JP2014057003A - Solar cell and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solar cell which exhibits a high photoelectric conversion rate with a simple structure, and a method of manufacturing the same.SOLUTION: The solar cell is manufactured by laminating, on at least one surface of a conductive transparent substrate (1), a photoelectric conversion layer containing inorganic particles (3) capable of photoelectric conversion and conductive polymers (4, 5) having a three-dimensional network structure substantially the whole of which is composed of a π-conjugated system. The conductive polymers (4, 5) have a sensitizing function and/or a charge transport function. Therefore, the photoelectric conversion layer contains the inorganic particles capable of photoelectric conversion, a sensitizer for optically exciting the particles, and a charge transport agent, and the sensitizer and/or the charge transport agent may be constituted of the conductive polymers.

Description

  The present invention relates to a solar cell that exhibits a high photoelectric conversion rate with a simple structure and a method for manufacturing the solar cell.

  Solar cells are attracting attention and being put to practical use as clean energy with a low environmental impact. At present, inorganic solar cells using crystalline silicon for photoelectric conversion sites are widely used. However, since high-purity silicon is used, there are problems such as high power generation cost and low conversion efficiency for weak light such as indoors. In order to solve such problems, organic solar cells using organic materials for photoelectric conversion sites have been widely developed. Examples of the organic solar cell include a thin film solar cell and a dye-sensitized solar cell.

  In WO2011 / 129386 (Patent Document 1), an aromatic polycarbonyl compound having a carbonyl group as a reaction site, an aromatic polyamine having an amino group as a reaction site, and a heteroatom of a heterocyclic ring, and At least one aromatic reaction component selected from an aromatic heterocyclic compound having a plurality of unmodified α-carbon positions as a reaction site, and at least of the aromatic polycarbonyl compound and the aromatic reaction component, An organic semiconductor film is described in which one component is formed of a crosslinkable composition having three or more reaction sites in one molecule. This document describes an inorganic semiconductor composed of at least one kind of metal selected from Group 2B-4B elements of the periodic table or an oxide thereof, and an organic-inorganic composite semiconductor in which the organic semiconductor film is stacked on the inorganic semiconductor. It is also described that it is suitable for use in photoelectric conversion devices such as solar cells. The example of this document also describes an example in which a thin-film solar cell is manufactured by sequentially laminating the organic semiconductor film and the transparent electrode on a p-type silicon semiconductor. However, this thin-film solar cell has a small area (effective surface area) that contributes to photoelectric conversion, and its output characteristics are not sufficient.

Dye-sensitized solar cells have been developed and studied extensively by Graetzel et al., Lausanne University of Technology. FIG. 1 schematically shows the structure of a general dye-sensitized solar cell. In this example, a photoelectrode in which a transparent substrate 1, a transparent conductive layer 2, an inorganic particle 3 capable of photoelectric conversion and a semiconductor layer containing a sensitizing dye 4 adsorbed on the inorganic particle are sequentially laminated, and the photoelectrode A counter electrode in which the catalyst layer 7, the transparent conductive layer 2, and the transparent substrate 1 are sequentially laminated from the facing portion side, an electrolyte solution 5 that fills the space between the electrodes, and seals the electrolyte solution It is comprised with the sealing material 6 for doing. When this solar cell is irradiated with light, the sensitizing dye 4 is excited and emits electrons. The emitted electrons are injected into the inorganic particles 3 and pass through the transparent conductive layer 2 of the photoelectrode, It moves to the transparent conductive layer 2 of the counter electrode through the circuit. When these electrons are received by triiodide ions (I ₃ ⁻ ) contained in the electrolytic solution 5, they are reduced to iodide ions (I ⁻ ). The iodide ion is oxidized again to triiodide ion when electrons are transferred to the sensitizing dye 4. A current flows by repeating such a cycle.

As the semiconductor layer, for example, Japanese Patent No. 2664194 (Patent Document 2) discloses a polycrystalline metal oxide semiconductor layer having a surface having a surface roughness coefficient greater than 20, and in the examples, , An example of manufacturing a semiconductor layer of titanium oxide having a surface roughness of 200 is described. Further, as a sensitizing dye, a low molecular organic dye (particularly a dye having a complex structure) is widely used. Among them, a ruthenium complex is known as a dye exhibiting a high photoelectric conversion ability, for example, Japanese Patent No. 3731752. The publication (Patent Document 3) includes cis- (X) ₂ bis (2,2′-bipyridyl-4,4′-dicarboxylate) -ruthenium (II) complex (X═Cl, Br, CN, SCN). Is disclosed.

  Such a dye-sensitized solar cell has a complicated layer structure and insufficient output characteristics. In addition, there is a risk that the electrolyte solution leaks when the performance deteriorates due to the volatilization of the electrolyte solution or when the electrolyte solution is damaged. Furthermore, the sensitizing dye is chemically or physically fixed to the surface of the metal oxide via an acidic group (for example, carboxyl group), and is easily detached by heating at several tens of degrees Celsius to lose photoelectric conversion ability. It is difficult to use it outdoors exposed to direct sunlight for a long time.

WO2011 / 129386 (claims, paragraphs [0186] [0187], examples) Japanese Patent No. 2664194 (Claims and Examples) Japanese Patent No. 3731552 (Claims, page 8, lines 31-33)

  Therefore, the objective of this invention is providing the solar cell which shows a high photoelectric conversion rate with a simple structure, and its manufacturing method.

  Another object of the present invention is to provide a solar cell that is stable and safe without the problem of volatilization or leakage of the electrolyte and a method for manufacturing the solar cell.

  Still another object of the present invention is to provide a solar cell capable of exhibiting a high photoelectric conversion rate without using a low-molecular sensitizing dye such as a ruthenium complex and a method for producing the solar cell.

  Another object of the present invention is to provide a solar cell capable of easily controlling the absorption wavelength of a sensitizing dye in accordance with the emission spectrum of a light source and a method for producing the solar cell.

  Still another object of the present invention is to provide a solar cell that is excellent in heat resistance and can be used even in an environment where it is exposed to direct sunlight for a long time, and a method for manufacturing the solar cell.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when a photoelectric conversion layer containing inorganic particles capable of photoelectric conversion and a specific conductive polymer is laminated on a conductive transparent substrate, the conductive high It was found that the molecule can function as a sensitizer and / or a charge transport agent, and that a solar cell having such a laminate exhibits a high photoelectric conversion rate while having a simple structure, thereby completing the present invention. did.

  That is, the solar cell (or photoelectric conversion device) of the present invention includes a conductive transparent substrate and a photoelectric conversion layer laminated on at least one surface of the conductive transparent substrate. The photoelectric conversion layer includes inorganic particles (or photo-semiconductor particles) capable of photoelectric conversion and a conductive polymer having a three-dimensional network structure (or a crosslinked structure) substantially consisting entirely of a π-conjugated system. Since such a conductive polymer forms a π-conjugated system, it has a high light absorbency, and has a function as a sensitizer for photoexciting inorganic particles and / or a function as a charge transport agent. . Therefore, the conductive polymer can constitute a sensitizer and / or a charge transport agent, and the single conductive polymer can constitute a sensitizer and / or a charge transport agent.

  The conductive polymer is at least one selected from carbon-carbon single bond, carbon-carbon double bond, carbon-carbon triple bond, carbon-nitrogen double bond, amide bond, imidazole ring, oxazole ring and thiazole ring. It may be a polymer in which a plurality of aromatic rings are three-dimensionally connected via a unit. The conductive polymer may be formed of a crosslinkable composition.

  The crosslinkable composition comprises an aromatic carbonyl compound having one or more carbonyl groups as a reactive site, an aromatic polyamine having a plurality of amino groups (reactive groups with a carbonyl group) as a reactive site, and a heterocyclic ring. At least one aromatic reaction component selected from aromatic heterocyclic compounds adjacent to the heteroatom and having a plurality of unmodified α-carbon positions (reaction sites with formyl groups) as reaction sites You may go out.

  When the aromatic reaction component is an aromatic polyamine, the aromatic carbonyl compound is an aromatic polycarbonyl compound having a plurality of carbonyl groups as reaction sites, and at least one of the aromatic polycarbonyl compound and the aromatic polyamine These components may have three or more reaction sites. Further, when the aromatic reaction component is an aromatic heterocyclic compound, the aromatic carbonyl compound is an aromatic aldehyde compound having one or more formyl groups as a reaction site, and the formyl group of the aromatic aldehyde compound When the number is “T” and the number of unmodified α-carbon positions of the aromatic heterocyclic compound is “U”, T ≧ 2 and / or U ≧ 3 may be satisfied. Furthermore, when the aromatic reaction component is a combination of an aromatic polyamine and an aromatic heterocyclic compound, the aromatic carbonyl compound may be an aromatic polyaldehyde compound having a plurality of formyl groups as reaction sites.

  A typical crosslinkable composition includes an aromatic polyaldehyde compound having 2 to 4 formyl groups as a reactive site in one molecule and an aromatic having 2 to 4 amino groups as a reactive site in one molecule. A polyamine, and at least one of these components may be a composition having 3 or more reactive sites; an aromatic polyaldehyde compound having 2 to 4 formyl groups as reactive sites in one molecule And an aromatic heterocyclic compound adjacent to the hetero atom of the heterocyclic ring and having 2 to 8 (for example, 2 to 4) unmodified α-carbon positions as a reactive site in one molecule It may be a composition.

  The aromatic carbonyl compound may be a compound represented by the following formula (Ia).

(In the formula, L represents a linker, A represents an aromatic ring, R ¹ represents a carbonyl group-containing group, R ² represents a non-reactive group, n is 0 or 1, and k1 is 1 or more. An integer, k2 is 0 or an integer of 1 or more, p is 1 when n is 0, and p is an integer of 2 or more when n is 1)
In the compound represented by the formula (Ia), (a1) ring A is monocyclic or condensed bi- to heptacyclic aromatic hydrocarbon ring, monocyclic or condensed bi- to heptacyclic aromatic heterocyclic ring, porphyrin ring or phthalocyanine A compound in which n is 0, k1 is 2 to 4, and p is 1, and (a2) ring A is a monocyclic ring or a condensed bi- to heptacyclic aromatic hydrocarbon ring Or a monocyclic or condensed bi- to heptacyclic aromatic heterocycle, and the linker L is a direct bond, nitrogen atom, oxygen atom, sulfur atom, vinylene group, 2-4 valent aromatic ring group, 2-4 valent aromatic ring group The compound may be an aromatic ring assembly group or a combination thereof, n is 1, k1 is 1 or 2, and p is 2 to 4.

  The aromatic polyamine may be a compound represented by the following formula (IIa).

