JP2015151365A - Conductive oligothiophene, method for producing the same, conductive composition, coating, antistatic coating material, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive oligothiophene having a well controlled polymerization degree, which has excellent adhesiveness to a substrate to be coated, provides a smooth film quality since it has low crystallinity, and does not cause film cracks, light scattering, and the like, when applied as a coating film and an antistatic coating material.SOLUTION: The conductive oligothiophene is obtained by doping a linear thiophene oligomer or an oligothiophene dendrimer being a molecule formed by bonding six or more thiophene derivatives having a substituent at the 3-position, with an acid or its salt having an anion containing a fluoro group or a sulfonyl group.

Description

  The present invention generally relates to a conductive oligothiophene, and more specifically, when applied as a coating film and an antistatic coating, it has excellent adhesion to a coating substrate and forms a smooth film quality. The present invention relates to a conductive linear thiophene oligomer or a conductive oligothiophene dendrimer improved so as not to cause cracking, light scattering, and the like. The present invention also relates to a conductive composition, a paint, an antistatic coating, and an electronic member containing such a conductive linear thiophene oligomer or conductive oligothiophene dendrimer.

  In recent years, it has become important to impart antistatic properties to resins. To achieve this, antistatic agents such as surfactants have been conventionally applied to the surface of resin molded products, or antistatic properties have been achieved. A method of kneading an agent into a resin is known. However, in the former method, the antistatic property is remarkably lowered after a long time, so that it is difficult to put it into practical use as a highly antistatic resin having durability. On the other hand, in the latter method, the compatibility between the antistatic agent and the resin is poor, and the antistatic agent is peeled off from the surface of the molded product, or bleeding or blooming occurs.

  Antistatic agents such as surfactants are dependent on humidity, and at low humidity, the antistatic effect is deactivated, or after molding the resin, the antistatic effect is at least 1 to It took 3 days and there was a problem that it was slow-acting.

  In addition, a method of kneading carbon black or carbon fiber into a resin has been proposed. According to this method, a resin composition having excellent antistatic properties and durability in antistatic properties can be obtained. However, this method has problems such as the kneaded material being peeled off, a transparent molded product not being obtained, and the selection of the color of the molded product being restricted.

  As a method for solving the above problems, the present inventors have prepared a solution in which a metal salt composed of a cation that is an alkali metal or an alkaline earth metal is dissolved in a polyamide resin, a polyetheresteramide resin, an aliphatic polyester, An antistatic composition formed by adding to a polylactic acid resin, a thermoplastic elastomer and rubber has been proposed (see, for example, Patent Document 1).

  Also, as a method for producing salt-modified electrostatic dissipative polymers made of polyurethane, there is a method in which lithium bis (fluoroalkylsulfonyl) imide is dissolved in a co-solvent and added. It has been proposed (see Patent Document 2).

  As the conductive polymer, polyaniline-based, polypyrrole-based, and polythiophene-based conductive polymers are well known. In particular, conductive poly (3,4-ethylenedioxythiophene) (PEDOT) has excellent transparency. And it has already been commercialized as a PEDOT colloid aqueous solution (trade name Pylon P, manufactured by Bayer), and is widely used in the field of electronic components as a conductive coating agent.

  Also proposed is a method of forming a porous material on the surface of an electrode substrate by electrolytic polymerization of 3,4-ethylene dioxythiophene (EDOT) in a solution containing bis (perfluoroalkanesulfonyl) imide or a salt thereof. (See Patent Document 3).

  There has also been proposed a method for producing PEDOT-PSS by subjecting EDOT to chemical oxidative polymerization using persulfate in an aqueous medium in the presence of polystyrene sulfonic acid (PSS) (see Patent Document 4).

International Publication WO 01/79354 A1 (Claims) US Pat. No. 6,140,405 (Claim 1, 14 and 15) JP 2006-351289 A (Claims 1 and 5) Japanese Patent Laid-Open No. 7-90060

  However, in the method described in Patent Document 1, the antistatic performance may not be sufficient depending on the type of metal salt added to the antistatic composition. Further, when metal salts such as perchloric acid are used, when the metal is packaged using a film or sheet made of this antistatic composition, there is a problem that the metal surface is corroded, rusted or contaminated.

