JP2013095820A - Conductive composition, and conductive film and conductive laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition which contains a conductive polymer, is good in the dispersibility of CNT, exhibits excellent coatability, and is suitable for producing conductive films excellent in both conductivity and durability; to provide a conductive film which is formed from the composition and is excellent in both conductivity and durability; to provide a conductive laminate having the conductive film; to provide a thermo-electric conversion element containing the conductive film or the conductive laminate; and to provide a thermoelectric power-generating article using the thermoelectric conversion element.SOLUTION: There are provided the conductive composition comprising (A) carbon nanotubes, (B) a conductive polymer, (C) an onium salt compound, and (D) a polymerizable compound; the conductive film using the composition; the conductive laminate having the conductive film; the thermoelectric conversion element containing the conductive film or the conductive laminate; and the thermoelectric power-generating article using the thermoelectric conversion element.

Description

  The present invention relates to a conductive composition, and a conductive film and a conductive laminate using the same. The present invention also relates to a method for producing a conductive film and a conductive laminate. Furthermore, the present invention relates to a thermoelectric conversion material using the composition and a thermoelectric conversion element using the conductive film or conductive laminate.

  In recent years, with the development of the electronics field, new electronic materials have been researched and developed one after another. New nanocarbon materials such as carbon nanotubes and graphene are one of them. The properties of these materials have been studied, and because of their high electrical conductivity, development and application research are progressing as new conductive materials that replace conventional metal-based materials.

On the other hand, image display elements (displays) represented by liquid crystal displays (LCDs), plasma displays (PDPs), electroluminescence (EL) elements, etc., are used in various types of mobile devices such as televisions and computers, which have recently become widespread. It is applied to the field and has made remarkable progress. In recent years, the transition from fossil energy to renewable energy has been studied in consideration of the global environment. For example, the spread of solar power generation, wind power generation, wave power generation, vibration power generation, thermoelectric conversion and improvement of these performances. It has been demanded.
Under such circumstances, thermoelectric conversion materials and elements are capable of utilizing enormous amounts of unused thermal energy such as solar thermal power generation, geothermal power generation, hot water thermal power generation, and power generation using exhaust heat from industrial furnaces and automobiles. Has been attracting attention.

In such display elements and thermoelectric conversion materials / elements, conductive materials are used as members related to performance. For example, in the former, a transparent conductive film using a metal material such as ITO (indium tin oxide) is used. This transparent conductive film is usually produced by forming a metal material on a glass substrate by a vapor phase method such as a vacuum deposition method or a sputtering method. However, in the production by the vapor phase method, it is not easy to control the process conditions, the production apparatus and the like are expensive, and it is difficult to increase the film production area.
In addition, for electrical devices such as mobile phones and mobile devices, there is a great demand for weight reduction and flexibility. For this reason, it has been studied to shift the substrate material from glass to plastic. If a plastic substrate is used, the weight of the display device can be reduced to half or less that of a glass substrate, and the strength and impact resistance can be significantly improved. However, the conventional vapor phase manufacturing requires heat resistance of the substrate, so that the plastic substrate lacks heat resistance. Moreover, the adhesiveness with respect to the board | substrate of the formed film fell and produced problems, such as being easy to peel off.

On the other hand, in thermoelectric conversion materials and elements, there is a problem of improving the conductivity of the conductive material used therefor. The figure of merit ZT related to thermoelectric conversion is represented by the formula (A), and improvement in conductivity is important along with thermoelectromotive force for performance improvement.

Figure of merit ZT = S ² · σ · T / κ (A)
S (V / K): Thermoelectromotive force (Seebeck coefficient) σ (S / m): Conductivity
κ (W / mK): Thermal conductivity T (K): Absolute temperature

Conventionally, inorganic materials have been mainly studied as thermoelectric conversion materials. For example, bismuth / tellurium compounds, lead / tellurium compounds, zinc / antimony compounds, skutterudite compounds (CoSb ₃ , FeSb ₃ etc.), class Rate compounds (Si, Ge, etc.), Heusler compounds (Fe ₂ VAl, TiNiSn, etc.), silicide compounds (FeSi ₂ , Mg ₂ Si, etc.), boron compounds, layered oxide compounds, etc. have been developed. ,It is used. In thermoelectric conversion materials / elements, as with the above display elements, there are demands for weight reduction and flexibility, and there are great expectations for organic materials, and conductive polymers are typically studied (for example, patent documents). 1-3, non-patent documents 1, 2). The organic material is advantageous in that the thermal conductivity κ in the formula (A) is lower than that of the inorganic material, but the problem is that the electrical conductivity σ is greatly reduced.

  As means for improving the electrical conductivity of organic materials, the use of carbon nanotubes (hereinafter abbreviated as CNT) has been studied (for example, Non-Patent Documents 3 and 4). If conductive materials containing CNTs can be prepared based on organic materials, film formation by spin coating and other coating methods is possible, so high temperature and vacuum conditions are not essential, the manufacturing process is simple, and manufacturing costs are reduced. Can be suppressed. Since a material such as plastic can be used as a substrate, it is possible to cope with lightening and flexibility of the element, and in addition, the strength and impact resistance can be remarkably improved. It is also suitable for manufacturing large area films and the like. Because of these advantages, development and practical application of new conductive materials using CNTs are being promoted, and application to thermoelectric conversion materials is also expected.

On the other hand, when CNT is used as a conductive material, the liquid dispersibility is a problem to be solved. For example, when forming a thin film using CNTs, it is necessary to disperse CNTs in a medium such as water or an organic solvent. However, CNT easily aggregates and is not easily dispersed. Therefore, the dispersion of CNTs is improved by adding a dispersant, and the obtained dispersion is applied and formed into a film (see, for example, Non-Patent Documents 5 and 6). Specific methods for improving the dispersibility of CNTs with a dispersant include a method of dispersing in an aqueous solution containing a surfactant such as sodium dodecyl sulfonate (see, for example, Patent Document 4), a cationic surfactant, A method using an anionic surfactant and a nonionic surfactant (see Patent Document 5), a method using an anionic dispersant (see Patent Document 6), and the like have been proposed.
However, these dispersion methods are limited to dispersion in an aqueous medium, and defects may occur in CNTs during dispersion. In addition, when a non-conductive dispersant adheres to the surface of the CNT, there is a problem that the original conductivity and semiconductor characteristics of the CNT are impaired and the performance is lowered (see Non-Patent Document 7).
On the other hand, a method has been proposed in which a conjugated polymer capable of transferring charge to and from CNTs, a so-called conductive polymer, is used to disperse CNTs in a solution of the polymer and to increase dispersibility. (For example, refer to Patent Documents 7 to 11 and Non-Patent Document 8). However, even with this method, it is difficult to sufficiently exhibit the original high conductivity of CNT.
Moreover, the compatibility with the organic material used together with CNT is not necessarily sufficient, and it has been a problem to improve the durability and wear resistance of the produced coating film.

Japanese Unexamined Patent Publication No. 2000-323758 Japanese Patent Laid-Open No. 2001-326393 Japanese Patent Laid-Open No. 2002-100815 JP-A-6-228824 JP 2008-24523 A JP 2009-242144 A JP 2003-96313 A JP 2004-195678 A JP 2005-89738 A JP 2006-265534 A JP 2010-18696 A

Journal of the Thermoelectric Society of Japan, Volume 6, Number 1, Page 8 (2009) Functional Materials, February 2009 (Vol. 29, No. 2), p. 38 ACS Nano Volume 4 (No. 1), 513 (2010) J. Polymer Science Part B: Polymer Physics Vol. 49, p. 467 (2011) Chemistry A European Journal Vol. 12, p. 7595, 2006 Nano Letters Volume 3, Page 269, 2003 Advanced Materials Volume 21, Page 1, 2009 Advanced Materials Volume 20, 4433, 2008

The present invention is a conductive composition containing a conductive polymer, having good dispersibility of CNTs and showing excellent coating properties, and suitable for the production of a conductive film excellent in both conductivity and durability. It is an object to provide a conductive composition.
In addition, the present invention provides a conductive film excellent in both conductivity and durability formed using the composition, a conductive laminate including the conductive film, the conductive film or the conductive laminate. It is an object to provide a thermoelectric conversion element including a body and a thermoelectric power generation article using the thermoelectric conversion element.
Moreover, this invention makes it a subject to provide the manufacturing method of the electroconductive film and electroconductive laminated body which are excellent in both electroconductivity and durability.

The present inventors have conducted intensive studies in view of the above problems. As a result, it has been found that in a composition containing an onium salt compound together with CNT and a conductive polymer, the onium salt compound generates an acid and functions as an excellent dopant by applying a specific external energy. Furthermore, in this composition, the defect of CNT was suppressed, the high electroconductivity which CNT originally has was maintained, and it discovered that a material with higher electroconductivity was obtained by using the said composition.
Also, commonly used acid and metal salt dopants are not sufficiently compatible and promote aggregation of conductive polymers and CNTs, but if onium salt compounds are used as dopants, unless specific external energy is imparted It has been found that the generation of acid is suppressed, and as a result, aggregation of the conductive polymer and CNT in the composition can be suppressed, and the coating property of the composition is excellent.
Furthermore, when a polymerizable compound is added to the above composition, the polymerization reaction is initiated by the radical species of the acid or the precursor of the acid generated from the onium salt compound by applying external energy, and the film can be cured. It has been found that a conductive material having greatly improved durability while maintaining conductivity can be obtained.
The present invention has been made based on these findings.