(Wherein R ³ represents an amino group, R ⁴ represents a hydrogen atom, an amino group, a mercapto group or a hydroxyl group, k3 is an integer of 1 or more, and L, n, A, R ² , k2 and p Is the same as above, except that when n is 0, k3 is an integer of 2 or more.)
In the compound represented by formula (IIa), (b1) ring A is monocyclic or condensed bi to heptacyclic aromatic hydrocarbon ring, monocyclic or condensed bi to heptacyclic aromatic heterocyclic ring, porphyrin ring or phthalocyanine A ring, n is 0, k3 is 2 to 4, and p is 1, and (b2) Ring A is a monocyclic ring or a condensed bi- to heptacyclic aromatic hydrocarbon ring The linker L is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a diazo group, a disulfide group, a vinylene group, a divalent to tetravalent aromatic ring group, or a combination thereof, n is 1, and k3 is The compound which is 1 or 2 and p is 2-4 may be sufficient.

  The aromatic heterocyclic compound may be at least one selected from a monocyclic compound, a condensed cyclic compound, and a ring assembly compound, and the aromatic heterocyclic compound is an oxygen atom as a hetero atom of the heterocyclic ring. , A sulfur atom, a nitrogen atom or imino group, or a 5- to 8-membered aromatic heterocycle having at least one heteroatom selected from selenium atoms. The aromatic heterocyclic compound may be a compound represented by the following formula (III).

(In the formula, Het represents an aromatic heterocyclic ring, X represents a hetero atom, R ⁵ represents a non-reactive group, r represents an integer of 0 to 3, and L, n and p are the same as above. )
The inorganic particles include at least one metal oxide selected from calcium titanate, strontium titanate, barium titanate, titanium oxide, zirconium oxide, niobium oxide, tantalum oxide, tungsten oxide, zinc oxide, and tin oxide (for example, Titanium oxide) may be used.

  The present invention relates to a sensitizer for photoexciting photoelectrically convertible inorganic particles, which is composed of a conductive polymer having a three-dimensional network structure substantially consisting entirely of a π-conjugated system. Include. Further, the present invention includes a photoelectric conversion composition containing the inorganic particles and the conductive polymer (or the inorganic particles, a sensitizer for photoexciting the particles, and a charge transport agent, And a sensitizer and / or a charge transfer agent comprising the above-described conductive polymer). Furthermore, the present invention includes a step of applying a paste containing inorganic particles capable of photoelectric conversion on at least one surface of a conductive transparent substrate, and applying the crosslinkable composition to a coating film obtained in this step. And a solar cell manufacturing method including a heat treatment step.

  Note that in this specification, the “π-electron conjugated system” means a conjugated system including an atom having a non-conjugated electron pair (for example, a nitrogen atom, an oxygen atom, or a sulfur atom). In the present specification, in the terms “aromatic polycarbonyl compound” and “aromatic polyamine”, “poly” means that the carbonyl group and the amino group (reactive group with carbonyl group) are 2 or more, respectively. Means. Furthermore, in the present specification, the “aromatic ring” means that a plurality of aromatic rings (such as a pyrrole ring) form a π-conjugated system (for example, —N =, —C =), for example, a bead shape In this sense, it also includes cyclic aromatic rings that are cyclically bonded to each other, such as porphyrin rings such as porphyrin derivatives and phthalocyanines.

  In the present invention, since a conductive polymer having a three-dimensional network structure substantially consisting entirely of a π-conjugated system is used as a sensitizer and / or a charge transport agent, a high photoelectric conversion rate can be achieved with a simple structure. Can be achieved. In particular, the conductive polymer is less bound to excitons generated by light absorption than a low-molecular sensitizing dye (such as a ruthenium complex), can be easily separated by charge, has low resistance, and has a high carrier mobility. The photoelectric conversion rate can be significantly improved. In the present invention, since the electrolytic solution is substantially unnecessary, there is no problem of volatilization or leakage of the electrolytic solution, and it is stable and safe. In the present invention, the absorption wavelength of the sensitizer can be easily adjusted in accordance with the emission spectrum of the light source by adjusting the type and amount of the polymerization component (or reaction component) constituting the conductive polymer. Can be controlled. Furthermore, in this invention, it is excellent in heat resistance, and can be used also in the environment (outdoors etc.) exposed to direct sunlight for a long time.

FIG. 1 is a schematic view showing a conventional dye-sensitized solar cell. FIG. 2 is a schematic view showing an example of the solar cell of the present invention. FIG. 3 is a graph showing current-voltage characteristics of the solar cell of the example. FIG. 4 is a graph showing an absorption spectrum of the conductive polymer of the example.

  A solar cell (for example, a photosensitized solar cell) of the present invention includes a conductive transparent substrate and a photoelectric conversion layer laminated (or formed) on at least one surface (one surface or both surfaces) of the conductive transparent substrate. Yes.

(Conductive transparent substrate)
The conductive transparent substrate may be a transparent substrate showing conductivity as a whole, but is usually a transparent substrate having at least one surface showing conductivity, and a base substrate and at least one surface of the base substrate ( And a transparent conductive layer laminated on one side or both sides.

  The base substrate is not particularly limited as long as it has transparency. For example, a glass plate may be used from the viewpoint of strength and heat resistance, or a transparent resin film may be used from the viewpoint of lightness and flexibility. Good. Transparent resin films include transparent resins [for example, (meth) acrylic resins, olefinic resins (polyethylene, polypropylene, etc.), cyclic olefinic resins (such as norbornene homo- or copolymers), styrene resins, polyester resins ( Polyalkylene arylate resins such as polyethylene terephthalate (PET), PET copolymer (PET-G), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) containing cyclohexanedimethanol as a diol component, polyarylate resin , Liquid crystalline polyester, etc.), polyamide resin (nylon 6, nylon 66, nylon 12, etc.), polycarbonate resin (bisphenol A type polycarbonate, etc.), cellulose resin (cellulose ester, etc.), Imide resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, etc.] and additives [for example, stabilizers (such as antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), Plasticizer, antistatic agent, etc.]. The transparent resin film may be a uniaxial or biaxially stretched film.

  The thickness of the base substrate can be selected from a range of about 10 μm to 1 mm, and is, for example, 10 to 500 μm, preferably 20 to 300 μm, and more preferably about 30 to 200 μm.

  The transparent conductive layer is not particularly limited, and may be a metal oxide that absorbs less visible light, such as indium oxide; tin oxide that may be doped with fluorine, antimony, or the like; aluminum oxide, gallium, or the like. You may comprise with zinc oxide etc. The metal oxide may be a composite oxide [eg, indium-tin composite oxide (ITO), indium-zinc composite oxide (IZO), etc.]. These metal oxides can be used alone or as a mixed oxide. Of these metal oxides, ITO is widely used because it has a smooth surface and can reduce the specific resistance.

  The thickness of the transparent conductive layer can be selected from a range of about 1 to 1000 nm, and is, for example, about 5 to 500 nm, preferably 10 to 400 nm, and more preferably about 50 to 300 nm (for example, 100 to 200 nm).

  The transparent conductive layer can be produced by a conventional method, for example, a physical vapor phase (PVD) method (for example, a vacuum deposition method, an ion plating method, a sputtering method, etc.), a chemical vapor phase (CVD) method, or the like. it can.

(Photoelectric conversion layer)
The photoelectric conversion layer includes inorganic particles (or photo-semiconductor particles) capable of photoelectric conversion and a conductive polymer having a three-dimensional network structure (or a crosslinked structure) substantially consisting entirely of a π-conjugated system. Such a conductive polymer has a sensitizing action and / or a charge transporting action. Therefore, in a photoelectric conversion layer containing inorganic particles capable of photoelectric conversion, a sensitizer (or excited molecule) for photoexciting the particles, and a charge transport agent (or solid electrolyte), sensitization with a conductive polymer Agents and / or charge transport agents may be configured. In particular, it is preferable that the sensitizer and the charge transport agent are composed of the same or different kinds of conductive polymers (for example, the same conductive polymer) from the viewpoint that the photoelectric conversion rate can be improved with a simple structure.

  The inorganic particles (photosemiconductor particles) contained in the photoelectric conversion layer are not particularly limited as long as photoelectric conversion is possible, and may be composed of, for example, a metal oxide. The metal constituting the metal oxide is not particularly limited, and for example, Group 2 metal of the periodic table (for example, calcium, strontium, barium, etc.), Group 3 metal of the periodic table (for example, scandium, yttrium, lanthanoid, etc.) , Periodic table group 4 metals (eg, titanium, zirconium, hafnium, etc.), periodic table group 5 metals (eg, vanadium, niobium, tantalum, etc.), periodic table group 6 metals (eg, chromium, molybdenum, tungsten, etc.) ), Periodic Table Group 7 metals (eg, manganese, etc.), Periodic Table Group 8 metals (eg, iron, etc.), Periodic Table Group 9 metals (eg, cobalt, etc.), Periodic Table Group 10 metals (eg, Nickel), Periodic Table Group 11 metal (for example, copper), Periodic Table Group 12 metal (for example, zinc, cadmium, etc.), Periodic Table Group 13 gold (Eg, aluminum, gallium, indium, thallium, etc.), periodic table group 14 metals (eg, germanium, tin, etc.), periodic table group 15 metals (eg, arsenic, antimony, bismuth, etc.), periodic table group 16 Metal (for example, tellurium etc.) etc. are mentioned. These metals may be used alone or in combination of two or more.

Typical metal oxides are metal oxides exhibiting n-type semiconductor characteristics, and have a wide band gap. From the viewpoint of having a wide band gap, calcium titanate (CaTiO ₃ ), strontium titanate (SrTiO ₃ ), barium titanate (BaTiO _3). ), Titanium oxide, zirconium oxide (ZrO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), These composite oxides are widely used. Of these, titanium oxide is preferable from the viewpoint of photoelectric conversion.

Examples of titanium oxide include TiO ₂ , Ti ₂ O ₅ , Ti ₂ O ₃ , hydrous titanium oxide (metatitanic acid, orthotitanic acid, etc.), but TiO ₂ (titanium dioxide) is generally used. In addition, the titanium oxide may be amorphous or crystalline (rutile, anatase, brookite, etc.), but has high orientation and a relatively large contact area between the titanium oxides. The rutile type is preferable from the viewpoint of improving conductivity and durability.

  As the metal oxide, a different type of metal oxide from the metal oxide constituting the transparent conductive layer is usually used. Further, the metal oxide may be doped with other elements (or ions). Further, the band gap of the metal oxide is not particularly limited, and may be, for example, about 3 eV or more (for example, 3 to 4 eV), preferably about 3.2 eV or more (for example, 3.2 to 3.5 eV). .

  The shape of the inorganic particles is not limited to a spherical shape, and may be an ellipsoidal shape, a regular octahedral shape, a star shape, a needle shape, a fiber shape, a rod shape, or the like, and these shapes may be mixed.