  Further, in the method described in Patent Document 2, an auxiliary solvent (ethylene carbonate, dimethyl sulfoxide, tetramethylene sulfone, N-methyl-2-pyrrolidone, etc.) for dissolving metal salts is used for the molded article of the antistatic composition. Bleeding or blooming on the surface contaminates the product. Further, the antistatic property is lowered by wiping the surface of the molded product, and the durability of the antistatic property is not sufficient. In particular, in a high temperature and high humidity atmosphere, bleeding and blooming are promoted.

  Moreover, although the said PEDOT-PSS which patent document 4 discloses shows the outstanding electroconductivity, there exists the following restrictions on the industrial application from the restrictions of the manufacturing conditions on the characteristic. That is, there are restrictions such as strong acidity, insufficient adhesion to the coated substrate, low moisture resistance and light resistance, low compatibility with general-purpose resins, and low solubility in water and organic solvents. . The electropolymerization method disclosed in Patent Document 3 also produces many by-products having different molecular weights, and there are restrictions on production conditions.

  The present invention has been made in view of the above problems, and when applied as a coating film and an antistatic coating, it has excellent adhesion to a coated substrate, forms a smooth film quality, and is free from cracks and light of the film. An object is to provide a conductive oligothiophene that does not cause scattering.

  Another object of the present invention is to provide a conductive oligothiophene having both ion conduction type antistatic characteristics and electron conduction type antistatic characteristics.

  Another object of the present invention is to provide a conductive oligothiophene that forms a transparent film.

  Another object of the present invention is to provide a conductive linear thiophene oligomer or a conductive oligothiophene dendrimer having a precisely controlled degree of polymerization.

  Another object of the present invention is to provide a method for producing such a conductive oligothiophene.

  Still another object of the present invention is to provide a paint, an antistatic coating and an electronic material using such a conductive oligothiophene.

  Another object of the present invention is to have excellent thermal stability, no bleeding, blooming and migration contamination, no dependence on humidity, high immediate effect, no deterioration of physical properties, and excellent antistatic property. An object of the present invention is to provide a conductive composition having sustained properties.

  Oligothiophene has been studied as a model compound of polythiophene. Oligothiophene can be easily synthesized by typical organic chemical reactions such as Grignard reaction, and the degree of polymerization can be controlled. Oligothiophenes are roughly classified into linear oligothiophenes and branched oligothiophenes (Mori et al., Chem. Eur. J. 2013, 19, 1658-1665). In this specification, for the sake of convenience, a linear oligothiophene is referred to as a linear thiophene oligomer, and a branched oligothiophene is referred to as an oligothiophene dendrimer to distinguish them.

  Dendrimer means a dendritic polymer with a structure that is regularly branched from the center. Dendrimers are composed of a central molecule called the core and side chain parts called the dendron. In addition, the number of branches in the dendron portion is expressed as a generation. In general, polymers have a certain molecular weight distribution, but high-generation dendrimers have the distinctive feature that they have a molecular weight of tens of thousands but are almost single molecular weight.

  The conductive oligothiophene according to the present invention has a linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which 6 or more thiophene derivatives having a substituent at the 3-position are bonded, and has an anion having a fluoro group and a sulfonyl group. Doped with an acid or a salt thereof.

  Ion conduction is an image in which ions move within and between molecules to hand baton, whereas electron conduction is an image in which electrons move within and between molecules as a ball rolls into a cylinder. The latter is faster in static electricity and more effective as an antistatic agent. The conductive oligothiophene according to the present invention has a property of electron conduction derived from a linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which 6 or more thiophene derivatives having a substituent at the 3-position are bonded. It has been found that the effect as an antistatic agent is enhanced because it also has the characteristics of ion conduction derived from an acid having an anion having a group and a sulfonyl group or a salt thereof.

  The thiophene derivative having a substituent at the 3-position preferably contains 3-alkoxythiophene or 3-alkylthiophene. The alkoxy group includes a polyether group whose one end is an alkoxyl group.

（式中、Ｒ_１は、片末端がアルコキシル基であるポリエーテル基又はアルキル基、ｎは４以上の整数を表す。）

（式中、Ｒ_２は、片末端がアルコキシル基であるポリエーテル基又はアルキル基である。） Among these, a linear thiophene oligomer having a skeleton as shown in the following “Chemical Formula 1” or an oligothiophene dendrimer having a skeleton as shown in the following “Chemical Formula 2”, an acid having an anion having a fluoro group and a sulfonyl group or Conductive oligothiophenes obtained by doping with their salts are particularly preferred.

