. 16:=Electrical article' is a mixture of the conductive material of any of claims 1 to 9 and a substrate. An electroconductive composition comprising: a ruthenium (IV) conductive polymer; and a phenolic compound represented by the following formula (1): [Chem. 5] (1) (wherein R is a carbon number 1 to an alkyl group, a dilute or a decyl group, a decyl group, an aryl group, a decylaryl group or an aralkyl group); 70 The above-mentioned test compound is electrically conductive with the above-mentioned redundant conjugated system The ratio of the polymer (the compound of the π-group-based conductive polymer) is the substituted or desubstituted polyaniline of the above-mentioned π-conjugated conductive polymer. A total of conductive polymer systems are used to make organic sulfonic acid doped. 149505.doc