  The average diameter (average particle diameter or average primary particle diameter) of the inorganic particles can be selected from a range of, for example, 100 μm or less (for example, 50 μm or less, preferably 10 μm or less, more preferably 1 μm or less), and 5 to 1000 nm, preferably It may be about 10 to 500 nm, more preferably about 15 to 400 nm (for example, 20 to 300 nm). If the average diameter is too small, the particles tend to aggregate and the conductivity tends to decrease. If the average diameter is too large, the effective surface area cannot be increased too much. The average diameter can be measured by a conventional method such as a laser diffraction method.

  The conductive polymer contained in the photoelectric conversion layer is not particularly limited as long as it has a three-dimensional network structure substantially consisting entirely of a π-conjugated system. For example, a π-electron conjugated unit [carbon-carbon single bond (-C -C-), carbon-carbon double bond (-C = C-), carbon-carbon triple bond (-C≡C-), carbon-nitrogen double bond (-C = N-), amide bond (- It may be a polymer in which a plurality of aromatic rings [or units containing aromatic rings (fullerene, etc.)] are linked three-dimensionally via NHCO-), imidazole ring, oxazole ring, thiazole ring, etc.]. Such a conductive polymer forms a pseudo band structure as a whole, and can rapidly transfer electrons within a delocalized molecule, not between molecules (hopping). In addition, the conductive polymer having a three-dimensional network structure is insoluble or hardly soluble in a solvent, and the band gap is often smaller than the band gap of the polymerization component (or reaction component).

  The conductive polymer may be, for example, a polymer (aromatic conjugated polymer) generated by the following crosslinkable composition (or polymerizable composition).

  The crosslinkable composition can react with a π-electron conjugated bond [for example, carbon-carbon single bond, carbon-carbon double bond, carbon-carbon triple bond, carbon-nitrogen double bond, amide bond, imidazole ring, oxazole ring. , A thiazole ring, and the like], and a polymerization component (or reaction component) having a reaction site (or functional group) capable of being generated. This polymerization component only needs to be able to generate 2 or more (for example, about 2 to 8, preferably 2 to 6, more preferably about 2 to 4) π-electron conjugated bonds by reaction, and at least one polymerization component is 3 The above (for example, 3 to 8, preferably 3 to 6, more preferably about 3 to 4) π-electron conjugated bonds can be generated. When the crosslinkable composition contains a polymerization component (crosslinking or branching component) capable of generating three or more π-electron conjugated bonds, a three-dimensional network structure (or crosslinked structure) can be formed by a polymerization reaction. . In addition, when the polymerization component itself has a π-electron conjugated structure (such as an aromatic ring), the polymer can be electrically conducted over the whole three-dimensionally.

  Specifically, the crosslinkable composition comprises an aromatic carbonyl compound having one or more carbonyl groups as a reaction site, and at least one aromatic reaction component selected from an aromatic polyamine and an aromatic heterocyclic compound. The aromatic polyamine has a plurality of amino groups as reactive sites, the aromatic heterocyclic compound is adjacent to the heteroatom of the heterocyclic ring, and has a plurality of unmodified (or unmodified) as reactive sites. Substituted) α-carbon position. When the aromatic reaction component is an aromatic heterocyclic compound, an aromatic aldehyde compound is used as the aromatic carbonyl compound. That is, the crosslinkable composition includes (1) an embodiment containing an aromatic carbonyl compound and an aromatic polyamine, (2) an embodiment containing an aromatic aldehyde compound and an aromatic heterocyclic compound, and (3) an aromatic aldehyde compound. And an aromatic heterocyclic compound and an aromatic polyamine are included.

  The composition of the embodiment (1) is a combination that produces a carbon-nitrogen double bond, an amide bond, an imidazole ring, an oxazole ring, or a thiazole ring, that is, a plurality of carbonyl groups (carbonyl groups) A π electron conjugated compound (aromatic polycarbonyl compound) having a containing group) and a π electron conjugated compound (aromatic polyamine) having a plurality of amino groups. This composition is a π-electron conjugated compound having 3 or more reactive sites [3 or more amino groups or carbonyl groups (reactive carbonyl groups that react with amino groups)] in one molecule from the point of forming a crosslinked structure. Is included.

  The composition of the aspect (2) is a combination that forms a carbon-carbon single bond or a carbon-carbon double bond, that is, a π-electron conjugated compound (aromatic aldehyde compound) having one or more formyl groups and a plurality of It consists of a combination with a π-electron conjugated compound (aromatic heterocyclic compound) containing a heterocyclic ring having an unmodified α-carbon position. This composition is a π-electron conjugate having three or more reaction sites [two or more formyl groups (aldehyde groups) or three or more unmodified α-carbon positions] in one molecule from the viewpoint of forming a crosslinked structure. Contains system compounds. In the reaction between an aromatic aldehyde compound and an aromatic heterocyclic compound, one formyl group functions as a bifunctional reactive group, and thus can be calculated as two reaction sites. The composition of aspect (2) has high stability and can form a conductive polymer by heat treatment at a low temperature.

  The composition of the aspect (3) corresponds to a composition obtained by combining the aspect (1) and the aspect (2). For example, the composition of the aspect (3) includes a π-electron conjugated compound (aromatic polyaldehyde compound) having a plurality of formyl groups, a π-electron conjugated compound (aromatic polyamine) having a plurality of amino groups, And a π-electron conjugated compound (aromatic heterocyclic compound) containing a heterocyclic ring having an unmodified α-carbon position.

(Aromatic carbonyl compounds)
The aromatic carbonyl compound is not particularly limited as long as it is an aromatic compound having one or more carbonyl groups (carbonyl group-containing groups), and may be, for example, a compound represented by the following formula (Ia).

(In the formula, L represents a linker, A represents an aromatic ring, R ¹ represents a carbonyl group-containing group, R ² represents a non-reactive group, n is 0 or 1, and k1 is 1 or more. An integer, k2 is 0 or an integer of 1 or more, p is 1 when n is 0, and p is an integer of 2 or more when n is 1)
In the formula (Ia), the aromatic ring represented by A includes an aromatic hydrocarbon ring [for example, a monocyclic aromatic hydrocarbon ring (such as a benzene ring), a condensed polycyclic aromatic hydrocarbon ring (indene, Condensed bicyclic hydrocarbon rings such as naphthalene ring; condensed tricyclic hydrocarbon rings such as acenaphthylene, fluorene, phenalene, anthracene, phenanthrene ring; condensed tetracyclic hydrocarbon rings such as pyrene, naphthacene ring; pentacene, picene ring Condensed hexacyclic hydrocarbon rings such as hexaphene, hexacene rings, etc .; condensed heptacyclic hydrocarbon rings such as coronene rings)], aromatic heterocycles [eg, monocyclic heterocycles Ring (5- to 6-membered heterocycle containing a sulfur atom such as a thiophene ring; 5- to 6-membered heterocycle containing a nitrogen atom such as pyrrole, pyrazole, imidazole ring; oxygen atom such as a furan ring 5-6 membered heterocyclic ring containing; 5-6 membered heterocyclic ring containing nitrogen atom and oxygen atom such as oxazole and oxadiazole ring; 5-6 membered heterocyclic ring containing nitrogen atom and sulfur atom such as thiazole, thiadiazole ring, etc. ), Polycyclic heterocycles (fused bicyclic heterocycles such as quinoline ring; condensed tricyclic heterocycles such as xanthene, carbazole, acridine, phenanthridine, phenazine, phenothiazine, phenoxazine ring; porphine ring (or porphyrin) Ring); phthalocyanine ring etc.]], derivatives thereof (hydrocarbon cyclic ketones such as anthraquinone, heterocyclic ketones such as pyrazolone) and the like. These aromatic rings may have a substituent (such as a non-reactive group R ² described later).

Ring A is a monocyclic ring or a condensed 2 to 20 ring aromatic ring (for example, a condensed 2 to 10 ring aromatic ring), for example, a monocyclic ring or a condensed bi to heptacyclic arene ring (benzene, naphthalene, fluorene, pyrene, Monocyclic or condensed bi to tetracyclic arene rings such as anthraquinone ring), monocyclic or condensed bi to heptacyclic aromatic heterocyclic rings (thiophene, carbazole, phenanthridine ring, etc. monocyclic or condensed bi to tetracyclic rings Formula aromatic heterocycles and the like). Ring A is at least one selected from a C _6-24 arene ring (C _6-14 arene ring such as benzene and naphthalene ring, particularly C _6-10 arene ring), nitrogen atom, oxygen atom and sulfur atom. A 5- or 6-membered aromatic heterocyclic ring (such as a thiophene ring) containing one hetero atom as a ring constituent atom is also preferable.

Examples of the carbonyl group-containing group represented by R ¹ include formyl group (aldehyde group); group — (CH═CH) _m —CHO (m is an integer of 1 or more, for example, 1 to 10, preferably 1 to 5. And more preferably 1-2) formyl group-containing groups such as (for example, 2-formylvinyl group); ketone group-containing groups such as acyl groups (C _2-5 acyl groups such as acetyl group); carboxyl groups; Examples thereof include an alkoxycarbonyl group ( _C1-2 alkoxy-carbonyl group); a halocarbonyl group (such as a chlorocarbonyl group) and the like. Of these carbonyl group-containing groups, formyl group-containing groups such as formyl group and 2-formylvinyl group, and carboxyl groups (particularly formyl group) are preferable.

The substitution number k1 of R ¹ can be selected from the range of, for example, about 1 to 10, and when n is 0, k1 is 1 to 8, preferably 2 to 6, more preferably 2 to 4 (for example, 2 or When n is 1, k1 is 1 to 4, preferably 1 to 3, and more preferably 1 to 2 (for example, 1). In addition, when ring A is a condensed ring, R ¹ may be substituted on at least one ring. Further, the substitution position of R ¹ is not particularly limited. For example, when a plurality of R ¹ are substituted on ring A, any two R ¹ may be substituted at adjacent positions, but from the viewpoint of reactivity, Substitution at non-adjacent positions is preferred. Furthermore, when the total number of R ¹ contained in one molecule is 2 or more, the types of R ¹ may be different from each other but are usually the same.

The “non-reactive group” represented by R ² is non-reactive with respect to the reaction between a carbonyl group-containing group and an amino group and / or the reaction between a formyl group and an unmodified α-carbon position (or Inactive) group. Non-reactive groups include hydrocarbon groups, halogenated hydrocarbon groups, alkoxy groups, haloalkoxy groups, cycloalkoxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, haloalkylthio groups, cycloalkylthio groups, arylthio groups, Examples thereof include an aralkylthio group, an N, N-disubstituted amino group, a sulfo group, and a sodium sulfonate group.