(In the formula, R ₁ is a polyether group or an alkyl group whose one end is an alkoxyl group, and n represents an integer of 4 or more.)

(In the formula, R ₂ is a polyether group or an alkyl group whose one end is an alkoxyl group.)

  The acid having an anion having the fluoro group and the sulfonyl group or a salt thereof is 1 mol or more with respect to one molecule of the linear thiophene oligomer or oligothiophene dendrimer, and one molecule of the linear thiophene oligomer and oligothiophene dendrimer. It is preferable to dope less than 100 mol% with respect to the number of repeating units (number of moles).

  It has been found that high conductivity is exhibited when 6 or more thiophene derivatives having a substituent at the 3-position are linked.

  A linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which 6 or more thiophene derivatives having a substituent at the 3-position are bonded, generates a carrier that can move freely. Will have. These are excellent in adhesiveness to the coated substrate and are low in crystal, so that a smooth film quality is formed, and a transparent film that does not cause cracking or light scattering of the film is provided.

  The acid having an anion having a fluoro group and a sulfonyl group includes bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide or trifluoromethanesulfonic acid, and the salt having the fluoro group and the sulfonyl group is lithium bis (Fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide or lithium trifluoromethanesulfonate.

  In the method for producing a conductive oligothiophene according to the present invention, first, a linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which six or more thiophene derivatives having a substituent at the 3-position are bonded, is prepared. Next, the above-mentioned linear thiophene oligomer or oligothiophene dendrimer and an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof are added and stirred in the medium, and the anion having the fluoro group and the sulfonyl group is added. A solution containing a linear thiophene oligomer and an oligothiophene dendrimer doped with an acid having a salt or a salt thereof is obtained.

  The medium includes a volatile solvent, a polymerizable monomer, an oligomer, and a prepolymer described later.

  The conductive composition according to the present invention comprises a linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which six or more thiophene derivatives having a substituent at the 3-position are bonded, an acid having an anion having a fluoro group and a sulfonyl group. Alternatively, a conductive oligothiophene doped with a salt thereof (first salt) is included. The conductive oligothiophene is dispersed in a polymerizable monomer, oligomer or prepolymer in which an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof (second salt) is dissolved.

  In this specification, “dispersion” refers to a state in which the conductive oligothiophene is scattered or dissolved in the form of fine droplets in the composition. The conductive oligothiophene is dispersed alone or dissolved in a volatile solvent.

  Volatile solvent means a solvent that vaporizes at room temperature. Water, methanol, ethanol, isopropanol, 1-butanol, 2-butanol, cyclohexanol and other alcohols, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone A volatile solvent selected from the group consisting of ketones such as cyclohexanone, ethers such as tetrahydrofuran, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and esters such as methyl acetate, ethyl acetate, and butyl acetate Can do. The reason why the volatile solvent is selected is to facilitate drying after the composition is applied to the object. As long as it has volatility, it is not limited to the above, and any can be used.

  The polymerizable monomer means a compound having a functional group to be polymerized, and examples thereof include a polymerizable monomer having an acryloyl group, a methacryloyl group, a vinyl group and the like. Examples of the mode include monomers, oligomers, and those having three or more active energy ray-curable functional groups in the molecule.

  Examples of the polymerizable monomer include monofunctional monomers: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meta ) Acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, Bifunctional compounds such as dicyclopentenyloxyethyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl (meth) acrylate, vinyl acetate, styrene, etc .: Neopentylglyco Rudi (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Polyfunctional ones such as ethylene glycol di (meth) acrylate, glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, propylene: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tri (meth) acrylate of 3 mol propylene oxide adduct of trimethylolpropane, tri (meth) acrylate of 6 mol ethylene oxide adduct of trimethylpropane, glycerin propoxytri (meth) acrylate , Dipentane erythritol hexa (meth) acrylate, hexa (meth) acrylate of a caprolactone adduct of dipentaerythritol, and the like.

  Furthermore, as the activated energy ray-curable (meth) acrylate-based compound, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, (Meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4-vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyl Loxycyclohexyl, 4-vinyloxymethylcyclohexyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- ( Vinyloxyethoxyethoxy) ethyl, (meth) acrylic acid 2- It can be mentioned vinyloxy ethoxy ethoxy ethoxy) ethyl and the like.