That is, said subject was achieved by the following means.
<1> A conductive composition containing (A) a carbon nanotube, (B) a conductive polymer, (C) an onium salt compound, and (D) a polymerizable compound.
<2> The conductive composition according to <1>, wherein the (C) onium salt compound is a compound having an oxidizing ability with respect to (A) carbon nanotubes and / or (B) a conductive polymer.
<3> (C) The conductive composition according to <1> or <2>, wherein the onium salt compound is a compound that generates an acid by application of heat or active energy ray irradiation.
<4> (C) The onium salt compound is one or more of the compounds represented by any one of the following general formulas (I) to (V), and any one of <1> to <3> The electroconductive composition as described.

(In the general formulas (I) to (V), R ^{21 to} R ²³ , R ^{25 to} R ²⁶ and R ^{31 to} R ³³ are each independently a linear, branched or cyclic alkyl group, an aralkyl group, an aryl group, R ^{27 to} R ³⁰ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, an aryloxy group R ²⁴ represents a linear, branched or cyclic alkylene group or an arylene group.
X ⁻ represents an anion of a strong acid.
Any two groups of R ^{21 to} R ²³ in the general formula (I), R ²¹ and R ^{23 in} the general formula (II), R ²⁵ and R ^{26 in} the general formula (III), R ²⁷ in the general formula (IV) Any two groups of -R ³⁰ and any two groups of R ³¹ -R ³³ in the general formula (V) are bonded to each other in the general formula to form an aliphatic ring, an aromatic ring, or a heterocyclic ring May be formed. )
<5> in the general formula (I) ~ (V), X - is an anion of arylsulfonic acids, anions of perfluoroalkyl sulfonic acid, an anion of perhalogenated Lewis acids, perfluoroalkyl sulfonimide anion, or, The conductive composition according to <4>, which is an alkyl or aryl borate anion.
<6> (D) The conductive composition according to any one of <1> to <5>, wherein the polymerizable compound is a compound having two or more cationically polymerizable groups.
<7> (D) The conductive composition according to <6>, wherein the cationically polymerizable group of the polymerizable compound is an epoxy group, an oxetane group, and / or a vinyl ether group.
<8> The conductive composition according to any one of <1> to <7>, including a solvent.
<9> In the total solid content of the conductive composition, (A) 3 to 50% by mass of carbon nanotubes, (B) 30 to 80% by mass of conductive polymer, and (C) 1 to 50 of onium salt compound. The electrically conductive composition in any one of <1>-<8> containing 5-50 mass% of (mass%) and (D) polymeric compound.
<10> The conductive composition according to any one of <1> to <9>, which is for thermoelectric conversion.
<11> A conductive film formed using the conductive composition according to any one of <1> to <10>.
<12> (D) The conductive film according to <11>, including a polymer containing a polymerizable compound as a constituent component.
<13> A conductive laminate comprising a base material and the conductive film according to <11> or <12> provided on the base material.
<14> The conductive laminate according to <13>, wherein the substrate is a resin film.
<15> A thermoelectric conversion element using the conductive film according to <11> or <12> or the conductive laminate according to <13> or <14>.
The thermoelectric conversion element according to <15>, having a <16> electrode.
<17> A thermoelectric power generation article using the thermoelectric conversion element according to <15> or <16>.
<18> A method for producing a conductive film or a conductive laminate, comprising a step of forming a film using the conductive composition according to any one of <1> to <10>.
<19> The production method according to <18>, wherein the film forming step includes a step of applying a conductive composition onto a substrate.
<20> The production method according to <18> or <19>, comprising a step of performing heating or active energy ray irradiation after film formation.
<21> The production method according to <20>, comprising a step of heating at 60 to 150 ° C. for 1 to 20 minutes after heating or irradiation with active energy rays.

The conductive composition of the present invention is excellent in dispersibility of CNT and conductive polymer, and is excellent in handling such as coating property on a substrate. Moreover, since the outstanding electroconductivity which CNT has is not impaired, it can use suitably for preparation of the electroconductive film | membrane (film) and electroconductive laminated body which were more excellent in electroconductivity. Furthermore, since the electroconductive film and electroconductive laminate obtained from the electroconductive composition of the present invention contain a polymerizable compound, they can be cured by a polymerization reaction to further enhance durability.
The conductive film and the conductive laminate of the present invention have higher conductivity and good thermoelectric conversion performance associated therewith, and are also excellent in durability.
The thermoelectric conversion element and thermoelectric power generation article of the present invention are excellent in thermoelectric conversion efficiency and at the same time have high durability.

It is a figure which shows typically an example of the thermoelectric conversion element of this invention. The arrows in FIG. 1 indicate the direction of the temperature difference applied when the element is used. It is a figure which shows typically an example of the thermoelectric conversion element of this invention. The arrows in FIG. 2 indicate the direction of the temperature difference applied when the element is used.

The conductive composition of the present invention contains (A) CNT, (B) a conductive polymer, (C) an onium salt compound, and (D) a polymerizable compound. The conductive composition of the present invention may contain other components such as a solvent.
Hereinafter, the conductive composition of the present invention will be described in detail.

[(A) Carbon nanotube (CNT)]
A CNT is a single-walled CNT in which a single carbon film (graphene sheet) is wound in a cylindrical shape, a double-walled CNT in which two graphene sheets are wound in a concentric shape, and a plurality of graphene sheets in a concentric circle There are multi-walled CNTs wound in a shape. In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone, or two or more kinds may be used in combination. In particular, it is preferable to use single-walled CNT and double-walled CNT having excellent properties in terms of conductivity and semiconductor properties, and more preferably single-walled CNT.
Single-walled CNTs may be semiconducting or metallic, and both may be used in combination. When both semiconducting CNT and metallic CNT are used, the content ratio of both in the composition can be appropriately adjusted according to the use of the composition. For example, when used as an electrode, it is preferable that the content ratio of metallic CNT is high from the viewpoint of conductivity. When used as a semiconductor application, it is preferable that the content ratio of semiconducting CNT is high from the viewpoint of semiconductor characteristics. The CNT may contain a metal or the like, or may contain a molecule such as fullerene. Note that the conductive composition of the present invention may contain nanocarbons such as carbon nanohorns, carbon nanocoils, and carbon nanobeads in addition to CNTs.

CNT can be produced by an arc discharge method, a chemical vapor deposition method (hereinafter referred to as a CVD method), a laser ablation method, or the like. The CNT used in the present invention may be obtained by any method, but is preferably obtained by an arc discharge method and a CVD method.
When producing CNTs, fullerene, graphite, and amorphous carbon are simultaneously generated as by-products, and catalyst metals such as nickel, iron, cobalt, and yttrium remain. In order to remove these impurities, purification is preferably performed. The method for purifying CNTs is not particularly limited, but acid treatment with nitric acid, sulfuric acid, etc., and ultrasonic treatment are effective for removing impurities. In addition, it is more preferable to perform separation and removal using a filter from the viewpoint of improving purity.

After purification, the obtained CNT can be used as it is. Moreover, since CNT is generally produced in a string shape, it may be cut into a desired length depending on the application. For example, when used for semiconductor applications, it is preferable to use CNT shorter than the distance between element electrodes in order to prevent short circuit between element electrodes. CNTs can be cut into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, freeze pulverization method or the like. In addition, it is also preferable to perform separation using a filter from the viewpoint of improving purity.
In the present invention, not only cut CNTs but also CNTs produced in the form of short fibers in advance can be used in the same manner. Such short fibrous CNTs, for example, form a catalytic metal such as iron or cobalt on a substrate and thermally decompose carbon compounds on the surface at 700 to 900 ° C. by CVD to grow CNTs in a vapor phase. Thus, a shape oriented in the direction perpendicular to the substrate surface is obtained. The short fiber CNTs thus produced can be taken out by a method such as peeling off from the substrate. In addition, the short fibrous CNTs can be obtained by supporting a catalytic metal on a porous support such as porous silicon or an anodic oxide film of alumina and growing the CNTs on the surface by the CVD method. Using oriented molecules such as iron phthalocyanine containing a catalytic metal in the molecule as a raw material and producing CNTs on a substrate by performing CVD in an argon / hydrogen gas flow, producing oriented short fiber CNTs You can also. Furthermore, it is also possible to obtain short fiber CNTs oriented on the SiC single crystal surface by an epitaxial growth method.

  The average length of the CNTs used in the present invention is not particularly limited, and can be appropriately selected according to the use of the composition. For example, when the conductive composition of the present invention is used for semiconductor applications, the average length of CNTs is 0.01 μm or more and 1000 μm from the viewpoints of manufacturability, film formability, conductivity, etc., depending on the distance between electrodes. Or less, more preferably 0.1 μm or more and 100 μm or less.

  The diameter of the CNT used in the present invention is not particularly limited, but is preferably 0.4 nm or more and 100 nm or less, more preferably 50 nm or less, and still more preferably, from the viewpoint of durability, transparency, film formability, conductivity, and the like. Is 15 nm or less.

[(B) Conductive polymer]
The conductive polymer used in the present invention is a polymer compound having a conjugated molecular structure. The polymer having a conjugated molecular structure refers to a polymer having a structure in which a single bond and a double bond are alternately connected in a carbon-carbon bond on the main chain of the polymer. Further, the conductive polymer used in the present invention is not necessarily a high molecular weight compound, and may be an oligomer compound.
By using the conductive polymer together with the aforementioned CNT, the CNTs are uniformly dispersed without being aggregated in the composition, and the coating property of the composition is improved. Moreover, a highly conductive composition can be obtained. This is because the conductive polymer has a long conjugated structure, so that the charge transfer between the polymer and CNT is smooth, and as a result, the original high conductivity and semiconductor characteristics of CNT can be effectively used. This is probably because of this.