As the hydrocarbon group, an alkyl group (for example, a linear or branched C _1-12 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl group, preferably Is a linear or branched C _1-10 alkyl group, etc.), an alkenyl group (such as a C _2-6 alkenyl group such as a vinyl group), a cycloalkyl group (a C _5-8 cycloalkyl group such as a cyclohexyl group). Etc.), aryl groups [for example, C _1-4 alkylphenyl groups such as phenyl and alkylphenyl groups (mono or dimethylphenyl groups (tolyl group, 2-methylphenyl group, xylyl group, etc.)), naphthyl groups, etc. _6-10 an aryl group, and aralkyl group (such as _{C 6-10} aryl _{-C 1-4} alkyl group such as benzyl group) example It can be.

As the halogenated hydrocarbon group, a group in which a hydrogen atom of a hydrocarbon group is substituted with a halogen atom (fluorine, chlorine, bromine, etc.), for example, halo C such as a trichloromethyl group, a trifluoromethyl group, or a tetrafluoroethyl group Examples thereof include _1-6 alkyl groups (such as mono to perfluoro C _1-6 alkyl groups).

Examples of the alkoxy group include linear or branched C _1-10 alkoxy groups (preferably C _1-6 alkoxy groups) such as methoxy, ethoxy, propoxy, n-butoxy, and t-butoxy groups. Examples of the alkoxy group include linear or branched halo C _1-10 alkoxy groups such as trifluoromethoxy, 2,2,2-trifluoroethoxy, and perfluoroethoxy groups (preferably halo C _1-6 alkoxy groups). The cycloalkoxy group can be exemplified by a C _5-8 cycloalkyloxy group such as a cyclohexyloxy group, and the aryloxy group can be exemplified by a C _6-10 aryloxy group such as a phenoxy group. the group, _{C 6-10} aryl _{-C 1-4} alkyl group such as a benzyloxy group It can be shown.

  Examples of the alkylthio group, haloalkylthio group, cycloalkylthio group, arylthio group and aralkylthio group include groups corresponding to the above alkoxy group, haloalkoxy group, cycloalkoxy group, aryloxy group and aralkyloxy group.

Examples of the N, N-disubstituted amino group include N, N-dialkylamino groups (N, N-diC _1-6 alkylamino groups such as N, N-dimethylamino group) and the like.

The substitution number k2 of R ² can be selected from a range of, for example, about 0 to 10, and may be 0 to 5, preferably 0 to 3, and more preferably about 0 to 2 (for example, 0 or 1). Incidentally, the substitution position of R ² is not particularly limited. When the total number of R ² contained in one molecule is 2 or more, the types of R ² may be the same or different from each other.

As the linker (unit or linking group) represented by L, for example, a direct bond (−), an oxygen atom, a sulfur atom, a nitrogen atom or an imino group, a heteroatom such as a boron atom or a phosphorus atom; Constructed linker (azo group, disulfide group, etc.); linker corresponding to ethylene (vinylene group, etc.); linker corresponding to acetylene (ethynylene group); linker corresponding to aromatic ring (or two or more polyvalent groups); Examples include a linker (or two or more polyvalent groups) corresponding to an aromatic ring assembly. Incidentally, the linker L may have a substituent (such as a non-reactive group R ^2).

  In the linker corresponding to the aromatic ring, the aromatic ring can be exemplified by the same aromatic ring as the ring A, and is monocyclic or condensed bi- to heptacyclic arene rings (monocyclic such as benzene, naphthalene and fluorene rings or condensed bi- to tetra-cyclic). A cyclic arene ring, etc.), a 5- or 6-membered aromatic heterocyclic ring containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom (such as an oxazole or oxadiazole ring) or a porphyrin ring is preferred.

In the linker corresponding to the aromatic ring aggregate, the aromatic ring constituting the aromatic ring aggregate can be exemplified by the same aromatic ring as ring A, and C _6-14 arene ring (C _6-12 arene such as benzene and naphthalene ring) A 5- or 6-membered aromatic heterocycle (such as a thiophene ring) containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. The aromatic ring assembly may be composed of one or more types of aromatic rings. The aromatic ring assembly may be composed of about 2 to 1000 aromatic rings (for example, 2 to 500, preferably 2 to 250, more preferably 2 to 200), for example, You may comprise about 10 (for example, 2-5 pieces, preferably 2-4 pieces) aromatic rings.

  The linker L includes a linker constituted by combining two or more of the above linkers, for example, a group represented by the following formula (Ib).

[Wherein, Y represents an oxygen atom, a sulfur atom or an azo group, Z represents an aromatic ring, and q1 to q5 are 0 or 1, respectively. However, q1 + q2 + q4 is 1-3 (preferably 1-2), and q3 + q5 is 1 or 2. ]
In the formula, the following chemical bond

Represents a double bond or a triple bond.

In the formula (Ib), examples of the ring Z include the same aromatic rings as the ring A, for example, C _6-24 arene rings (for example, C _6-14 arene rings such as benzene and naphthalene rings). Ring Z may have a substituent (such as a non-reactive group R ² ).

  Specifically, the group represented by the formula (Ib) includes an arene diazo group [the following formula (Ib-1) and the like], a diarylethene diazo group [the following formula (Ib-2) and the like], a biaryl dioxy group [the following Formula (Ib-3) etc.], arenedietinylene groups [arenedietinylene groups such as the following formula (Ib-4)] and the like.

Among these linkers, a direct bond, an oxygen atom, a sulfur atom, a nitrogen atom, a disulfide group, a diazo group, a vinylene group, a 2- to 4-valent aromatic ring group [C _6-24 arene ring, a 5- to 6-membered aromatic heterocycle] A group composed of one kind of aromatic ring selected from a ring and a porphyrin ring, for example, a C _6-24 arylene group (C ₆ such as o-, m- or p-phenylene group, 9,9-fluorene-diyl group). _-20 arylene groups, especially C _6-14 arylene groups, etc., C _6-24 arene-triyl groups (C _6-20 arene-triyl groups such as 1,3,5-benzene-triyl groups, especially C _6-14 Arene-triyl group), thiophene-diyl group (such as 2,5-thiophene-diyl group), oxazole-diyl group (such as 2,5-oxazole-diyl group), oxadiazole- Diyl group (such as 2,5-oxadiazole-diyl group), porphyrin-tetrayl group (such as 5,10,15,20-porphyrin-tetrayl group)], divalent to tetravalent aromatic ring assembly group [multiple A group to which a C _6-14 arene ring and / or a 5- to 6-membered aromatic heterocycle is linked, for example, a bi-C _6-14 aryl-diyl group (a bi-C _6-12 aryl-diyl group such as a biphenylene group, C _6-10 aryl-diyl groups, etc.), ter C _6-14 aryl-diyl groups (ter-C _6-12 aryl-diyl groups such as o-, m- or p-ter-phenylene groups, especially ter C _{6- 10} aryl - diyl group), bithiophene - diyl group, terthiophene - diyl group], C, such as combinations thereof _{[e.g., C 6-24} Arenjiazo group (phenylene azo group _-14 etc. arylene azo group), such as _{di-C 6-14} aryl ethene diazo group, such as _{di-C 6-24} aryl ethene diazo group (diphenylethene diazo group), a bicycloalkyl _{C 6-24} aryl dioxy group (biphenyl dioxy group _etc.) bicycloaryl _{C 6-14} aryl dioxy group such _as such as _{C 6-14} arene diethylene Chini alkylene groups such as _{C 6-24} arene diethylene Hee alkylene group (anthracene diethyl Hee alkylene group), etc.] is preferable.

  When the linker L is absent (n is 0), p is 1, and when the linker L is present (n is 1), p is selected from a range of 2 or more depending on the valence of the linker L For example, it is about 2 to 10, preferably about 2 to 8 (for example, 2 to 6), and more preferably about 2 to 4 (for example, 2 or 3). When p is 2 or more, the type of A, the value of k1, and the value of k2 may be the same as or different from each other.

Among the compounds represented by the formula (Ia), an aromatic polycarbonyl compound (aromatic polyaldehyde compound, aromatic polycarboxylic acid, etc.) in which the total number of R ¹ contained in one molecule is 2 or more, for example, Compounds (a1) to (a2) are preferred.

(A1) Ring A is monocyclic or condensed bi- to heptacyclic aromatic hydrocarbon ring (C _6-24 arene ring such as benzene, naphthalene, anthracene, pyrene ring, etc.), monocyclic or condensed bi- to heptacyclic aroma A group heterocycle (such as a 5- to 15-membered heterocycle such as a carbazole ring), a porphyrin ring or a phthalocyanine ring, n is 0, k1 is 2 to 4 (for example, 2 or 3), and p is 1. A compound.

As the compound (a1), for example, diformyl _{C 6-20} arene such as di-formyl anthracene; Tetorahorumiru _{C 6-20,} such as tetra-formyl pyrene; triformyl _{C 6-20} arene such as 1,3,5-formylbenzene Arene: heterocyclic dialdehyde (5- or 6-membered heterocyclic dialdehyde) optionally having a substituent (alkyl group and the like) such as 9- (2-ethylhexyl) carbazole-3,6-dicarbaldehyde A condensed heterocyclic dialdehyde of a 5- or 6-membered heterocyclic ring and a benzene ring, etc.); in these compounds, a compound having a carboxyl group instead of a formyl group can be exemplified.

  Further, as the compound (a1), tetraformyl phthalocyanine (2,9,16,23-tetraformyl phthalocyanine, 3,10,17,24-tetraformyl phthalocyanine, etc.), and in this compound, a carboxyl group is used instead of the formyl group. The compound which has can be illustrated.

(A2) Ring A is a monocyclic ring or a condensed bi to heptacyclic aromatic hydrocarbon ring (C _6-24 arene ring such as benzene and naphthalene ring), or a monocyclic ring or a condensed bi to heptacyclic aromatic heterocycle The linker L is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a vinylene group, a 2- to 4-valent aromatic ring group [C _6-24 arene ring, 2 to 4 valent groups corresponding to one kind of aromatic ring selected from 5 to 6-membered aromatic heterocycle and porphyrin ring, for example, C _6-18 arylene group (C _6-14 arylene group etc.), C _6-18 Arene-triyl group (C _6-14 arene-triyl group etc.), thiophene-diyl group, porphyrin-tetrayl group etc.], divalent to tetravalent aromatic ring assembly group [plural C _6-14 arene rings (benzene ring etc.) _{C 6-12} of a Or a combination of 5 to 6-membered aromatic heterocycles (thiophene rings, etc.)] or a combination thereof, n is 1, k1 is 1 or 2, and p is A compound that is 2-4.