  An oligomer refers to a polymer having a relatively low molecular weight to which a finite number of monomers (generally up to 100) are bonded. A polymer means a state in which a very large number (several hundreds or more) of monomers are bonded to an oligomer. Examples of the oligomer include unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate. Among these, polyethylene glycol mono- or di (meth) acrylate is preferably used. Among them, polyethylene glycol mono- or di (meth) acrylate having at least 6 oxyethylene units is preferably used.

  A prepolymer is an intermediate product that stops the polymerization or condensation reaction of the monomer at an appropriate point. It is in the pre-stage of becoming a polymer, and it can easily cause polymerization or crosslinking reaction by using a curing agent or the like. Includes urethane resin-based prepolymers and silicon resin-based prepolymers. Examples of the prepolymer having three or more functional groups include diisocyanate: hexamethylene diisocyanate, isophorone dicyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate dicyclohexylmethane diisocyanate, and 2,2,4-trimethylhexacene. Methylene diisocyanate, lysine diisocyanate, norbornane diisocyanate and the like, and hydroxyl group-containing (meth) acrylate: monofunctional ones such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, Reacted with trifunctional or higher functional groups such as dipentaerythritol penta (meth) acrylate And the like.

The acid having the fluoro group and the sulfonyl group is preferably bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide or trifluoromethanesulfonic acid. The salt having a fluoro group and a sulfonyl group is preferably lithium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NLi) or lithium trifluoromethane sulfonate (CF ₃ SO ₃ Li).

  The cations to be paired are preferably selected from cations of the group consisting of alkali metals, group 2A elements, transition metals and amphoteric metals in addition to lithium.

  The conductive oligothiophene is added in an amount of 0.005 to 50 with respect to 100 parts by mass of the polymerizable monomer, oligomer or prepolymer in which the salt having the anion having the fluoro group and the sulfonyl group (second salt) is dissolved. It is preferable to contain 0.0 part by mass.

  In the polymerizable monomer, oligomer or prepolymer before dispersing the conductive oligothiophene, the salt having the anion having the fluoro group and the sulfonyl group (second salt) is the polymerizable monomer, oligomer, It is contained in an amount of 0.01 to 50 parts by mass with respect to 100 parts by mass of the composition containing the prepolymer, resin, elastomer or adhesive resin. This composition is an ion conductive composition.

The conductive oligothiophene may be dissolved in an ionic liquid and dispersed in the polymerizable monomer, oligomer or prepolymer. An ionic liquid can be used as a medium for dissolving the electron conductive polymer. An ionic liquid refers to a salt (en) present in the liquid. Basically, the ionic liquid is classified into three types: pyridine, alicyclic amine, and aliphatic amine. . As an ionic liquid with good dispersibility, bis (trifluoromethanesulfonylimide) methyltributylammonium salt ((CF ₃ SO ₂ ) ₂ N ⁻ .N ⁺ (CH ₃ ) (C ₄ H ₉ ) ₃ ) (third Salt).

  The conductive composition of the present invention further includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, a colorant, a pigment, an antibacterial / antifungal agent, a light fastener, a plasticizer, and a tackifier. If necessary, known additives such as agents, dispersants, antifoaming agents, curing catalysts, curing agents, leveling agents, water repellents, coupling agents, fillers, vulcanizing agents, chelating agents, vulcanization accelerators, etc. Can be added.

  Using the conductive composition of the present invention, a film, a paint, an electronic member or the like can be obtained. Further, the antistatic composition of the present invention can be cured on the molding surface to form an antistatic coating. The composition of the present invention works particularly effectively when used as a film, paint or coating.

  Polymerization of the (meth) acryloyl group and alkenyl group for curing is performed by energy such as heating, ultraviolet light, visible light, and electron beam, and a known polymerization initiator may be used as appropriate.

  When the conductive oligothiophene according to the present invention is applied as a coating film and an antistatic coating, it has excellent adhesion to the coated substrate and low crystallinity, thereby forming a smooth film quality and cracking of the film. And light scattering are fast, and the flow of static electricity is fast, so that it is highly effective as an antistatic agent and can be usefully applied to electronic device applications. In addition, by dispersing this conductive oligothiophene in a polymerizable monomer, oligomer or prepolymer in which a second salt having an anion having a fluoro group and a sulfonyl group is dissolved, the conductive property having a high antistatic property is obtained. A composition was obtained.

It is a figure explaining the effect of this invention.