  Specific examples of the conductive polymer used in the present invention include thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene. Compound, p-fluorenylene vinylene compound, polyacene compound, polyphenanthrene compound, metal phthalocyanine compound, p-xylylene compound, vinylene sulfide compound, m-phenylene compound, naphthalene vinylene compound, p- A repeating unit derived from a phenylene oxide compound, a phenylene sulfide compound, a furan compound, a selenophene compound, an azo compound, a metal complex compound, or a derivative in which a substituent is introduced into these compounds. Have That conjugated polymer and the like.

The substituent in the above derivative is not particularly limited, but is preferably selected and introduced in consideration of compatibility with other components and the type of medium used.
For example, when an organic solvent is used as a medium, an alkoxyalkyleneoxy group, an alkoxyalkyleneoxyalkyl group, a crown ether group, an aryl group, etc. are preferably used in addition to a linear, branched, or cyclic alkyl group, alkoxy group, or thioalkyl group. be able to. These groups may further have a substituent. The number of carbon atoms of the substituent is not particularly limited, but is preferably 1 to 12, more preferably 4 to 12, and particularly a long-chain alkyl group, alkoxy group or thioalkyl group having 6 to 12 carbon atoms. An alkoxyalkyleneoxy group and an alkoxyalkyleneoxyalkyl group are preferred.
When an aqueous medium is used, it is preferable to introduce a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a hydroxyl group, or a phosphoric acid group to the terminal of each monomer or the above substituent.
In addition, dialkylamino group, monoalkylamino group, amino group, carboxyl group, ester group, amide group, carbamate group, nitro group, cyano group, isocyanate group, isocyano group, halogen atom, perfluoroalkyl group, perfluoro An alkoxy group or the like can be introduced as a substituent, which is preferable.
The number of substituents that can be introduced is not particularly limited, and one or more substituents can be appropriately introduced in consideration of the dispersibility, compatibility, conductivity, and the like of the conductive polymer.

  Examples of the conjugated polymer having a repeating unit derived from a thiophene compound and a derivative thereof include polythiophene, a conjugated polymer including a repeating unit derived from a monomer having a substituent introduced into the thiophene ring, and a condensation containing a thiophene ring Examples thereof include conjugated polymers containing a repeating unit derived from a monomer having a polycyclic structure.

  Examples of the conjugated polymer containing a repeating unit derived from a monomer having a substituent introduced into a thiophene ring include poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, and poly-3-cyclohexyl. Thiophene, poly-3- (2′-ethylhexyl) thiophene, poly-3-octylthiophene, poly-3-dodecylthiophene, poly-3- (2′-methoxyethoxy) methylthiophene, poly-3- (methoxyethoxyethoxy) ) Poly-alkyl-substituted thiophenes such as methylthiophene, poly-3-methoxythiophene, poly-3-ethoxythiophene, poly-3-hexyloxythiophene, poly-3-cyclohexyloxythiophene, poly-3- (2'-) Ethylhexyloxy) thiophene, poly-3- Poly-alkoxy substituted thiophenes such as decyloxythiophene, poly-3-methoxy (diethyleneoxy) thiophene, poly-3-methoxy (triethyleneoxy) thiophene, poly- (3,4-ethylenedioxythiophene), poly- Poly-3-alkoxy-substituted-4-alkyl-substituted thiophenes such as 3-methoxy-4-methylthiophene, poly-3-hexyloxy-4-methylthiophene, poly-3-dodecyloxy-4-methylthiophene, poly- Examples thereof include poly-3-thioalkylthiophenes such as 3-thiohexylthiophene, poly-3-thiooctylthiophene, and poly-3-thiododecylthiophene.

  Of these, poly-3-alkylthiophenes and poly-3-alkoxythiophenes are preferable. Regarding polythiophene having a substituent at the 3-position, anisotropy occurs depending on the direction of bonding at the 2,5-position of the thiophene ring. In polymerization of 3-substituted thiophene, those in which the 2-positions of the thiophene ring are bonded to each other (HH conjugate: head-to-head), those in which the 2-position and 5-position are bonded (HT conjugate: head-to-tail) It becomes a mixture of those in which 5-positions are bonded (TT conjugate: tail-to-tail), but the higher the ratio of those in which 2-position and 5-position are bonded (HT conjugate), the more the polymer main chain The planarity is improved, a π-π stacking structure between polymers is easily formed, and it is preferable for facilitating the movement of charges. The proportion of these bonding modes can be measured by H-NMR. The proportion of the HT conjugate in which the 2-position and 5-position of the thiophene ring are bonded in the polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.

  More specifically, a conjugated polymer including a repeating unit derived from a monomer having a substituent introduced into a thiophene ring, and a conjugated polymer including a repeating unit derived from a monomer having a condensed polycyclic structure including a thiophene ring. The following compounds can be exemplified as: In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from a pyrrole compound and a derivative thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from an aniline compound and a derivative thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from an acetylene compound and a derivative thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from a p-phenylene compound and a derivative thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from a p-phenylene vinylene compound and derivatives thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from a p-phenylene ethynylene compound and a derivative thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Examples of the conjugated polymer having a repeating unit derived from a compound other than the above and derivatives thereof include the following compounds. In the following formula, n represents an integer of 10 or more.

  Among the conjugated polymers, it is preferable to use a linear conjugated polymer. For example, in the case of a polythiophene polymer or a polypyrrole polymer, such a linear conjugated polymer is obtained by bonding the thiophene ring or pyrrole ring of each monomer at the 2,5-positions. In poly-p-phenylene polymer, poly-p-phenylene vinylene polymer, and poly-p-phenylene ethynylene polymer, the phenylene group of each monomer is bonded at the para position (1, 4 position). can get.

  The conductive polymer used in the present invention may have one or more of the above-mentioned repeating units (hereinafter, the monomer giving this repeating unit is also referred to as “first monomer (group)”). You may have in combination. Further, in addition to the first monomer, a repeating unit derived from a monomer having another structure (hereinafter referred to as “second monomer”) may be included. In the case of a polymer composed of a plurality of types of repeating units, it may be a block copolymer, a random copolymer, or a graft polymer.

  Examples of the second monomer having another structure used in combination with the first monomer include a fluorenylene group, a carbazole group, a dibenzo [b, d] silole group, a thieno [3,2-b] thiophene group, and a thieno [ 2,3-c] thiophene group, benzo [1,2-b; 4,5-b ′] dithiophene group, cyclopenta [2,1-b; 3,4-b ′] dithiophene group, pyrrolo [3,4] -C] pyrrole-1,4 (2H, 5H) -dione group, benzo [2,1,3] thiadiazole-4,8-diyl group, azo group, 1,4-phenylene group, 5H-dibenzo [b, d] Compounds having a silole group, a thiazole group, an imidazole group, a pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione group, an oxadiazole group, a thiadiazole group, a triazole group, and the like of Derivatives obtained by introducing a substituent group to the compound and the like. Examples of the substituent to be introduced include the same substituents as described above.

  The conductive polymer used in the present invention has a total of 50% by mass or more of repeating units derived from one or more monomers selected from the first monomer group in the conductive polymer. Preferably, it is more preferably 70% by mass or more, and further preferably consists of only a repeating unit derived from one or more types of monomers selected from the first monomer group. Particularly preferred is a conjugated polymer comprising only a single repeating unit selected from the first monomer group.

  Among the first monomer group, a polythiophene polymer containing a repeating unit derived from a thiophene compound and / or a derivative thereof is more preferably used. In particular, a polythiophene polymer having a thiophene ring represented by the following structural formulas (1) to (5) or a thiophene ring-containing condensed aromatic ring structure as a repeating unit is preferable.

In the structural formulas (1) to (5), R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, an amino group, a thioether group, or polyethylene. An oxy group and an ester group are represented, Y represents a carbon atom or a nitrogen atom, and n represents an integer of 1 or 2. Moreover, * represents the connection part of each repeating unit.

The molecular weight of the conductive polymer is not particularly limited, and may be a high molecular weight oligomer or an oligomer having a lower molecular weight (for example, a weight average molecular weight of about 1000 to 10,000).
From the viewpoint of conductivity, the conductive polymer is preferably one that is not easily decomposed by acid, light, and heat. In order to obtain high conductivity, intramolecular carrier transmission and intermolecular carrier hopping through a long conjugated chain of a conductive polymer are required. For this purpose, the molecular weight of the conductive polymer is preferably large to some extent. From this viewpoint, the molecular weight of the conductive polymer used in the present invention is preferably 5000 or more in terms of weight average molecular weight, and is preferably 7000 to 300,000. It is more preferable that it is 8000-100,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

These conductive polymers can be produced by polymerizing the above monomer as a constituent unit by a usual oxidative polymerization method.
Moreover, a commercial item can also be used, for example, the poly (3-hexyl thiophene-2,5-diyl) regioregular product made from an Aldrich company is mentioned.