As the compound (a2), for example, bis (2-formylphenyl) such as ether bis (formyl _{C 6-12} aryl) ether; 4,4'-formyl like mill stilbene 1,2-bis (formyl _{C 6- 12} aryl) ethene; tri (formyl C _6-12 aryl) amine such as tris (4-formylphenyl) amine; tri (formyl C _6-12 aryl such as 1,3,5-tris (4-formylphenyl) benzene ) Tetra (formyl C _6-12 aryl) porphyrins such as C _6-12 arene, 5,10,15,20-tetrakis (4-formylphenyl) porphyrin; compounds having a carboxyl group instead of a formyl group in these compounds Etc. can be exemplified.

  Examples of the compound (a2) include compounds represented by the following formula (Ic).

[Wherein, rings A ^{1 to} A ² are each an aromatic ring (an aromatic ring similar to ring A, for example, a C _6-12 arene ring such as a benzene ring; a 5- or 6-membered aromatic heterocycle such as a thiophene ring, etc. ), P1 is 0 or an integer of 1 or more, and R ¹ , R ² , k1 and k2 are the same as above]
Incidentally, the same in the formula (Ic), the type of ^{A 1} located at both ends, the type of ^R 1, ^{R 2} is substituted with ^{A 1,} the values of k1, k2, respectively, and one end and the other end May be different.

  The coefficient p1 is, for example, 0 to 10, preferably 0 to 8 (for example, 0 to 6), more preferably 0 to 4 (for example, 0 to 3), particularly about 0 to 2 (for example, 0 or 1). There may be. The coefficient p1 may be, for example, about 0 to 1000, preferably about 0 to 500 (for example, 1 to 250), and more preferably about 0 to 200 (for example, 1 to 150).

As the compound represented by the formula (Ic), a ring assembly compound in which a plurality of C _6-10 arene rings or 5-6 membered aromatic heterocycles of about 2 to 10 (preferably 2 to 5) are bonded, for example, Diformylbi C _6-10 aryl (such as 2,2′-diformylbiphenyl, 4,4′-diformylbiphenyl), diformylter C _6-10 aryl (such as 4,4 ″ -diformylterphenyl), diformylbithiophene (Such as 2,2′-bithiophene-5,5′-dicarbaldehyde), diformylterthiophene (such as 2,2 ′: 5 ′, 2 ″ -terthiophene-5,5 ″ -dicarbaldehyde), these Examples of the compound include a compound having a carboxyl group instead of a formyl group.

  The aromatic carbonyl compound may be a carbonyl compound having a fullerene unit, and examples thereof include a compound represented by the following formula (Id).

(In the formula, R ^1a represents a hydrogen atom, a carbonyl group-containing group or a non-reactive group, R ^1b represents a carbonyl group-containing group, L ₁ represents a direct bond or an alkylene group, and t is 1 or 2. )
The compound represented by the formula (Id) is presumed to form a π-electron conjugated structure throughout because the π-electron cloud distorted on the outside of the fullerene overlaps with or between the fullerenes.

In the formula (Id), examples of the carbonyl group-containing group represented by R ^1a and R ^1b include the same carbonyl group-containing groups as R ¹ , such as a formyl group and a carboxyl group. Examples of the non-reactive group represented by R ^1a include the same non-reactive groups as R ² , for example, a C _6-10 aryl group such as a phenyl group; a thienyl group (such as a 2-thienyl group), a furyl group (2 And 5- or 6-membered aromatic heterocyclic groups such as -furyl group. Examples of the alkylene group represented by L ₁ include C _1-10 alkylene groups (such as C _1-6 alkylene groups) such as methylene, ethylene, propylene, trimethylene, and tetramethylene groups.

  The compound represented by the formula (Id) is commercially available from ATR Co., Ltd. under the trade names “[60] PCB-A”, “FA-06-02-BIS”, “FA-06-03 [60] PCBA”, “ FA-06-03-BIS [60] PCBA-BIS "," FA-09-01 [60] PCPA "," FA-09-01-BIS [60] PCPA-BIS ", and the like.

Carbonyl compounds having the fullerene unit may be a compound having a C ₇₀ fullerene units instead of C ₆₀ fullerene units in formula (Id). Such compounds are available from ATR Co., Ltd. under the trade names “FA-09-02 [70] PCBA”, “FA-09-02-BIS [70] PCBA-BIS”, “FA-09-03 [70]. PCPA "," FA-09-03-BIS [70] PCPA-BIS "," FA-09-04 "," FA-09-04-BIS "," FA-09-05 ", and the like.

These aromatic carbonyl compounds can be used alone or in combination of two or more. Among aromatic carbonyl compounds, aromatic polyaldehyde compounds, that is, R ¹ is a formyl group, and the total number of R ¹ contained in one molecule is 2 or more (for example, 2 to 4, preferably 3 to 4). Are preferable (for example, compounds shown in Tables 1 to 3).

(Aromatic polyamine)
The aromatic polyamine is not particularly limited as long as it is an aromatic compound having a plurality of amino groups (primary amino groups), and may be, for example, a compound represented by the following formula (IIa).

(Wherein R ³ represents an amino group, R ⁴ represents a hydrogen atom, an amino group, a mercapto group or a hydroxyl group, k3 is an integer of 1 or more, and L, n, A, R ² , k2 and p Is the same as above, except that when n is 0, k3 is an integer of 2 or more.)
In the formula (IIa), the substitution number k3 of a pair of R ³ and R ⁴ in contact with each other at the ortho position can be selected from the range of, for example, about 1 to 10, and when n is 0, k3 is 2 to 2. 10, preferably 2 to 8, more preferably about 2 to 6 (for example, 2 to 4), and when n is 1, k3 is 1 to 4, preferably 1 to 3, more preferably 1 to 2. It is about (for example, 1). When ring A is a condensed ring, a pair of R ³ and R ⁴ groups may be substituted on at least one ring. In addition, the substitution position of the pair of groups R ³ and R ⁴ is not particularly limited. For example, when ring A is substituted in plural, any two pairs of groups may be substituted at adjacent positions. From the viewpoint of property, substitution to a non-adjacent position is preferable. Further, when two or more rings A, R ² and R ⁴ are contained in one molecule, the types may be the same or different from each other. When p is 2 or more, the values of k2 and k3 may be the same or different from each other.

  Of the compounds represented by the formula (IIa), the following compounds (b1) to (b2) are preferable.

  (B1) Ring A is monocyclic or condensed bi- to heptacyclic aromatic hydrocarbon ring (benzene, naphthalene, fluorene, pyrene, anthraquinone, coronene ring, etc.), monocyclic or condensed bi- to heptacyclic aromatic heterocycle ( A 5- to 15-membered heterocyclic ring such as a carbazole or phenanthridine ring), a porphyrin ring or a phthalocyanine ring, n is 0, k3 is 2 to 4 (for example, 2 or 3), and p is 1 A compound.

Examples of the compound (b1) include phenylenediamine, diaminonaphthalene, diaminofluorene, diaminopyrene, 2,5-diamino-1,4-benzenedithiol, diaminocarbazole, diaminoanthraquinone, diamino-6-phenylphenanthridine, and the like. Examples of the substituent include di- to triamino C _6-20 arene, which may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, a mercapto group, and an alkylthio group.

  Examples of the compound (b1) include tetraaminophthalocyanine (2,9,16,23-tetraaminophthalocyanine, 3,10,17,24-tetraaminophthalocyanine, etc.).

(B2) Ring A is a monocyclic ring or a condensed bi- to heptacyclic aromatic hydrocarbon ring (C _6-24 arene ring such as benzene and naphthalene ring), and linker L is directly bonded, nitrogen atom, oxygen atom, sulfur Atom, diazo group, disulfide group, vinylene group, divalent to tetravalent aromatic ring group [corresponding to a kind of aromatic ring selected from C _6-24 arene ring, 5- to 6-membered aromatic heterocyclic ring and porphyrin ring To tetravalent group, for example, C _6-18 arylene group (such as C _6-14 arylene group), C _6-18 arene-triyl group (such as C _6-14 arene-triyl group), oxazole-diyl group, oxadi azole - diyl group, a porphyrin - tetrayl group, etc.], or combinations thereof _{[e.g., (such} as _{C 6-10} Arenjiazo group) _{C 6-14} Arenjiazo group, di _{C 6-14} arylene Etenjiazo group (such as _{di-C 6-10} aryl ethene diazo group), a bi _{C 6-14} aryl dioxy group (such as a bi _{C 6-10} aryl dioxy group) etc.], n is 1, k3 is 1 Or the compound which is 2, and p is 2-4.

Examples of the compound (b2) include tri (amino C _6-10 aryl) amine such as tris (4-aminophenyl) amine; bis (amino C _6-10 aryl) sulfide such as bis (2-aminophenyl) sulfide. Di (amino C _6-10 aryl) disulfides such as di (2-aminophenyl) disulfide; di (amino C _6-10 aryl) ethene such as 4,4′-diaminostilbene; 4,4′-diaminobiphenyl and the like; of Jiaminobi _{C 6-10} aryl; 4,4 "- Jiaminota _{C 6-10} aryl, such as diamino -p- terphenyl; 9,9-bis (4-aminophenyl) fluorene such as 9,9-bis (amino C _6-10 aryl) fluorene; 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole, etc. Di (amino _{C 6-10} aryl) oxadiazole; 1,3-bis (3,5-diamino - phenylazo) bis benzene (mono- to diamino _{C 6-10 arylazo) C 6-10} arene 4,4 Substituents such as' -bis (4-amino-1-naphthylazo) -stilbene, 4,4'-bis (4-amino-1-naphthylazo) stilbene-2,2'-disulfonic acid (alkyl group, hydroxyl group, Bis (amino C _6-10 arylazo) stilbene optionally having an alkoxy group, mercapto group, alkylthio group, sulfonyl group, sulfinyl group, etc .; bis such as 4,4′-bis (4-aminophenoxy) biphenyl (amino _{C 6-10} aryloxy) bicycloaryl _{C 6-10} aryl; 5,10,15,20-tetrakis (4-aminophenyl Such as tetra (amino _{C 6-10} aryl) porphyrin and porphyrin can be exemplified.

  Examples of the compound (b2) include compounds represented by the following formula (IIb).

(Wherein A ¹ , A ² , R ² , R ³ , R ⁴ , k2, k3 and p1 are the same as above)
Examples of the compound represented by the formula (IIb) include 2,2′-bis (trifluoromethyl) benzidine, 3,3′-diaminobenzidine, 3,5′-dihydroxybenzidine, and 3,5′-dimercapto. Benzidine optionally having a substituent such as benzidine; naphthidine optionally having a substituent such as 3,3′-dimethylnaphthidine and the like can be exemplified, and examples of the substituent include an alkyl group and a haloalkyl group. , Hydroxyl group, alkoxy group, haloalkoxy group, mercapto group, alkylthio group, haloalkylthio group and the like.