（式中、Ｒ_１は、片末端がアルコキシル基であるポリエーテル基又はアルキル基、ｎは４以上の整数を表す。）

（式中、Ｒ_２は、片末端がアルコキシル基であるポリエーテル基又はアルキル基である。） A linear thiophene oligomer as shown in the following “chemical formula 1”, which is a molecule in which six or more thiophene derivatives having a substituent at the 3-position are bonded for the purpose of obtaining a conductive oligothiophene having a precisely controlled degree of polymerization. Alternatively, an oligothiophene dendrimer represented by the following “Chemical Formula 2” was realized by doping with an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof.

(In the formula, R ₁ is a polyether group or an alkyl group whose one end is an alkoxyl group, and n represents an integer of 4 or more.)

(In the formula, R ₂ is a polyether group or an alkyl group whose one end is an alkoxyl group.)

Next, in the case of the linear thiophene oligomer shown in Chemical Formula 1, 3- {2- [2- (2-methoxyethoxy) ethoxy] ethoxy} thiophene (3EOXTH) hexamer (Head to Tail bond) is obtained. The operation and effect will be described by exemplifying the case of using lithium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NLi) as a doping agent.

Lithium bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ NLi was added to a linear thiophene oligomer consisting of a hexamer of 3- {2- [2- (2-methoxyethoxy) ethoxy] ethoxy} thiophene (3EOXTH). ) As a doping agent has been found to have a higher conductivity than those without a doping agent.

  In general, in a conductive polymer, electrons are delocalized along a conjugated system. This is usually through the overlap of π orbitals, and the π system is expanded to form a valence band. When electrons are removed from this π system (p doping) or given electrons (n doping), charged units called bipolarons are generated. As the bipolaron moves through the polymer chain, macroscopic conductivity develops.

According to the present invention, as shown in FIG. 1, a dopant anion ((CF ₃ SO ₂ ) ₂ N ⁻ ) which is an anion of a super strong acid and has high nucleophilicity is represented by 3- {2- [2- (2 -Methoxyethoxy) ethoxy] ethoxy} thiophene (3EOXTH) is strongly correlated with a linear thiophene oligomer composed of a hexamer, and a polaron (radical cation) or bipolarone (dication) having a cation radical property is generated. Stabilize. That is, the dopant anion (CF ₃ SO ₂ ) ₂ N ⁻ acts as a p-doping agent. On the other hand, Li ions that are cations are surrounded by ether oxygen to form a chelate compound and stabilize.

  Then, when an electric field is applied to the conductive linear thiophene oligomer from the outside, in the cured film, Li ion species use the molecular motion of ether oxygen atoms toward the corresponding pole (film surface). It moves (ion transport) and develops ion conduction type antistatic characteristics. That is, it is an image in which Li ions move within and between molecules so as to hand baton. On the other hand, a linear thiophene oligomer having a cation radical property exhibits an electron conduction type antistatic property. That is, it is an image in which radicals (electrons) move in and between molecules so as to roll the ball into the cylinder.

  The acid having an anion having a fluoro group and a sulfonyl group or a salt thereof is 1 mol or more, more preferably 2 mol or more, and the number of repeating units of one molecule of the linear thiophene oligomer (1 It is preferable that the doping is less than 100 mol% with respect to the number of moles).

  For example, one molecule of the thiophene derivative shown in FIG. 1 has 6 repeating units. When the thiophene oligomer forms a polaron (radical cation), 1 mol of an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof is required for one molecule of the thiophene oligomer. When the amount is less than 1 mol, the resulting thin film contributes little to the conductivity. In the case of forming a bipolaron (dication) as shown in Chemical Formula 1, the contribution to the conductivity of the thin film is greater than in the case of forming a polaron. When forming this bipolaron, the acid or its salt which has an anion provided with a fluoro group and a sulfonyl group is required 2 mol with respect to 1 molecule of thiophene oligomers. On the other hand, when the number of repeating units (number of moles) of one molecule of thiophene oligomer is 100 mol% or more, that is, in the case of FIG. Therefore, it is preferable to suppress the dope amount of the acid having an anion having a fluoro group and a sulfonyl group or a salt thereof to less than 100 mol% with respect to the number of repeating units (number of moles) of one molecule of the oligothiophene derivative. .

  The number of oxyethylene units in the polyethylene glycol chain constituting the polyether group is preferably 3 or more. When configured in this manner, as shown in FIG. 1, lithium ions are surrounded by ether oxygen to form a tetracoordinate chelate, and lithium ions move to the adjacent ether oxygen one after another due to the molecular motion of the polyether chain. It moves and moves and develops antistatic properties strongly. On the other hand, the total number of oxyethylene units is preferably 50 or less. This is because when the number of oxyethylene units exceeds 50, the liquid property is weakened and becomes waxy, which makes handling difficult.