[(C) Onium salt compound]
The conductive composition of the present invention contains an onium salt compound, and the onium salt compound can dramatically improve the conductivity of the composition. The details of the mechanism by which the conductivity is improved are not yet clear, but the onium compound is appropriately activated by applying energy such as light and heat from the outside to the CNT and / or conductive polymer. And expresses oxidizing ability. It is considered that an acid is generated during the oxidation process, and the generated acid acts as a dopant. The dopant improves the conductivity because the conductive polymer and the charge transfer between the conductive polymer and the CNT become smoother.
In the conventional doping technique, an acid such as a protonic acid or a Lewis acid is used as a dopant. Therefore, CNTs and conductive polymers are aggregated, precipitated, and precipitated at the time when the acid is added to the composition. Such a composition is inferior in coating property and film forming property, and as a result, conductivity is also lowered.
The onium salt compound of the present invention is neutral and does not aggregate, precipitate, or precipitate CNTs or conductive polymers. It is also a compound that generates an acid when energy such as light and heat is applied, and the start timing of acid generation can be controlled. The composition can be prepared under conditions that do not generate an acid to prevent aggregation, and the composition can be molded while maintaining good dispersibility and coating properties. Therefore, high conductivity can be imparted by appropriately applying energy after molding and film formation.
Although the composition of the present invention realizes improvement of CNT dispersibility by a conductive polymer, the onium salt compound can maintain good dispersibility and coatability even when used together with these. The film quality after coating is also good, and CNT, conductive polymer, and onium salt compound are uniformly dispersed. Therefore, by applying external energy such as heat and light as needed after coating, high conductivity is achieved. Show.

  For the above reasons, the onium salt compound used in the present invention is preferably a compound having an oxidizing ability with respect to CNT and / or a conductive polymer. Furthermore, the onium salt compound used in the present invention is preferably a compound (acid generator) that generates an acid upon application of energy such as light or heat. Examples of the energy application method include irradiation with active energy rays and heating.

  Examples of such onium salt compounds include sulfonium salts, iodonium salts, ammonium salts, carbonium salts, phosphonium salts, and the like. Of these, sulfonium salts, iodonium salts, ammonium salts and carbonium salts are preferable, sulfonium salts, iodonium salts and carbonium salts are more preferable, and sulfonium salts and iodonium salts are particularly preferable. Examples of the anion moiety constituting the salt include a strong acid counter anion.

  Specifically, compounds represented by the following general formulas (I) and (II) are used as sulfonium salts, compounds represented by the following general formula (III) are used as iodonium salts, and the following general formulas are used as ammonium salts. Examples of the compound represented by (IV) and the carbonium salt include compounds represented by the following general formula (V), which are preferably used in the present invention.

In the general formulas (I) to (V), R ^{21 to} R ²³ , R ^{25 to} R ²⁶ and R ^{31 to} R ³³ are each independently a linear, branched or cyclic alkyl group, an aralkyl group, an aryl group, Represents an aromatic heterocyclic group. R ^{27 to} R ³⁰ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, or an aryloxy group. R ²⁴ represents a linear, branched or cyclic alkylene group or an arylene group. R ^{21 to} R ³³ may further have a substituent. X ⁻ represents an anion of a strong acid.
Any two groups of ^R 21 ^{to R 23} in the general formula (I) is, ^{R 21} and ^{R 23} in the general formula (II) is, the ^{R 25} and ^{R 26} in formula (III), general formula (IV) Any two groups of R ^{27 to} R ³⁰ are bonded to any two groups of R ^{31 to} R ³³ in the general formula (V) to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. May be.

In R ^{21 to} R ²³ and R ^{25 to} R ³³ , the linear or branched alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, n- A butyl group, a sec-butyl group, a t-butyl group, a hexyl group, an octyl group, a dodecyl group, and the like can be given.
The cyclic alkyl group is preferably an alkyl group having 3 to 20 carbon atoms, and specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a bicyclooctyl group, a norbornyl group, an adamantyl group, and the like.
As the aralkyl group, an aralkyl group having 7 to 15 carbon atoms is preferable, and specific examples include a benzyl group and a phenethyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and specific examples include a phenyl group, a naphthyl group, an anthranyl group, a phenanthyl group, and a pyrenyl group.
Examples of the aromatic heterocyclic group include pyridyl group, pyrazole group, imidazole group, benzimidazole group, indole group, quinoline group, isoquinoline group, purine group, pyrimidine group, oxazole group, thiazole group, thiazine group and the like.

In R ^{27 to} R ³⁰ , the alkoxy group is preferably a linear or branched alkoxy group having 1 to 20 carbon atoms, specifically, a methoxy group, an ethoxy group, an iso-propoxy group, a butoxy group, or a hexyloxy group. Etc.
The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and specific examples include a phenoxy group and a naphthyloxy group.

In R ²⁴ , the alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and specific examples include an ethylene group, a propylene group, a butylene group, and a hexylene group. The cyclic alkylene group is preferably a C 3-20 cyclic alkylene group, and specific examples include a cyclopentylene group, cyclohexylene, bicyclooctylene group, norbornylene group, adamantylene group and the like.
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, and specific examples include a phenylene group, a naphthylene group, and an anthranylene group.

When R ^{21 to} R ³³ further have a substituent, the substituent is preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, an iodine atom), Aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxyl group, carboxy group, acyl group, alkoxycarbonyl group, alkylcarbonylalkyl group, aryl A carbonylalkyl group, a nitro group, an alkylsulfonyl group, a trifluoromethyl group, —S—R ^{41 and the} like can be mentioned. R ⁴¹ has the same meaning as R ²¹ .

X ⁻ is preferably an anion of an aryl sulfonic acid, an anion of a perfluoroalkyl sulfonic acid, an anion of a perhalogenated Lewis acid, an anion of a perfluoroalkylsulfonimide, a perhalogenate anion, or an alkyl or aryl borate anion. These may further have a substituent, and examples of the substituent include a fluoro group.
Specific examples of anions of aryl sulfonic acids include p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , PhSO ₃ ⁻ , naphthalene sulfonic acid anions, naphthoquinone sulfonic acid anions, naphthalenedisulfonic acid anions, anthraquinone sulfonic acid anions Is mentioned.
Specific examples of the anion of perfluoroalkylsulfonic acid include CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , and C ₈ F ₁₇ SO ₃ ^— .
Specific examples of the anion of the perhalogenated Lewis acid include PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , and FeCl ₄ ⁻ .
Specific examples of the anion of perfluoroalkylsulfonimide include CF ₃ SO ₂ —N ^— SO ₂ CF ₃ and C ₄ F ₉ SO ₂ —N ^— SO ₂ C ₄ F ₉ .
Specific examples of the perhalogenate anion include ClO ₄ ⁻ , BrO ₄ ⁻ and IO ₄ ⁻ .
Specific examples of the alkyl or aryl borate anion include (C ₆ H ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (p-CH ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ H _{4 F)} 4 B ^-, and the like.
X ^- is more preferably an anion of perhalogenated Lewis acid, a fluoro group is an alkyl or aryl borate anions were replaced, more preferably fluoro substituted aryl borate anions, particularly preferably a pentafluorophenyl borate anion.

  Specific examples of the onium salt are shown below, but the present invention is not limited thereto.

In the above specific examples, X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ⁻ , BF ₄ ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , RfSO ₃ ⁻ , ( C ₆ F ₅ ) ₄ B ⁻ , or an anion represented by the following formula

Rf represents a perfluoroalkyl group having an optional substituent.

  In the present invention, an onium salt compound represented by the following general formula (VI) or (VII) is particularly preferable.

In general formula (VI), Y represents a carbon atom or a sulfur atom, Ar ¹ represents an aryl group, and Ar ^{2 to} Ar ⁴ each independently represents an aryl group or an aromatic heterocyclic group. Ar ^{1 to} Ar ⁴ may be further substituted.
Ar ¹ is preferably a fluoro-substituted aryl group, more preferably a pentafluorophenyl group or a phenyl group substituted with at least one perfluoroalkyl group, and particularly preferably a pentafluorophenyl group.
The aryl group and aromatic heterocyclic group of Ar ^{2 to} Ar ^{4 have} the same meanings as the aryl group and aromatic heterocyclic group of R ^{21 to} R ²³ and R ^{25 to} R ³³ described above, preferably an aryl group. Yes, more preferably a phenyl group. These groups may be further substituted, and examples of the substituent include the above-described substituents R ^{21 to} R ³³ .

In General Formula (VII), Ar ¹ represents an aryl group, and Ar ⁵ and Ar ⁶ each independently represent an aryl group or an aromatic heterocyclic group. Ar ¹ , Ar ⁵ and Ar ⁶ may be further substituted.
Ar ¹ has the same meaning as Ar ^{1 in the} general formula (VI), and the preferred range is also the same.
Ar ⁵ and Ar ⁶ are synonymous with Ar ^{2 to} Ar ^{4 in} the general formula (VI), and preferred ranges thereof are also the same.

The said onium salt compound can be manufactured by normal chemical synthesis. Moreover, a commercially available reagent etc. can also be used.
One embodiment of the method for synthesizing the onium salt compound is shown below, but the present invention is not limited thereto. Other onium salts can be synthesized by the same method.
2.68 g of triphenylsulfonium bromide (manufactured by Tokyo Chemical Industry), 5.00 g of lithium tetrakis (pentafluorophenyl) borate-ethyl ether complex (manufactured by Tokyo Chemical Industry), and 146 ml of ethanol were placed in a 500 ml three-necked flask and 2 at room temperature. After stirring for a period of time, 200 ml of pure water is added, and the precipitated white solid is collected by filtration. By washing the white solid with pure water and ethanol and vacuum drying, 6.18 g of triphenylsulfonium tetrakis (pentafluorophenyl) borate can be obtained as an onium salt.