These aromatic polyamines can be used alone or in combination of two or more. Of the aromatic polyamines, compounds in which the total number of R ³ contained in one molecule is 2 to 4 (preferably 2 to 3) are preferred. The aromatic polyamine is usually used in combination with an aromatic polyaldehyde compound having a plurality of (for example, 2 to 4, particularly 3 to 4) formyl groups in one molecule. The aromatic polyamine is preferably a compound having low toxicity (or non-toxicity) (for example, compounds shown in Tables 4 to 9) from the viewpoint of handleability.

In the formula (IIa), the compound in which R ⁴ is a hydrogen atom is a carbon-nitrogen compound in which the amino group represented by R ³ reacts with a carbonyl group-containing group in the reaction with an aromatic polycarbonyl compound. A double bond or an amide bond is formed. On the other hand, a compound (ring-forming polyamine) in which R ⁴ is an amino group, a hydroxyl group or a mercapto group is adjacent to R ³ and R ^{4 in} the reaction with an aromatic polycarbonyl compound (especially an aromatic polyaldehyde compound). And a carbonyl group-containing group often participate in the reaction to form a ring. For example, when R ⁴ is (i) an amino group, an imidazole ring is formed, (ii) a hydroxyl group is an oxazole ring, and (iii) a mercapto group is often a thiazole ring. .

The ratio of the aromatic polycarbonyl compound to the aromatic polyamine is the ratio of carbonyl group to amino group [reactive group with carbonyl group, for example, in the formula (IIa), when R ⁴ is an amino group, a hydroxyl group or a mercapto group , R ³ and R ⁴ are regarded as one reactive group], for example, the former / the latter = 70/30 to 30/70, preferably 60/40 to 40/60, more preferably 55 It may be about / 45 to 45/55.

(Aromatic heterocyclic compounds)
The aromatic heterocyclic compound only needs to have a plurality of reaction sites (α-carbon site adjacent to the hetero atom of the heterocyclic ring) with the aromatic aldehyde compound. Any of a formula compound, a condensed cyclic compound, and a ring assembly compound may be sufficient. The heterocyclic ring of the heterocyclic compound may be a 5- to 8-membered ring, preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring. The heterocycle usually contains an aromatic 5-membered ring. Further, the heterocyclic ring usually has at least one heteroatom selected from an oxygen atom, a sulfur atom, a nitrogen atom or imino group, a selenium atom, and a tellurium atom. These heterocyclic compounds can be used alone or in combination of two or more.

  The aromatic heterocyclic compound can be represented by the following formula (III).

(In the formula, Het represents an aromatic heterocyclic ring, X represents a hetero atom, R ⁵ represents a non-reactive group, r represents an integer of 0 to 3, and L, n and p are the same as above. )
Examples of the hetero atom X of the heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom or an imino group (NH group), a selenium atom, a tellurium atom, and the like, and the heterocyclic ring of the heterocyclic compound is a single hetero atom. May be included, and a plurality of heteroatoms of the same or different types may be included. The hetero atom of the heterocyclic ring is usually an oxygen atom, a sulfur atom, a nitrogen atom or an imino group, particularly a sulfur atom in many cases.

  The aromatic heterocycle Het may be a compound having the plurality of α-carbon moieties in one molecule, and typical monocyclic heterocycles include, for example, 5-membered heterocycles having 1 or 2 heteroatoms. Examples thereof include a 6-membered heterocyclic ring having 1 or 2 heteroatoms. Examples of typical fused ring heterocycles include fused heterocycles in which the same or different heterocycles are fused, and fused heterocycles in which a benzene ring and a heterocycle are fused. The heterocyclic compound usually contains a 5-membered aromatic heterocycle having at least one heteroatom selected from a sulfur atom, an oxygen atom, a nitrogen atom or an imino group as a heteroatom of the heterocycle.

Low-boiling heterocyclic compounds (for example, monocyclic heterocyclic compounds, particularly monocyclic 5-membered heterocyclic compounds) have reduced film-forming properties, and liquid heterocyclic compounds at room temperature (for example, 20 to 25 ° C.) The performance of the crosslinked coating film formed by the heat treatment after film formation is likely to deteriorate. Therefore, a low-boiling heterocyclic compound (or monocyclic heterocyclic compound) such as furan preferably has a non-reactive substituent R ⁵ to increase the boiling point, and the heterocyclic compound is solid at room temperature. And a heterocyclic compound having high solubility in a solvent. From such a viewpoint, the boiling point of the monocyclic heterocyclic compound is preferably 50 ° C. or higher (for example, 75 to 350 ° C., preferably 100 to 300 ° C., more preferably 120 to 250 ° C.).

As the non-reactive group R ⁵ , in addition to the same non-reactive group as the non-reactive group R ² , a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), carboxyl group, alkoxycarbonyl group ( For example, linear or branched C _1-10 alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl group, etc.), hydroxyalkyl group (eg, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, A hydroxy C _1-10 alkyl group such as 3-hydroxypropyl and 4-hydroxybutyl group), a cyanoalkyl group (eg, a cyano C _1-10 alkyl group such as cyanomethyl, 2-cyanoethyl, 3-cyanopropyl group, etc.) Carboxyalkyl group (for example, carboxymethyl, 2-carboxyl Carboxy -C _1-6 alkyl group such as Kishiechiru group, di-carboxymethyl group, 2,2-like dicarboxy C _1-6 alkyl group such as di-carboxyethyl group), an alkoxycarbonyl group (e.g., linear or Branched chain C _1-10 alkoxy-carbonyl-C _1-6 alkyl group etc.), dihydroxybornyl group (—B (OH) ₂ ), heterocyclic group (pyridyl group, oxolan-yl group etc. nitrogen atom, sulfur And a 5- or 6-membered heterocyclic group having a hetero atom selected from an atom and an oxygen atom). As the non-reactive group R ⁵ , an acidic group such as a carboxyl group is advantageous in that it binds to a surface functional group (hydroxyl group) of inorganic particles such as titanium oxide particles. In the present invention, unlike a conventional low molecular weight dye, since it has a three-dimensional network structure, the conductive polymer is not released from the titanium oxide surface by a temperature increase of several tens of degrees Celsius, and functions as a sensitizer. Will not be damaged.

As the non-reactive group R ⁵ , a halogen atom; a linear or branched C _1-10 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, hexyl, 2-ethylhexyl, octyl group; C _5-10 cycloalkyl group such as cyclohexyl group; C _6-10 aryl group such as phenyl group; linear or branched C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, butoxy group; linear Or a branched C _1-10 alkoxy-carbonyl group; a hydroxy C _1-4 alkyl group; a cyano C _1-4 alkyl group; a carboxy C _1-4 alkyl group; a dihydroxybornyl group (—B (OH) ₂ ); In many cases, they are fullerene units bonded via a linking group.

  r represents an integer of 0 to 3, and is usually 0 to 2 (for example, 0 or 1).

  Examples of the linker L include a direct bond, a linker corresponding to ethylene (such as vinylene group), an arylene group (such as phenylene group), a linker corresponding to a 5- or 6-membered aromatic heterocycle (thiophene-diyl group, pyrrole-diyl group, etc. ), And the same linker as described above for a linker corresponding to an aromatic ring assembly (a group in which a plurality of 5- or 6-membered aromatic heterocycles are linked, for example, an oligo or polythiophene-diyl group).

  Examples of the compound represented by the formula (III) include the following compounds (c1) to (c3).

(C1) Ring Het is a monocyclic or fused-ring aromatic heterocycle containing a 5-membered heterocycle, X is a sulfur atom, oxygen atom, nitrogen atom or imino group (NH group), and r is 0 A compound having an integer of ˜2 (unreactive group R ⁵ is unsubstituted or substituted), n is 0 (no linker L), and p is 1.

  Among the compound (c1), as an unsubstituted monocyclic compound, for example, a 5-membered heterocyclic compound (thiophene, furan, pyrrole, imidazole, pyrazole, isothiazole, isoxazole, etc.), a 6-membered heterocyclic compound (pyridine) , Pyrazine, pyrimidine, etc.), and examples of the condensed cyclic compound include thieno [3,2-b] thiophene, dithieno [3,2-b: 2 ′, 3′-d] thiophene, naphthyridine and the like. A compound in which a heterocycle of the same type (5-membered or 6-membered heterocycle) is condensed, a compound in which a heterocycle of a different type (5 or 6-membered heterocycle) such as thieno [2,3-b] furan is condensed, isobenzofuran Examples thereof include compounds in which a benzene ring and a heterocyclic ring are condensed, such as isoindole, isoquinoline, and phthalazine.

Among the monocyclic compounds having the non-reactive group R ⁵ , examples of the thiophene derivative include 3-halothiophene (3-chlorothiophene, 3-bromothiophene, etc.), 3,4-dihalothiophene (3,4). -Dichlorothiophene, 3,4-dibromothiophene, etc.), 3-alkylthiophene (3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-octylthiophene, 3- (2-ethylhexyl) thiophene, 3-C _1-12 alkylthiophene such as 3- _{decylthiophene} ), 3,4-dialkylthiophene (3,4-dimethylthiophene, 3,4-diethylthiophene, 3,4-dibutyl such as _{3,4-di-C 1-10} alkyl thiophene, such as thiophene), -Hydroxythiophene, 3-alkoxythiophene (3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, etc. 3-C ₁ such as -C _1-12 alkoxythiophene), 3-arylthiophene (such as 3-phenylthiophene), 3-carboxythiophene, 3-alkoxycarbonylthiophene (3-methoxycarbonylthiophene, 3-ethoxycarbonylthiophene, etc.) _-6 alkoxy - carbonyl thiophene), 3-cyano-thiophene, 3-cyano-alkylthiophene (thiophene-3-acetonitrile such as _{3-cyano-C 1-6} alkyl thiophene), 3- (arsenate Rokishiarukiru) thiophene (3-hydroxymethyl-thiophene, 3- (2-hydroxyethyl) thiophene such as 3- (hydroxy _{C 1-6} alkyl) thiophene), 3-thiophene malonic acid, 3-thienylboronic acid, 2- ( Examples include 3-thienyl) -1,3-dioxolane.

Examples of the fused cyclic thiophene derivative include thieno [3,2-b] thiophene, dithienothiophene, halodithienothiophene (3,5-dibromodithieno [3,2-b: 2 ′, 3′-d] thiophene. And alkyldithienothiophene (3,5-diC _1-10 alkyldithieno [3,2-b: 2 ′, 3′-d] thiophene and the like).

Examples of the furan derivative include halofuran (3-chlorofuran, 3-bromofuran, etc.), 3-alkylfuran (3-C _1-10 alkylfuran, such as 3-methylfuran), 3-hydroxyalkylfuran (3- Examples thereof include 3- (hydroxy-C _1-6 alkyl) furan such as furan methanol) and 3-furylboronic acid.