  The same applies to the conductive oligothiophene dendrimer obtained by doping the oligothiophene dendrimer represented by Chemical Formula 2 with an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof.

  As described above, the conductive oligothiophene obtained in the present invention has both an ion conduction type antistatic property and an electronic conduction type antistatic property. It becomes a polymer. This conductive oligothiophene is also characterized by high transparency.

  In addition, this conductive oligothiophene is dispersed in a polymerizable monomer, oligomer or prepolymer in which a salt having an anion having a fluoro group and a sulfonyl group is dissolved, so that bleeding, blooming and migration of the antistatic agent are performed. A conductive composition is provided that is free from contamination.

Examples of the present invention will be described below. In the text, an index may be displayed. For example, “1.5E + 02” means 1.5 × 10 ² .

(Synthesis of linear thiophene oligomer)
The linear thiophene oligomer is synthesized by the method shown in [Chemical Formula 3] according to the synthesis method of Mori et al. (J. Am. Chem. Soc., 2011, 133, 16734-16737). -Methoxyethoxy) ethoxy] ethoxy} thiophene (3EOXTH) hexamer (6 (3EOXTH), Head-to-Tail bond) was obtained. According to this method, since the catalyst 2,2,6,6-tetramethylpiperidine (TMPH) and the ethyl Grignard reagent (EtMgCl) are used, the 5-position proton of 3-alkylthiophene is highly selectively metallized, A linear thiophene oligomer which is a linear oligothiophene having a precisely controlled molecular weight is obtained.

  (Preparation of bis (trifluorosulfonyl) imide dove 6 (3EOXTH) in methyl ethyl ketone (MEK) solution)

  To 100 ml of MEK, 0.033 mol (7.9 parts by mass) of 6 (3EOXTH) and 0.011 mol (3.16 parts by mass) of bis (trifluorosulfonyl) imide were added and stirred at 20 ° C. for 4 hours. Then, it filtered with the filter paper made from glass fiber, and obtained the MEK solution. Further, elemental analysis showed that the doping rate of bis (trifluoro) imide was about 33 mol%.

(Synthesis of conductive composition)
In the obtained MEK solution, 5 parts by mass of an acrylic resin (MP-1600, manufactured by Soken Chemical Co., Ltd.) was dissolved as a resin to obtain a conductive 6 (3EOXTH) composition.

(Formation of antistatic coating)
The conductive 6 (3EOXTH) composition was added to bar coater No. 4 is applied to a highly transparent cycloolefin polymer film (COP) (manufactured by ZEON Corporation, ZEONOR film ZF14, thickness 100 μm), dried at a temperature of 100 ° C. for 3 minutes, and a conductive film (calculated coating thickness). 0.5 μm) was obtained. The conductivity of the film was 40 S / cm. The spectral transmittance (550 nm) was 89%. The film was held at 105 ° C. for 500 hours for a heat resistance test. The conductivity after the heat test was 37 S / cm. The conductive coating exhibited the same conductivity and transparency characteristics as the ITO coated film.

(Synthesis of 3-hexylthiophene (3HEXTH) 12mer (12 (3HEXTH)))
In Example 1, 12 (3HEXTH) was obtained in the same manner as the synthesis formula shown in “Chemical Formula 3” except that 3-hexylthiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 3EOXTH. Synthesized.

  (Preparation of an acrylate solution of lithium bis (trifluoromethanesulfonyl) imide dope 12 (3HEXTH))

  12 (3HEXTH) 0.005 mol was added to 20 parts by mass of a pentaerythritol triacrylate solution (trade name Sanconol PETA-20R, manufactured by Sanko Chemical Co., Ltd.) in which 20 parts by weight of lithium bis (trifluoromethanesulfonyl) imide was dissolved. After stirring at 20 ° C. for 6 hours, the mixture was filtered with a glass fiber filter paper to obtain a conductive acrylate composition.