  An onium salt compound can be used individually by 1 type or in combination of 2 or more types. The content of the onium salt compound is preferably 3 parts by mass or more, more preferably 5 to 50 parts by mass, and further preferably 10 to 40 parts by mass with respect to 100 parts by mass of the conductive polymer from the viewpoint of the doping effect. It is.

[(D) Polymerizable compound]
As the polymerizable compound used in the present invention, a cationic polymerizable compound and / or a radical polymerizable compound can be used. Preferably, it is a cationically polymerizable compound, and is a compound that initiates a polymerization reaction by the radical species of the acid or precursor of the acid generated from the (C) onium salt compound upon application of heat or active energy ray irradiation, and cures. There are no particular restrictions.
As the cationic polymerizable compound, various known cationic polymerizable monomers known as photo cationic polymerizable monomers can be used. Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and 2001-2001. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aromatic epoxides.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts and epichlorohydrin, such as bisphenol A or its alkylene oxides. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkene ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably.
Examples of aliphatic epoxides include dihydric polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or 1,6. -Diglycidyl ether of alkylene glycol such as diglycidyl ether of hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, diglycidyl of polyethylene glycol or its alkylene oxide adduct Diglycidyl of polyalkylene glycol typified by diglycidyl ether of ether, polypropylene glycol or its alkylene oxide adduct Ether and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The monofunctional and polyfunctional epoxy compounds that can be used in the present invention are exemplified in detail.
Examples of monofunctional epoxy compounds include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene. Monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. Is mentioned.

  Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy Hexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy- 6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8 -Diepoxyoctane, 1,2,5,6-diepoxycyclooctane and the like.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylol. Di- or trivinyl ether compounds such as propane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-pro Vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

Below, monofunctional vinyl ether and polyfunctional vinyl ether are illustrated in detail.
Examples of monofunctional vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4 -Methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl D Ter, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloro Examples thereof include ethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether and the like.

Examples of the polyfunctional vinyl ether include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a substrate, surface hardness of the formed coating film, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound that can be used in the present invention refers to a compound having at least one oxetane ring, and is known oxetane as described in JP-A Nos. A compound can be arbitrarily selected and used.
As the compound having an oxetane ring that can be used in the conductive composition of the present invention, a compound having 1 to 4 oxetane rings in its structure is preferable. By using such a compound, it becomes easy to maintain the viscosity of the conductive composition within a good handling range, and to obtain high adhesion between the conductive film after curing and the substrate. Can do.

  Examples of the compound having 1 to 2 oxetane rings in the molecule include compounds represented by the following formulas (1) to (3).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.
R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxycarbonyl group, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, and 2-methyl-2. -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like. Examples of the group having an aromatic ring include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like. Can be mentioned. As the alkylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, etc., as an alkoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, etc., as an N-alkylcarbamoyl group, Examples thereof include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group. R ^a2 may have a substituent, and examples of the substituent include an alkyl group of 1 to 6 and a fluorine atom.

R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group Represents an alkylene group containing, an alkylene group containing a carbamoyl group, or a group shown below. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

When R ^a3 is the above polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, Represents a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure. In the following formula, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  As a compound represented by the formula (1), 3-ethyl-3-hydroxymethyloxetane (OXT-101: manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (OXT) -212: manufactured by Toagosei Co., Ltd.) and 3-ethyl-3-phenoxymethyloxetane (OXT-211: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (2) include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: Toagosei Co., Ltd.). ), Bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: Toagosei Co., Ltd.) is exemplified.

  Examples of the compound having 3 to 4 oxetane rings include a compound represented by the following formula (4).

In the formula (4), R ^a1 has the same ^{meaning as} in the formula (1). In addition, as R ^a9 which is a polyvalent linking group, for example, a branched polyalkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly ( An alkyleneoxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Another embodiment of the oxetane compound that can be suitably used in the present invention includes a compound represented by the following formula (5) having an oxetane ring in the side chain.

In the formula (5), R ^a8 has the same ^{meaning as} in the above formula. R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

Such a compound having an oxetane ring is described in detail in JP-A No. 2003-341217, paragraph numbers 0021 to 0084, and the compounds described therein can be suitably used in the present invention.
Oxetane compounds described in JP 2004-91556 A can also be used in the present invention. This is described in detail in paragraphs 0022 to 0058.

The cationically polymerizable compound that can be used in the present invention may be used alone or in combination of two or more, but from the viewpoint of effectively suppressing shrinkage during curing, an oxetane compound and It is preferable to use a vinyl ether compound in combination with at least one compound selected from epoxy compounds.
The radical polymerizable compound used in the present invention is preferably selected from compounds having at least one acrylate group, methacrylate group, acrylamide group, methacrylamide group, and N-vinyl group, more preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention.

  Specific examples of the compound having an acrylate group and a methacrylate group include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate, epoxy Acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethylphthalic acid, methoxy-polyethylene glycol acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, cyclic trimethylo Lepropane formal acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol EO adduct acrylate, phenoxy Diethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, lactone modified acrylate, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate, lactone modified acrylate, bis (4-acryloxypolyethoxy) Phenyl) propane, 1,6-hexanediol diacrylate, tripropylene glycol Diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipentaerythritol tetraacrylate, trimethylolpropane (PO-modified) triacrylate, oligoester acrylate, hydroxypivalate neopentyl glycol diacrylate, tetramethylol methane triacrylate, di Methylol tricyclodecane diacrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, PO adduct diacrylate of bisphenol A, EO adduct diacrylate of bisphenol A, dipentaerythritol hexa Acrylate, propylene glycol diglycidyl ether with acrylic acid Additives, acrylate compounds such as ditrimethylolpropane tetraacrylate, methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate 2,2-bis ( And methacrylate compounds such as 4-methacryloxypolyethoxyphenyl) propane. In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (4) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

General formula (4)
^{_{CH 2 = C (R 41)}} COOCH 2 CH (R 42) OH
(However, R ⁴¹ and R ⁴² represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. The PO represents propylene oxide, and EO represents ethylene oxide.

  Specific examples of the compound having an acrylamide group and a methacrylamide group include acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, and methylenebis. Acrylamide compounds such as acrylamide, 1,6-hexamethylene bisacrylamide, xylylene bisacrylamide, diethylenetriamine trisacrylamide, methacrylamide, N-methylol methacrylamide, diacetone methacrylamide, N, N-dimethylmethacrylamide, N, N- Diethylmethacrylamide, N-isopropylmethacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebismeta Riruamido, methacrylamide compounds such as xylylene bis methacrylamide.

  Specific examples of the N-vinyl compound include N-vinylformamide (NVF), N-vinylcaprolactam (NVC), N-vinylpyrrolidone, N-vinylcarbazole and the like. These radical polymerizable compounds can be used in combination with the cationic polymerizable compound.

  The polymerizable compound of the present invention is used in accordance with the performance design of the final conductive film. From the viewpoint of curability, a structure having a large polymerizable group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having 3 or more functional groups are used, but usually 6 or less functional groups. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in curability and film strength, but is not preferable in terms of compatibility with other components and dispersibility. For compatibility and dispersibility, the selection and use method of the polymerizable compound is important. For example, the compatibility may be improved by using two or more compounds in combination.

[solvent]
The conductive composition of the present invention preferably contains a solvent in addition to CNT, a conductive polymer and an onium salt compound.
The solvent only needs to be able to satisfactorily disperse or dissolve CNT, the conductive polymer, and the onium salt compound, and water, an organic solvent, and a mixed solvent thereof can be used. Preferred are organic solvents, halogen solvents such as alcohol and chloroform, polar organic solvents such as DMF, NMP, and DMSO, aromatic solvents such as chlorobenzene, dichlorobenzene, benzene, toluene, and xylene, cyclohexanone, acetone, and methyl A ketone solvent such as ethylkenton and an ether solvent such as diethyl ether, THF, t-butyl methyl ether, dimethoxyethane, and diglyme are preferably used.
The solvent is preferably degassed in advance. The dissolved oxygen concentration in the solvent is preferably 10 ppm or less. Examples of the degassing method include a method of irradiating ultrasonic waves under reduced pressure, a method of bubbling an inert gas such as argon, and the like.

[Other ingredients]
The conductive composition of the present invention may contain other components in the balance in addition to the components described above.
For example, in order to improve the dispersion stability, lithium hydroxide, ammonium persulfate, an ultraviolet absorber and the like can be contained. From the viewpoint of increasing the film strength, inorganic fine particles, polymer fine particles, silane coupling agents, etc., from the viewpoint of increasing the transparency by lowering the refractive index, fluorine compounds, etc., from the viewpoint of preventing unevenness during coating. Can appropriately contain a fluorine-based surfactant or the like according to the application.
The content of these components is preferably about 0.1 to 5% by mass relative to the total mass of the composition.