Examples of the pyrrole derivative include 3-alkylpyrrole (3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, etc. 3-C _1-10 alkyl pyrrole), 3,4-dialkyl pyrrole (3,4-diC _1-10 alkyl pyrrole such as 3,4-dimethyl pyrrole, 3,4-dibutyl pyrrole, etc.), N-alkyl Pyrrole (N-C _1-10 alkyl pyrrole such as N-methylpyrrole), 3-carboxy pyrrole, 3-alkoxycarbonyl pyrrole (3-C _1-6 alkoxy-carbonyl pyrrole such as 3-ethoxycarbonyl pyrrole), 3-hydroxypyrrole, 3-alkoxypyrrole (3-methoxypyrrole) Examples thereof include 3-C _1-6 alkoxypyrrole such as roll, 3-ethoxypyrrole, and 3-butoxypyrrole).

  Examples of the heterocyclic compound having a fullerene unit include a compound represented by the following formula (IIIa).

(Wherein R ⁶ represents an alkyl group, a cycloalkyl group or an aryl group, R ⁷ and R ⁸ each independently represents an alkylene group, L ₂ represents a linking group, and X ⁴ represents a hetero atom)
As the alkyl group represented by R ⁶ , the same alkyl group as described above (such as a linear or branched C _1-10 alkyl group), and as the cycloalkyl group, the same cycloalkyl group as described above (cyclohexyl group). such as _{C 5-10} cycloalkyl group, etc.), the aryl group include the same aryl group (such as _{C 6-10} aryl groups such as phenyl group) can be exemplified. Examples of the alkylene group represented by R ⁷ and R ⁸ include C _1-10 alkylene groups such as methylene, ethylene, propylene, trimethylene and tetramethylene groups. Examples of the linking group L ₂ include a direct bond (—), —C (O) O— (carbonyloxy group), —OC (O) — (oxycarbonyl group), an oxygen atom, and a sulfur atom. Examples of the hetero atom X ⁴ include a sulfur atom, an oxygen atom, a nitrogen atom, or an imino group (NH group) as described above.

In the compound having a fullerene unit, R ⁶ is a phenyl group, R ⁷ and R ⁸ are each independently a C _2-6 alkylene group, the linking group L ₂ is —C (O) O— (carbonyloxy group), a hetero atom A compound in which X ⁴ is a sulfur atom may be used. A compound having such a fullerene unit is commercially available, for example, as [6,6] -phenyl-C61 butyric acid (3-ethylthiophene) ester.

(C2) Ring Het represents a 5- or 6-membered aromatic heterocyclic ring, X is a sulfur atom, oxygen atom, nitrogen atom or imino group (NH group), and r is an integer of 0 to 2 (non-reactive group) R ⁵ is unsubstituted or substituted), the linker L is a direct bond, a vinylene group or a group composed of one or more 5- to 6-membered aromatic heterocycles, n is 1 (the linker L is absent) ), A compound in which p is an integer of 2 to 4 (for example, 2 or 3).

  Examples of the compound (c2) include 5- or 6-membered aromatic heterocyclic ring assembly compounds, for example, compounds represented by the following formula (IIIb).

[Wherein, rings Het _{1 to} Het ₃ independently represent a 5- or 6-membered aromatic heterocyclic ring, and X ^{1 to} X ³ independently represent a sulfur atom, an oxygen atom, a nitrogen atom or an imino group ( NH group), R ^{5a to} R ^5c independently represent a non-reactive group, r1 to r3 are each an integer of 0 to 2 (eg, 0 or 1), and p1 is 0 to 1000 (eg, , Represents an integer from 0 to 250)]
The rings Het _{1 to} Het ₃ are preferably monocyclic heterocycles exemplified in the section of ring Het, such as a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring, and in particular, a thiophene ring, a furan ring, and a pyrrole ring (for example, A thiophene ring). Examples of the non-reactive group represented by R ^{5a to} R ^5c include the same substituents as the non-reactive group R ⁵ .

The repeat coefficient p1 of the ring Het ₂ is, for example, 0 to 1000, preferably 0 to 500 (for example, 1 to 250), more preferably 0, depending on the presence or type of the non-reactive groups R ^{5a to} R ^5c. About 200 (for example, 1-150) may be sufficient.

In a heterocyclic compound having poor solubility in a solvent (for example, a non-reactive group R ^{5a to} R ^5c having a small number of carbon atoms, for example, a heterocyclic compound having a halogen atom, an aryl group, etc.), the coefficient p1 is, for example, 0 to It may be about 10, preferably 0 to 6, more preferably about 0 to 4 (for example, 1 to 3). In addition, non-reactive groups R ^{5a to} R ^5c (for example, an alkyl group (a linear or branched C _4-10 alkyl group such as a hexyl group) or the like for improving solubility in a solvent, an alkoxy group (direct In a heterocyclic compound having a chain or branched chain C _4-10 alkoxy group))), the coefficient p1 can be selected from the range of about 0 to 1000 as described above, for example. In addition, when the coefficient p1 becomes large, a mild three-dimensional crosslinked structure is likely to occur, and the resistance to an organic solvent is likely to be reduced. From such a viewpoint, the coefficient p1 can be generally selected from a range of about 0 to 250, preferably 0 to 100 (for example, 1 to 75), and more preferably 0 to 50 (for example, 0 to 10). In addition, when r1-r3 are each "0", p1 is 0-3 normally, Preferably it is about 0-2 (for example, 1 or 2).

Examples of the compound represented by the formula (IIIb) include bifuran, bithiophene (such as 2,2′-bithiophene), terthiophene (such as 2,2 ′: 5 ′, 2 ″ -terthiophene), and quarterthiophene (2 , 2 ': 5', 2 ": 5", 2 "'-quaterthiophene, etc.), bipyridine (such as 2,2'-bipyridine), quarterpyridine, 3,4'-dialkyl-2,2'-bithiophene ( 3,4′-dihexyl-2,2′-bithiophene, etc. 3,4′-diC _4-10 alkyl-2,2′-bithiophene), poly (3-alkyl-thiophene) (X ^{1 to} X ³ are A sulfur atom, rings Het _{1 to} Het ₃ are 2,5-thiophene-diyl groups, R ^{5a to} R ^5c are 3- or 4-position C _4-10 alkyl groups, and r 1 to r 3 are each 1 And p1 is 1 ˜25 polythiophene compounds), 2,5-di (2-thienyl) -1H-pyrrole, 2- (3-thienyl) pyridine and the like.

  Furthermore, the compound represented by the formula (IIIb) may be a compound in which an arylmethylene group (or arylvinylene group) is interposed between heterocycles. Such a compound can be represented by, for example, the following formula (IIIc) or (IIId).

(In the formula, A ³ and A ⁴ each independently represent an aromatic ring, p 2 and p 3 each independently represent an integer of 1 to 5, Het _{1 to} Het ₃ , X ^{1 to} X ³ , R ^{5a to} R ^5c and r1-r3 are the same as above)
Het _{1 to} Het ₃ are the same aromatic heterocycles as described above (such as 5-membered aromatic heterocycles such as thiophene rings), X ^{1 to} X ³ are the same heteroatoms (such as sulfur atoms) as described above, and R ^{5a to} R 3. ^5c is the same non-reactive group as described above (C _1-10 alkyl group such as hexyl group), r1 to r3 are the same integers of 0 to 2 (for example, 0 or 1) as above, and A ³ and A ⁴ can be exemplified by the same aromatic rings as described above (C _6-10 arene rings such as benzene and naphthalene rings), and p2 is about 1 to 5 (for example, 1 to 4, preferably 1 to 3). The integer, p3 is an integer of about 1 to 5 (for example, 1 to 4, preferably 1 to 3).

  The compound represented by the formula (IIIc) is obtained by reacting the same aromatic heterocyclic compound as described above with an aromatic monoaldehyde compound (aryl aldehydes such as benzaldehyde, heteroaryl aldehydes, etc.), and the above α-carbon moiety. The compound represented by the formula (IIId) can be obtained by forming a carbon-carbon single bond (—C—C—), and the compound represented by the formula (IIIc) is subjected to a dehydrogenation reaction. To generate a carbon-carbon double bond (—C═C—).

  Examples of the compound (c2) include a compound in which a plurality of aromatic heterocycles are linked via a vinylene group, such as 1,2-di (2-thienyl) ethylene.

  These aromatic heterocyclic compounds can be used alone or in combination of two or more. The aromatic heterocyclic compound has 2 to 8 (for example, 2 to 6, preferably 2 to 4, more preferably 2 to 3, for example, 2) reaction sites (unmodified) in one molecule. preferably having an α-carbon position). The aromatic heterocyclic compound is usually used in combination with an aromatic polyaldehyde compound having a plurality of (for example, 2 to 4, particularly 3 to 4) formyl groups in one molecule. Aromatic heterocyclic compounds can be shown, for example, in Tables 10 to 12 below.

  The aromatic heterocyclic compound is adjacent to the hetero atom of the heterocyclic ring and has a plurality of unmodified α-carbon positions, and the number of α-carbon positions in one molecule is 2 to 5, preferably 2 to 4, especially about 2 or 3. The α-carbon moiety adjacent to the heteroatom is usually located at the 2,5-position for a monocyclic 5-membered heterocycle and at the 2,6-position for a monocyclic 6-membered heterocycle. In a heterocyclic compound in which a 5-membered heterocyclic ring is condensed (for example, thieno [3,2-b] thiophene, dithieno [3,2-b: 2 ′, 3′-d] thiophene), the α-carbon moiety Is located at the 2-position and / or 5-position, and in a heterocyclic compound in which a 6-membered heterocyclic ring is condensed, the α-carbon moiety is located at the 2-position and / or the 6-position.

  The ratio of the aromatic polyaldehyde compound to the aromatic heterocyclic compound is, for example, the former / the latter = 70 in terms of the equivalent ratio of the formyl group to the free (or unsubstituted) α-carbon moiety of the heterocyclic compound. / 30 to 30/70, preferably 60/40 to 40/60, more preferably about 55/45 to 45/55.

  When an aromatic polyamine and an aromatic heterocyclic compound are combined as an aromatic reaction component, the ratio of the aromatic polyamine and the aromatic heterocyclic compound is the former / the latter = 70/30 in terms of the equivalent ratio of reaction sites. It may be about 30/70, preferably 60/40 to 40/60, and more preferably about 55/45 to 45/55. The ratio between the aromatic polyaldehyde compound and the aromatic reaction component is the same as the ratio between the aromatic polyaldehyde compound and the aromatic polyamine or aromatic heterocyclic compound.