(Formation of antistatic coating)
0.6 parts by mass of Irgacure 907 (manufactured by Ciba Geigy) was added as a photopolymerization initiator to the conductive acrylate composition to prepare a liquid composition. This composition was applied to the surface of a prism-acrylic resin (pitch 500 μm, apex angle 88 °) placed on the surface of a pace film (PET, thickness 250 μm), and then ultraviolet light in the air using a high-pressure mercury lamp. To obtain a transparent prism plate having a hardness of 1.0 μm and a hardness of 2H. The surface resistivity of this prism plate was 6.0E + 02Ω / sq. Then, after being left for 1 hour under conditions of 70% humidity and 80 ° C., the surface resistivity was measured and found to be 7.0E + 03Ω / sq.

  The MEK solution of conductive linear thiophene oligomer 6 (3EOXTH) obtained in Example 1 and a binder acrylic resin was applied to a 1 mm thick stainless steel plate, and then dried at 50 ° C. under reduced pressure. This is punched into two circular shapes and set facing each other as an electrode, and a nylon non-woven fabric impregnated with an electrolytic solution [0.5M lithium bis (trifluoromethanesulfonyl) imide aqueous solution] is sandwiched between them as a separator. An electrochemical capacitor was made by caulking with a coin-shaped case made of metal. The discharge capacity of constant current discharge (100 μA) of this capacitor was 0.1F. The internal resistance of the constant resistance discharge song was 50Ω.

To 100 parts by mass of a MEK solution of bis (fluorosulfonyl) imide lithium-doped 6 (3EOXTH) prepared in the same manner as in Example 1, 50 parts by mass of 2-hydroxyethylacrylamide and bis (trifluoromethanesulfonylimide) methyltributylammonium salt After adding 3 parts by mass and stirring, MEK was removed under reduced pressure to obtain a conductive linear thiophene oligomer composition. This conductive linear thiophene oligomer composition was applied to a polyethylene terephthalate film (Toyobo Co., Ltd., A4300, thickness 38 μm) by a micro gravure coating method (thickness 1.5 μm). Next, using a high-pressure mercury lamp (80 W), ultraviolet rays were irradiated (200 mJ / cm ² ) in the air, and the film was crosslinked to obtain a film coated with a conductive polymer. The surface resistivity of this coating film was 7.3E + 02Ω / sq.

(Synthesis of oligothiophene dendrimers)
Oligothiophene dendrimer 7-mer (OTHDEN-1) was obtained by the synthesis method (Chem. Eur. J. 2013, 19, 1658-1665) by Mori et al. Since catalyst 2,2,6,6-tetramethylpiperidine (TMPH) and ethyl Grignard reagent (EtMgCl) are used, the 5-position proton of 3-alkylthiophene is highly selectively metallized, and the molecular weight is precisely controlled. 7-mer (OTHDEN-1) was obtained.

(Adjustment of MEK liquid composition)
MEK solution composition of lithium trifluorosulfonate-doped oligothiophene dendrimer 7-mer (OTHDEN-1) using 0.02 mol (3.1 parts by mass) of lithium trifluorosulfonate in the same manner as in Example 1 I adjusted things. In this case, lithium ions are coordinated to a lone pair of sulfur atoms. Further, a conductive oligothiophene dendrimer composition, which is a branched conductive oligothiophene, containing 5 parts by mass of a polyester resin (STAFLX, manufactured by Fuji Film Co., Ltd.) as a binder resin and containing a polyester binder resin. Obtained. This composition was dropped on a glass plate and dried at 50 ° C. for 1 hour to obtain a film having a thickness of 0.7 μm. The conductivity of the 4-probe method was 50 S / cm. The electrical conductivity after standing for 240 hours under the conditions of 85 ° C. and 85% relative humidity was 47 S / cm. The film composed of the present conductive oligothiophene dendrimer was useful as an antistatic agent excellent in moisture and heat resistance and excellent in antistatic property and as a cathode material for a solid electrolytic capacitor.

In the same manner as in Example 5, starting from 3- {2- [2- (2-methoxyethoxy) ethoxy] ethoxy} thiophene, the oligothiophene dendrimer 15-mer (OTHDEN-2) shown in “Chemical Formula 5” Got.

  An ethyl acetate solution (10 parts by mass) of bis (trifluorosulfonyl) imide-doped 15-mer (OTHDEN-2) was prepared. In this solution, 2 parts by mass of an acrylic resin (MP-1600, manufactured by Soken Chemical Co., Ltd.) was dissolved to obtain a conductive 15mer (OTHDEN-2) composition.

(Formation of antistatic coating)
The conductive 15-mer (OTHDEN-2) composition was applied to a transparent PET film to obtain a conductive film (calculated coating amount 0.5 μm). The surface resistivity of the film was 1.5E + 01Ω / sq.