[Preparation of conductive composition]
The conductive composition of the present invention contains CNT, a conductive polymer, an onium salt compound and a polymerizable compound, and optionally contains a solvent. The composition of the present invention is a CNT dispersion in which CNTs are dispersed in a solvent.
The conductive composition of the present invention can control the conductivity and semiconductor characteristics of the composition by changing the CNT content. The content of CNT, conductive polymer and onium salt compound, and polymerizable compound in the composition is appropriately selected and determined according to the use of the composition and the properties such as conductivity and transparency required for the use. be able to.
The CNT content in the composition is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass in the total solid content.
The content of the conductive polymer in the composition is preferably 30 to 80% by mass in the total solid content, more preferably 35 to 75% by mass, and further preferably 40 to 70% by mass. .
The onium salt compound in the composition is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 10 to 40% by mass in the total solid content.
The content of the polymerizable compound in the composition is preferably 5 to 50% by mass in the total solid content, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass. With regard to the content of the polymerizable compound, a larger amount is advantageous for curability, but if it is too much, phase separation may occur or problems in the production process due to the adhesiveness of the cured film (for example, the conductive film component) This may cause problems such as transfer and defective production due to adhesion.
In the case of using a solvent, the amount of the solvent used is preferably 60 to 99.9% by mass, more preferably 70 to 99.8% by mass, and more preferably 80 to 99.7% by mass in the composition of the present invention. It is more preferable that it is 90-99.6 mass%, and it is especially preferable that it is 95-99.5 mass%.

The conductive composition of the present invention can be prepared by mixing the above components. Preferably, it is prepared by adding at least CNT, a conductive polymer, an onium salt compound and a polymerizable compound to a solvent and dispersing them by a usual method. The order of addition and mixing of each component is not particularly limited, but it is preferable to add a predetermined amount of CNT after previously adding a predetermined amount of a conductive polymer in a solvent.
There is no restriction | limiting in particular in a preparation method, A normal method can be applied. For example, a dispersion method such as a mechanical homogenizer method, a jaw crusher method, an ultracentrifugation method, a cutting mill method, an automatic mortar method, a disk mill method, a ball mill method, or an ultrasonic dispersion method can be used. Further, if necessary, two or more of these methods may be used in combination. A preferred combination of dispersion methods is a mechanical homogenizer method and an ultrasonic dispersion method. There is no limitation on the order of the combination, and there are a method of dispersing sequentially by different dispersion methods or a method of dispersing simultaneously by different dispersion methods. Preferably, the dispersion is first performed by a dispersion method having a weak dispersion energy and then dispersed by a dispersion method having a second highest dispersion energy. By doing so, it becomes possible to disperse CNTs at a high concentration without defects. Specifically, it is preferable to combine the mechanical homogenizer method first and then the ultrasonic dispersion method.
In addition, when the onium salt compound to be used is a compound that generates an acid by applying energy such as heat or light, it is preferable to prepare the composition in a state where radiation or electromagnetic waves are shielded at a temperature at which no acid is generated. Aggregation by an acid or the like can be prevented, and uniform dispersibility or solubility of each component in the composition can be maintained during preparation and storage of the composition.

The composition can be prepared in the atmosphere, but is preferably performed in an inert atmosphere. An inert atmosphere refers to a state where the oxygen concentration is lower than the atmospheric concentration. Preferably, the atmosphere has an oxygen concentration of 10% or less. Examples of the method for making the inert atmosphere include a method of substituting the atmosphere with a gas such as nitrogen or argon, which is preferably used.
The temperature during preparation is preferably in the range of 0 ° C to 50 ° C.

  CNTs contained in the obtained conductive composition may contain defective CNTs. Such CNT defects are preferably reduced in order to reduce the conductivity of the composition. The amount of CNT defects in the composition can be estimated by the ratio G / D of the G-band and D-band of the Raman spectrum. It can be estimated that the higher the G / D ratio, the less the amount of defects, the CNT material. In the present invention, the G / D ratio of the composition is preferably 10 or more, and more preferably 30 or more.

[Conductive film]
The conductive film of the present invention is formed using the conductive composition. In the conductive film of the present invention, the polymerizable compound in the composition used for the preparation exists in a polymerized state. In the production of the conductive film of the present invention, any method that can form the conductive composition of the present invention into a film can be employed without any particular limitation. Preferably, the conductive composition of the present invention can be applied onto a substrate, formed into a film, and applied on the substrate by applying energy such as heat or active energy rays. Details of the film forming method and energy application will be described later. Furthermore, in order to accelerate and complete the curing of the polymerizable compound, after application of energy such as heat and active energy rays, it is 60 to 150 ° C, preferably 80 to 120 ° C, and 1 to 20 minutes, preferably 2 to 5 minutes. More preferably, a heating step is applied.

[Conductive laminate]
The conductive laminate of the present invention has a base material and the conductive film of the present invention provided on the base material. Details of the substrate will be described later. The conductive laminate of the present invention is formed, for example, by applying the conductive composition of the present invention on a substrate, drying it as necessary to form a film, and then applying energy such as heat or active energy rays. It is obtained by. More preferably, after application of energy such as heat or active energy rays, a heating step of 60 to 150 ° C., preferably 80 to 120 ° C., for 1 to 20 minutes, preferably 2 to 5 minutes is applied.

(Film formation method)
The method for forming the conductive film is not particularly limited, and for example, known coating methods such as extrusion die coating, blade coating, bar coating, screen printing, roll coating, curtain coating, spray coating, and dip coating can be used. .
After application, a drying process is performed as necessary. For example, the solvent can be volatilized and dried by blowing hot air.

  The amount of the conductive composition to be used is appropriately adjusted depending on the desired film thickness. What is necessary is just to select the film thickness of a conductive film suitably according to a use. For example, when used for a transparent electrode, the resistance value and the light transmittance are important. In the case of a transparent electrode for a display device such as an LCD, PDP, or EL element, the preferred resistance value is in the range of 0.001 to 100,000 Ω / □, more preferably in the range of 0.1 to 10,000 Ω / □. It is. The light transmittance is about 40% to 100%, preferably 50 to 100%, more preferably 60 to 100%, at 550 nm. In order to satisfy these, the film thickness is appropriately adjusted in consideration of the concentration of CNT, conductive polymer, onium salt compound, polymerizable compound and the like.

(Energy provision)
After film formation, doping is performed by applying external energy to the film by irradiating active energy rays or heating the film. At that time, the onium salt compound generates a radical species of an acid or a precursor thereof, and this acid or radical species causes a polymerization reaction (film curing reaction) of the polymerizable compound. Therefore, the doping and the film curing reaction can proceed simultaneously. Furthermore, after that, it is preferable to heat at 60 to 150 ° C. for 1 to 20 minutes to accelerate and complete the curing of the polymerizable compound.
Active energy rays include radiation and electromagnetic waves, and radiation includes particle beams (high-speed particle beams) and electromagnetic radiation. Particle rays include alpha rays (α rays), beta rays (β rays), proton rays, electron rays (which accelerates electrons with an accelerator regardless of nuclear decay), charged particle rays such as deuteron rays, Examples of the electromagnetic radiation include gamma rays (γ rays) and X-rays (X rays, soft X rays). Examples of electromagnetic waves include radio waves, infrared rays, visible rays, ultraviolet rays (near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays), X-rays, and gamma rays. The line type used in the present invention is not particularly limited. For example, an electromagnetic wave having a wavelength near the maximum absorption wavelength of the onium salt compound (acid generator) to be used may be appropriately selected.
Among these active energy rays, ultraviolet rays, visible rays, and infrared rays are preferable from the viewpoint of doping effect and safety, specifically, 240 to 1100 nm, preferably 300 to 850 nm, more preferably 350 to 670 nm. It is a light ray having absorption.

For irradiation with active energy rays, a radiation or electromagnetic wave irradiation device is used. The wavelength of the radiation or electromagnetic wave to be irradiated is not particularly limited, and a radiation or electromagnetic wave in a wavelength region corresponding to the sensitive wavelength of the onium salt compound to be used may be selected.
Equipment that can irradiate radiation or electromagnetic waves includes LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deep UV lamps, low-pressure UV lamps and other mercury lamps, halide lamps, xenon flash lamps, metal halide lamps, ArF excimer lamps, and KrF excimer lamps. There are exposure apparatuses that use an excimer lamp, an extreme ultraviolet lamp, an electron beam, or an X-ray lamp as a light source. The ultraviolet irradiation can be performed using a normal ultraviolet irradiation apparatus, for example, a commercially available ultraviolet irradiation apparatus for curing / adhesion / exposure (USHIO Inc. SP9-250UB, etc.).

The exposure time and the amount of light may be appropriately selected in consideration of the type of onium salt compound to be used and the doping effect. Specifically, it may be performed at a light amount of 10 mJ / cm ^{2 to} 10 J / cm ² , preferably 50 mJ / cm ^{2 to 5} J / cm ² .

  Doping by heating may be performed by heating the substrate (film formation) coated with the conductive composition at a temperature higher than the temperature at which the onium salt compound generates an acid. The heating temperature is preferably 50 ° C to 200 ° C, more preferably 70 ° C to 150 ° C. The heating time is preferably 1 minute to 60 minutes, more preferably 3 minutes to 30 minutes.

(Base material)
The base material used for the production of the conductive film of the present invention, that is, the base material provided in the conductive laminate of the present invention can be selected according to the use after the conductive film of the present invention is formed. For example, when the conductive film of the present invention is formed as an electrode of a display device such as an LCD, an electrophoretic display material, electronic paper, or an organic EL element, a glass substrate or a plastic substrate can be preferably used. A metal substrate provided with an insulating film between the conductive film and the conductive film can also be used. In addition, a base material is not restricted to plate shape, For example, what has a curved surface and what has unevenness | corrugation etc. can be selected according to a use. Moreover, when using the electroconductive film of this invention for a thermoelectric conversion use, the base material which provided various electrode materials in the crimping | compression-bonding surface of an electroconductive film can be used suitably. As this electrode material, transparent electrodes such as ITO and ZnO, metal electrodes such as silver, copper, gold, and aluminum, carbon materials such as CNT and graphene, organic materials such as PEDOT / PSS, and the like can be used.