As the salt having an anion having a fluoro group and the sulfonyl group used in the present invention, in addition to those described above, for _{example, LiN (C 2 F 5 SO} 2) 2, LiN (C 4 F 9 SO 2 ) (CF ₃ SO ₂ ), LiN (C ₈ F ₁₇ SO ₂ ) (CF ₃ SO ₂ ), LiN (CF ₃ CH ₂ OSO ₂ ) ₂ , LiN (CF ₃ CF ₂ CH ₂ OSO ₂ ) ₂ , LiN ( HCF ₂ CF ₂ CH ₂ OSO ₂ ) ₂ , LiN ((CF ₃ ) ₂ CHOSO ₂ ) ₂ , tris (fluoroalkylsulfonyl) methidolithium Li (CF ₃ SO ₂ ) ₃ C, and the like can also be used.

  It should be understood that the embodiments disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  When the conductive oligothiophene according to the present invention is applied as a coating film and an antistatic coating, it has excellent adhesion to the coated substrate and low crystallinity, thereby forming a smooth film quality and cracking of the film. And no light scattering. This electronic conductive polymer is used for antistatic and conductive coatings, capacitors, touch screens, organic LEDs, transparent conductive ink jet printing inks, semiconductor packaging materials by coating and printing on films, liquid crystal protective films, touch panels, Can be used in a wide range of electronic materials such as organic EL, organic TFT, organic semiconductor, dye-sensitized solar cell, conductive polymer electrode, solid electrolytic capacitor, conductive organic thin film, electronic device, printed electronics, flexible electronic paper, etc. .

Claims (12)

  Conductivity obtained by doping a linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which 6 or more thiophene derivatives having a substituent at the 3-position are bonded, with an anion having a fluoro group and a sulfonyl group or a salt thereof. Oligothiophene.   The conductive oligothiophene according to claim 1, wherein the thiophene derivative having a substituent at the 3-position includes 3-alkoxythiophene or 3-alkylthiophene.   The acid having an anion having a fluoro group and a sulfonyl group or a salt thereof is 1 mol or more with respect to one molecule of the linear thiophene oligomer or oligothiophene dendrimer, and one molecule of the linear thiophene oligomer and oligothiophene dendrimer. The conductive oligothiophene according to claim 1 or 2, doped with less than 100 mol% based on the number of repeating units (number of moles). The acid having an anion having a fluoro group and a sulfonyl group includes bis (trifluoromethanesulfonyl) imide or trifluoromethanesulfonic acid,
The conductive oligothiophene according to any one of claims 1 to 3, wherein the salt having a fluoro group and a sulfonyl group includes lithium bis (trifluoromethanesulfonyl) imide or lithium trifluoromethanesulfonate. Preparing a linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which 6 or more thiophene derivatives having a substituent at the 3-position are bonded;
In the medium, the linear thiophene oligomer or oligothiophene dendrimer and an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof are added and stirred, and the acid having an anion having the fluoro group and the sulfonyl group is stirred. Or a step of obtaining a solution containing a linear thiophene oligomer or oligothiophene dendrimer doped with a salt thereof, and a method for producing a conductive oligothiophene. A linear thiophene oligomer or oligothiophene dendrimer, which is a molecule in which six or more thiophene derivatives having a substituent at the 3-position are bonded, an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof (first salt) A conductive oligothiophene doped with
Conductive composition in which conductive oligothiophene is dispersed in a polymerizable monomer, oligomer or prepolymer in which an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof (second salt) is dissolved object.   0.005-50 with respect to 100 mass parts of the said polymerizable monomers, oligomers, or prepolymers which melt | dissolved the salt (2nd salt) which has an anion provided with the said fluoro group and a sulfonyl group for the said conductive oligothiophene. The conductive composition according to claim 6, comprising 0.0 part by mass.   The conductive composition according to claim 6 or 7, wherein the conductive oligothiophene is dissolved in an ionic liquid and dispersed in the polymerizable monomer, oligomer, or prepolymer.   The conductive composition according to claim 8, wherein the ionic liquid contains bis (trifluoromethanesulfonylimide) methyltributylammonium salt) (third salt).   The coating material containing the conductive oligothiophene of any one of Claims 1-4.   The antistatic coating containing the conductive oligothiophene of any one of Claims 1-4.   The electronic member containing the electroconductive oligothiophene of any one of Claims 1-4.

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