When heating or light irradiation is performed after coating and film formation, it is preferable to select a substrate that is not easily affected by these stimuli. Examples of the substrate that can be used in the present invention include substrates such as glass, transparent ceramics, metals, and plastic films. Glass and transparent ceramics lack flexibility compared to metal and plastic films. Further, when the metal and the plastic film are compared in price, the plastic film is preferable because it is less expensive and has flexibility.
From such a viewpoint, as the base material of the present invention, a resin film is preferable, and in particular, a polyester resin (hereinafter, appropriately referred to as “polyester”), a polycycloolefin resin, a polyimide resin, a polycarbonate resin, Polyether resins and polysulfide resins are preferred. The polyester is preferably a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.

  Specific examples of the resin film that can be used in the present invention include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-phthalenedicarboxyl. Polycycloolefin films such as rate, polyester films such as polyester films of bisphenol A and iso and terephthalic acid, product names ZEONOR film (manufactured by Nippon Zeon), ARTON film (manufactured by JSR), Sumilite FS1700 (manufactured by Sumitomo Bakelite) , Product name Kapton (made by Toray DuPont), Apical (made by Kaneka), Ubilex (made by Ube Industries), Pomilan (made by Arakawa Chemical Co., Ltd.), etc., product name Pure Ace ( Polycarbonate films such as Nitto Kasei Co., Ltd., Elmec (manufactured by Kaneka Corporation), polyether ether ketone films such as the product name Sumilite FS1100 (manufactured by Sumitomo Bakelite Co., Ltd.), polyphenyl sulfide films such as the product name Torelina (manufactured by Toray Industries, Inc.), etc. Is mentioned. Although it is appropriately selected depending on the use conditions and environment, commercially available polyethylene terephthalate, polyethylene naphthalate, various polyimides, polycarbonate films, and the like are preferable from the viewpoints of availability, preferably heat resistance of 100 ° C. or higher, economy, and effects.

  Moreover, as long as the effects of the present invention are not impaired, a copolymer of the above resin or a blend of these resins with other types of resins can also be used. The substrate used in the present invention preferably contains an additive such as an ultraviolet absorber. As the ultraviolet absorber, an oxazole, triazine, stilbene, or coumarin absorber can be suitably used. The substrate may be a single layer made of a single material, or may have a structure of two or more layers made of different materials.

  There is no restriction | limiting in particular in the thickness of the resin film used here, Although it can select suitably according to the intended purpose of a film, Generally, it is preferable to use a 5-500 micrometers thing.

  The conductive composition of the present invention has the advantage that the CNTs are excellent in dispersibility and contain few defects, and the types and contents of CNTs, conductive polymers, onium salt compounds, polymerizable compounds, etc. By appropriately adjusting the thickness, a conductive film having a high conductivity of about 10 to 2000 S / cm can be obtained. Therefore, the conductive composition, conductive film, and conductive laminate of the present invention are used for transparent electrodes, capacitors, capacitors, secondary batteries, etc. used in various display elements typified by liquid crystal displays and solar cells. Thermoelectric conversion materials used for environmental power generation such as solar power generation, hot water power generation, power generation using exhaust heat from electronic devices, sensor networks and health monitors using temperature differences between outside air and body temperature, etc. It is useful as a thermoelectric conversion element.

[Thermoelectric conversion element]
The thermoelectric conversion element of the present invention is not particularly limited as long as it includes the conductive film of the present invention or the conductive laminate of the present invention, and the configuration thereof is not particularly limited. It is preferable to have the thermoelectric conversion layer containing these and the electrode which electrically connects these.
Examples of the structure of the thermoelectric conversion element of the present invention include the structure of the element (1) shown in FIG. 1 and the element (2) shown in FIG. The element (1) shown in FIG. 1 includes a pair of electrodes including a first electrode (13) and a second electrode (15) on a first base (12), and a thermoelectric conversion layer between the electrodes. (14) is an element provided with the conductive film of the present invention. The second electrode (15) is disposed on the surface of the second base material (16), and the first base material (12) and the second base material (16) are arranged on the outer sides of the metal facing each other. A plate (17) is provided. In the element (2) shown in FIG. 2, a first electrode (23) and a second electrode (25) are disposed on a first base material (22), and a thermoelectric conversion material layer (24) is disposed thereon. ) Is provided with the conductive film of the present invention. 1 and 2, arrows indicate the direction of temperature difference when the thermoelectric conversion element is used.
The thermoelectric conversion element of the present invention may be provided with the conductive laminate of the present invention. In this case, the substrate constituting the conductive laminate of the present invention is the first substrate (12 , 22). That is, it is preferable that the above-mentioned various electrode materials are provided on the surface of the base material of the conductive laminate of the present invention (the pressure contact surface with the thermoelectric conversion material).
One surface of the formed thermoelectric conversion material layer (conductive film) is covered with a base material. When a thermoelectric conversion element is prepared using this layer, the other surface is also provided with a base material (second film). The base material (16, 26) is preferably pressure-bonded from the viewpoint of protecting the film. Moreover, you may provide the said various electrode material previously in this 2nd base material (16) surface (crimp surface with a thermoelectric conversion material layer). Moreover, it is preferable to perform the crimping | compression-bonding with a 2nd base material and a thermoelectric conversion material layer by heating to about 100 to 200 degreeC from a viewpoint of adhesive improvement.

In the thermoelectric conversion element of the present invention, the thickness of the thermoelectric conversion layer is preferably 0.1 μm to 1000 μm, and more preferably 1 μm to 100 μm. A thin film thickness is not preferable because it is difficult to provide a temperature difference and the resistance in the film increases.
In addition, the thickness of the first and second base materials is preferably 30 to 3000 μm, more preferably 100 to 1000 μm from the viewpoints of handleability and durability.
In general, in a thermoelectric conversion element, compared to a photoelectric conversion element such as an organic thin film solar cell element, the conversion layer may be applied and formed in one organic layer, and the element can be easily manufactured. In particular, when the thermoelectric conversion material of the present invention is used, it is possible to increase the film thickness by about 100 to 1000 times compared to the element for organic thin film solar cells, and the chemical stability against oxygen and moisture in the air is improved. To do.

[Thermoelectric power products]
The thermoelectric power generation article of the present invention includes an object, a device, a machine, an instrument, and the like that perform thermoelectric conversion using the thermoelectric conversion element of the present invention. More specifically, generators such as hot spring thermal generators, solar thermal generators, waste heat generators, wristwatch power supplies, semiconductor drive power supplies, small sensor power supplies, and the like can be given.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to them.

Example 1
10 mL of o-dichlorobenzene is added to 12 mg of CNT (single-walled carbon nanotube: ASP-100F, manufactured by Hanwha Nanotech, purity 95%) and 20 mg of the following conductive polymer 120, and the mixture is stirred for 20 minutes with a mechanical stirring device. Stir. Then, CNT dispersion liquid of dichlorobenzene was obtained by ultrasonically dispersing for 10 minutes at 30 ° C. using an ultrasonic cleaner (US-2 manufactured by Inoue Seieido Co., Ltd., output 120 W, indirect irradiation). To this solution, 8 mg of the exemplified compound (I-9) as an onium salt compound and 4 mg and 6 mg of the following polymerizable compounds 1 and 6 were added at room temperature, respectively, to prepare a dichlorobenzene dispersion of the conductive composition. did. The G / D ratio of this dispersion was measured by the following method and found to be 65. On the other hand, after a 1.1 mm thick, 40 mm × 50 mm glass substrate was ultrasonically cleaned in acetone, a UV-ozone treatment was performed for 10 minutes. A dichlorobenzene dispersion of the conductive composition was applied onto the glass substrate with a spin coater and then dried for 3 hours at room temperature under vacuum to form a conductive film having a thickness of about 1 μm. Thereafter, ultraviolet irradiation (light amount: about 500 mJ / cm ² ) was performed with an ultraviolet irradiation machine (ECS-401GX, manufactured by Eye Graphics Co., Ltd.) and post-heating treatment was performed at 80 ° C. for 2 minutes as appropriate.
The conductivity, thermoelectric conversion performance (ZT), film formability, and strength of the obtained film were measured and evaluated by the following methods. The results are shown in Table 1 below.

[G / D ratio]
By measuring the Raman spectrum of the dispersion (wavelength 633 nm, laser Raman spectrometer manufactured by Horiba, Ltd.), the degree of CNT defects was evaluated from the G-band and D-band spectral intensity ratios using the G / D ratio. The smaller the G / D ratio, the more CNT defects.

[Measurement of conductivity and thermoelectric conversion performance]
The obtained conductive film was evaluated for Seebeck coefficient (unit: μV / K) and conductivity (unit: S / cm) at 100 ° C. using a thermoelectric property measuring apparatus (OZawa Scientific Co., Ltd .: RZ2001i). did. Subsequently, the thermal conductivity (unit: W / mK) was calculated using a thermal conductivity measuring device (Eihiro Seiki Co., Ltd .: HC-074). Using these values, the ZT value at 100 ° C. was calculated according to the mathematical formula (A), and this value was used as the thermoelectric conversion performance value.

[Film formability]
The film formability was visually evaluated based on the following three levels.
1: Good 2: Agglomerates were slightly observed and film formability was deteriorated 3: Many aggregates were formed, and film formability was greatly degraded.

[Membrane strength]
The obtained conductive film was subjected to a pencil hardness test based on JIS K5600-4. The results are shown in Table 1. In the conductive film of the present invention, the allowable range of hardness is HB or more, and preferably H or more. A film having an evaluation result of B is not preferable because scratches may occur when the film is handled. The pencil used was UNI (registered trademark) manufactured by Mitsubishi Pencil Co., Ltd.

Examples 2-18
A conductive film was produced in the same manner as in Example 1 except that the types of the conductive polymer, onium salt compound, and polymerizable compound were changed as shown in Table 1, and the conductivity and thermoelectric conversion performance (ZT) The film forming property and film strength were evaluated. The results are shown in Table 1.

Example 19
Instead of mechanical stirring for 20 minutes in Example 1 and subsequent ultrasonic cleaning machine (US-2 manufactured by Inoue Seieido Co., Ltd., output 120 W, indirect irradiation) for 10 minutes, an ultrasonic crusher (Tokyo Rika Instruments) VCX-502 manufactured by Co., Ltd., output 250 W, direct irradiation) A conductive film was produced on a glass substrate in the same manner as in Example 1 except that a CNT dispersion was prepared by stirring for 30 minutes. Table 1 below shows the results obtained by evaluating the conductivity, thermoelectric conversion performance (ZT), film formability, and strength of the coating film in the same manner as in Example 1. The G / D ratio of the dispersion prepared in Example 19 was 12.

Example 20
In Example 1, a conductive film was produced on a glass substrate in the same manner as in Example 1 except that no post-heating treatment was performed. This coating film was evaluated for conductivity, thermoelectric conversion performance (ZT), film formability, and strength in the same manner as in Example 1. The results are shown in Table 1.

Examples 21 and 22
The same procedure as in Example 1 was conducted except that the addition amount of CNT / conductive polymer / onium salt compound / total polymerizable compound in Example 1 was changed to 14 mg / 20 mg / 6 mg / 10 mg and 16 mg / 15 mg / 4 mg / 15 mg, respectively. Thus, a conductive film was formed on the glass substrate. This coating film was evaluated in the same manner as in Example 1 for conductivity, thermoelectric conversion performance (ZT), film formability, and strength. The results are shown in Table 1.

Comparative Examples 1-6
In Example 1, instead of adding an onium salt compound and a polymerizable compound, CNTs and conductive materials were formed on a glass substrate in the same manner as in Example 1 except that no addition or other compounds shown in Table 1 were added. A comparative coating film containing a polymer was prepared. This coating film was evaluated for conductivity, thermoelectric conversion performance (ZT), film formability, and strength in the same manner as in Example 1. The results are shown in Table 1.

<Conductive polymer>
Conductive polymer having the following repeating unit 1: Poly (3-hexylthiophene) (weight average molecular weight 87,000)

  Conductive polymer 2 having the following repeating unit: Poly (3-((2 ″ -ethoxy) -2′-ethoxy) ethoxythiophene) (weight average molecular weight 65,000)

  Conductive polymer 3 having the following repeating unit: Poly (2,5-bis (3-dodecylthiophenyl) thieno [3,2-b] thiophene) (weight average molecular weight 79,000)

  Conductive polymer 4 having the following repeating unit: Poly (2,6- (4,4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b ′] dithiophene-co -4,7-benzo [c] [1,2,5] thiadiazole) (weight average molecular weight 48,000)

  Conductive polymer 5 having the following repeating unit: Poly (2,6-bis (3-hexylthiophenyl)-(4,4-dihexyldithieno [3,2-b; 2 ′, 3′-d] Silole) (weight average molecular weight 52,000)

  Conductive polymer 6 having the following repeating unit: Poly (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene) (weight average molecular weight 110,000)

<Polymerizable compound>
Polymerizable compound 1: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021: manufactured by Daicel UCB Co., Ltd.)
Polymerizable compound 2: 1,2: 8,9-diepoxy limonene (Celoxide 3000: manufactured by Daicel UCB Co., Ltd.)
Polymerizable compound 3: polyethylene glycol diglycidyl ether (manufactured by Nagase Comtex Co., Ltd.)
Polymerizable compound 4: Bisphenol A bis (triethylene glycol glycidyl ether) ether (Licarresin BEO-60E: manufactured by Shin Nippon Rika Co., Ltd.)
Polymerizable compound 5: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: manufactured by Toagosei Co., Ltd.)
Polymerizable compound 6: bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd.)
Polymerizable compound 7: Tetraethylene glycol divinyl ether (DVE-4: manufactured by BASF)
Polymerizable compound 8: Polyethylene glycol divinyl ether (PEG200-DVE: manufactured by BASF)

As is clear from Table 1, the conductive films of Examples 1 to 22 formed using a composition containing CNT, a conductive polymer, an onium salt compound, and a polymerizable compound have high conductivity and good properties. In addition to excellent film formability and good thermoelectric conversion performance, the film showed excellent film strength.
On the other hand, in Comparative Examples 1 to 5 in which no onium salt compound was used, the electrical conductivity and thermoelectric conversion performance were greatly reduced. Moreover, in Comparative Examples 3-5 using the conventional dopants, such as an acid and a metal halogen, it became a result inferior to film formability. Further, Comparative Example 1 in which no dopant was added, Comparative Examples 2 to 3 in which iodine or metal halogen was used as a dopant, and Comparative Example 6 in which no polymerizable compound was contained resulted in poor film strength.

DESCRIPTION OF SYMBOLS 1, 2 Thermoelectric conversion element 11, 17 Metal plate 12, 22 1st base material 13, 23 1st electrode 14, 24 Thermoelectric conversion layer 15, 25 2nd electrode 16, 26 2nd base material

Claims (21)

  A conductive composition containing (A) a carbon nanotube, (B) a conductive polymer, (C) an onium salt compound, and (D) a polymerizable compound.   The conductive composition according to claim 1, wherein the (C) onium salt compound is a compound having an oxidizing ability with respect to (A) carbon nanotubes and / or (B) a conductive polymer.   (C) The electrically conductive composition of Claim 1 or 2 whose onium salt compound is a compound which generate | occur | produces an acid by provision of a heat | fever or active energy ray irradiation. (C) The electroconductivity of any one of Claims 1-3 whose onium salt compound is 1 type, or 2 or more types of the compound represented by either of the following general formula (I)-(V). Sex composition.

(In the general formulas (I) to (V), R ^{21 to} R ²³ , R ^{25 to} R ²⁶ and R ^{31 to} R ³³ are each independently a linear, branched or cyclic alkyl group, an aralkyl group, an aryl group, R ^{27 to} R ³⁰ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, an aryloxy group R ²⁴ represents a linear, branched or cyclic alkylene group or an arylene group.
X ⁻ represents an anion of a strong acid.
Any two groups of R ^{21 to} R ²³ in the general formula (I), R ²¹ and R ^{23 in} the general formula (II), R ²⁵ and R ^{26 in} the general formula (III), R ²⁷ in the general formula (IV) Any two groups of -R ³⁰ and any two groups of R ³¹ -R ³³ in the general formula (V) are bonded to each other in the general formula to form an aliphatic ring, an aromatic ring, or a heterocyclic ring May be formed. ) In the general formulas (I) to (V), X ⁻ represents an anion of an aryl sulfonic acid, an anion of a perfluoroalkyl sulfonic acid, an anion of a perhalogenated Lewis acid, an anion of a perfluoroalkyl sulfonimide, or an alkyl or aryl The electrically conductive composition of Claim 4 which is a borate anion.   (D) The electrically conductive composition of any one of Claims 1-5 whose polymerizable compound is a compound which has a 2 or more cationically polymerizable group.   (D) The electrically conductive composition of Claim 6 whose cation polymeric group of a polymeric compound is an epoxy group, an oxetane group, and / or a vinyl ether group.   The electrically conductive composition of any one of Claims 1-7 containing a solvent.   In the total solid content of the conductive composition, (A) 3 to 50% by mass of carbon nanotubes, (B) 30 to 80% by mass of conductive polymer, (C) 1 to 50% by mass of onium salt compound, (D) The electroconductive composition of any one of Claims 1-8 which contains 5-50 mass% of polymeric compounds.   The conductive composition according to any one of claims 1 to 9, which is for thermoelectric conversion.   The electroconductive film which uses the electroconductive composition of any one of Claims 1-10.   (D) The electroconductive film of Claim 11 containing the polymer which uses a polymeric compound as a structural component.   The electroconductive laminated body provided with the base material and the electroconductive film of Claim 11 or 12 provided on this base material.   The conductive laminate according to claim 13, wherein the substrate is a resin film.   The thermoelectric conversion element using the electroconductive film of Claim 11 or 12, or the electroconductive laminated body of Claim 13 or 14.   The thermoelectric conversion element according to claim 15, comprising an electrode.   The thermoelectric power generation article using the thermoelectric conversion element of Claim 15 or 16.   The manufacturing method of a conductive film or a conductive laminated body including the process formed into a film using the conductive composition of any one of Claims 1-10.   The manufacturing method according to claim 18, wherein the film forming step includes a step of applying a conductive composition onto a substrate.   The manufacturing method of Claim 18 or 19 including the process of performing a heating or active energy ray irradiation after film-forming.   The manufacturing method according to claim 20, comprising a step of heating at 60 to 150 ° C for 1 to 20 minutes after heating or irradiation with active energy rays.

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