  In the present invention, the absorption wavelength of the conductive polymer can be easily adjusted by changing the type and ratio of the polymerization component (aromatic carbonyl compound, aromatic polyamine, aromatic heterocyclic compound). For example, when the polymerization component contains an aromatic heterocyclic compound [a compound in which ring A is an aromatic heterocyclic ring in formulas (Ia) and (IIa), a compound represented by formula (III), etc.] Absorption can be shifted to the wavelength side. Further, by introducing a bulky group (such as a trifluoromethyl group) as a non-reactive group into the polymerization component, the permeability can be improved relatively. Thus, the present invention is advantageous in that the absorption wavelength of the conductive polymer can be optimized in accordance with the emission spectrum of the light source.

(Dopant)
The polymerizable composition (or the crosslinkable composition) may further contain a dopant. The dopant is an electron donating dopant (for example, alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium). , Methyltriethylammonium, dimethyldiethylammonium, etc.)), and electron-accepting dopants (eg, halogens, organic cyano compounds, fulvalene compounds, protonic acids, Lewis acids, organometallic compounds, etc.). A preferred dopant is an electron accepting dopant. In addition, the polymerization component (or reaction component) is a compound that functions as a dopant, for example, a compound that includes an acidic group such as a sulfo group or a dihydroxybornyl group (—B (OH) ₂ ) (a compound that functions as a protonic acid). In some cases, these compounds are self-doping. Therefore, when the polymerization component (or reaction component) is a compound that functions as a dopant, the dopant is not necessarily required.

Examples of halogens include chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), iodine chloride (ICl), iodine bromide (IBr), and iodine fluoride (IF).

  Examples of organic cyano compounds include tetracyanoethylene, tetracyanobenzene, tetracyanoquinodimethane, and tetracyanoazanaphthalene. Examples of fulvalene compounds include tetrathiafulvalene compounds (for example, tetrathiafulvalene, 2 , 6-dimethyltetrathiafulvalene, tetramethyltetrathiafulvalene, 2,6-diphenyltetrathiafulvalene, octamethylenetetrathiafulvalene, hexamethylenetetrathiafulvalene, dibenzotetrathiafulvalene, bis (ethylenedioxy) tetrathiafulvalene, Bis (ethylenedithio) tetrathiafulvalene), tetraselenafulvalene compounds (eg, tetraselenafulvalene, tetramethyltetraselenafulvalene, hexamethyleneselena) Rubaren etc.), tetra-shine full Valentin compounds (e.g., tetra shine full Valentin, hexamethylene tetra shine full Valentin), and others.

Examples of Lewis acids include aluminum chloride AlCl ₃ , tin chloride SnCl ₂ , zinc chloride ZnCl ₂ , titanium chloride TiCl ₄ , boron fluoride BF ₅ , phosphorous fluoride PF ₅ , arsenic fluoride AsF ₅ , and antimony fluoride SbF _5. , Boron chloride BCl ₅ , boron ether complex salt and the like.

  Examples of the protonic acid include inorganic acids (for example, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, hydrofluoric acid, etc.) and organic acids. Examples of organic acids include organic carboxylic acids and organic sulfonic acids.

Examples of organic carboxylic acids include compounds having at least one carboxyl group (aliphatic, alicyclic, aromatic, heterocyclic carboxylic acid), such as organic monocarboxylic acids (alkane carboxylic acids such as formic acid and C _{1- 6} Alkane-carboxylic acids (acetic acid, propionic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, etc.); arene carboxylic acids, for example, C _6-12 arene-carboxylic acids such as benzoic acid, etc. Organic polycarboxylic acids (alkane polycarboxylic acids such as C _2-6 alkane-dicarboxylic acids such as oxalic acid, malonic acid and succinic acid; alkene polycarboxylic acids such as C ₂ such as maleic acid and fumaric acid _-6 alkene-dicarboxylic acids and the like; arene polycarboxylic acids such as phthalic acid and naphthalene C _6-12 arene-di to tetracarboxylic acids such as carboxylic acid and pyromellitic acid), hydroxy carboxylic acids (hydroxyalkane carboxylic acids such as hydroxy C _1-6 alkanes such as glycolic acid, lactic acid, tartaric acid, citric acid) -Carboxylic acid, etc .; hydroxyarene carboxylic acid, for example, hydroxy _C6-12 arene-carboxylic acid such as hydroxybenzoic acid) and the like.

Examples of the organic sulfonic acid include compounds having at least one sulfo group (—SO ₃ H) (aliphatic, alicyclic, aromatic, heterocyclic sulfonic acid), such as alkanesulfonic acid (methanesulfonic acid, ethanesulfone). Acid, C _1-6 alkanesulfonic acid such as 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid), haloalkanesulfonic acid (halo C _1-6 alkanesulfonic acid such as trifluoromethanesulfonic acid), Examples include arenesulfonic acid (benzenesulfonic acid, alkylbenzenesulfonic acid (p-toluenesulfonic acid etc.), C _6-12 arenesulfonic acid such as naphthalenesulfonic acid, styrenesulfonic acid etc.).

Examples of the polyanion include a sulfonate group (—O—SO ₃ H), a sulfo group (—SO ₃ H), a sulfino group (—SO ₂ H), a carboxyl group (—COOH), or a salt thereof (sodium, potassium, etc.) And an anionic group is a sulfo group, a carboxyl group, or a salt thereof. Examples thereof include an alkali metal salt, an alkaline earth metal salt such as calcium and magnesium, ammonia, an amine salt, and the like. There are many cases.

As a monomer that forms a polyanion, a polymerizable monomer having a sulfo group, for example, alkene sulfonic acid (C _2-10 alkene sulfonic acid such as vinyl sulfonic acid, C _4-10 alkadiene such as isoprene sulfonic acid) Sulfonic acid etc.), sulfoalkyl (meth) acrylate (sulfo C _2-6 alkyl (meth) acrylate etc. such as sulfoethyl methacrylate, 4-sulfobutyl methacrylate), vinylarene sulfonic acid (vinyl C ₆ -6 such as styrene sulfonic acid etc.) ₁₂ arene sulfonic acid), N- sulfoalkyl acrylamide (N- sulfoethyl acrylamide such as N- sulfo _{C 2-6} alkyl acrylamide), and others. These monomers may form a copolymer by homopolymer or a combination of two or more. The monomer may be a copolymerizable monomer (for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic monomers such as (meth) acrylamide), and fragrance such as styrene. A copolymer with an aromatic vinyl monomer) may be formed. Typical polyanions include, for example, polyvinyl sulfonic acid, polyisoprene sulfonic acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polystyrene sulfonic acid, and the like, and copolymers thereof can also be used. These polyanions can be used alone or in combination of two or more.

  The polyanion may be an oligomer or a polymer, and the number average molecular weight of the polyanion is, for example, 500 to 100,000, preferably 1000 to 50000, more preferably 2500 to 25000 in terms of polystyrene in gel permeation chromatography (GPC). It may be a degree.

  The amount of the dopant used is, for example, 0.001 to 50 parts by weight (for example, based on 1 part by weight of the total amount of the aromatic carbonyl compound and the aromatic reaction component (aromatic polyamine and / or aromatic heterocyclic compound)) 0.005 to 30 parts by weight), preferably 0.01 to 20 parts by weight (for example, 0.01 to 15 parts by weight), more preferably 0.1 to 10 parts by weight (for example, 0.1 to 5 parts by weight). ) Degree.

(Acid catalyst)
The composition containing an aromatic aldehyde compound and an aromatic heterocyclic compound preferably contains an acid catalyst. In addition, when an aromatic heterocyclic compound contains acidic groups, such as a sulfo group and a dihydroxyboryl group (-B (OH) ₂ ), an acid catalyst is not necessarily required. Further, even when the dopant is a compound having an acidic group (such as a sulfo group), the acid catalyst is not necessarily required.

  The acid catalyst may be either a protonic acid or a Lewis acid. Examples of the protic acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, perchloric acid, hydrofluoric acid, etc.), organic acids (organic carboxylic acids such as acetic acid, propionic acid, trichloroacetic acid, trifluoroacetic acid, etc.) Methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfonic acid such as styrenesulfonic acid, etc.). Examples of the Lewis acid include aluminum chloride, tin chloride, zinc chloride, titanium chloride, boron fluoride, and boron fluoride ether complex. These acid catalysts can be used alone or in combination of two or more.

  The usage-amount of an acid catalyst is the range of about 0.001-1 weight part (for example, 0.01-1 weight part) with respect to 1 weight part of total amounts of an aromatic aldehyde compound and an aromatic heterocyclic compound, for example. Usually, it may be 0.005 to 0.3 parts by weight, preferably 0.01 to 0.2 parts by weight, and more preferably about 0.02 to 0.1 parts by weight.

(solvent)
The polymerizable composition (or the crosslinkable composition) may further contain a solvent (or solvent). The solvent is not particularly limited as long as it is soluble in the aromatic carbonyl compound and aromatic polyamine and / or aromatic heterocyclic compound and does not inhibit the reaction. For example, water, hydrocarbons (toluene, Aromatic hydrocarbons such as xylene), halogenated hydrocarbons (dichloromethane, chloroform, chlorobenzene, etc.), ethers (chain ethers such as dimethyl ether and diethyl ether; cyclic ethers such as dioxane and tetrahydrofuran), Carbitols (such as C _1-4 alkyl carbitol such as methyl carbitol), cellosolves (such as C _1-4 alkyl cellosolv such as methyl cellosolve), ketones (chain ketones such as acetone and methyl ethyl ketone) Ring such as cyclohexanone Such ketones), esters (methyl acetate, ethyl acetate, butyl acetate), amides (formamide; N- methylformamide, N, N- mono- or _{di-C 1-4} alkyl formamide such as N- dimethylformamide; N -N-mono or di-C _1-4 alkylacetamide such as methylacetamide, N, N-dimethylacetamide), nitriles (acetonitrile, propionitrile, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N- Methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), sulfoxides (dimethyl sulfoxide, etc.) and the like may be used. These solvents can be used alone or as a mixed solvent. The polymerizable composition may be an organic solvent solution or an aqueous composition (aqueous solution, aqueous dispersion).

  The proportion of the solvent is 0.1 to 200 parts by weight (for example, 1 to 200 parts by weight with respect to 1 part by weight in total of the aromatic carbonyl compound and the aromatic reaction component (aromatic polyamine and / or aromatic heterocyclic compound)). 200 parts by weight, preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight), for example, 1 to 40 parts by weight (eg 1 to 35 parts by weight), preferably 3 to 20 parts by weight. It may be about 5 to 10 parts by weight, more preferably about 5 to 10 parts by weight.

  A conductive polymer obtained from a composition containing an aromatic polycarbonyl compound and an aromatic polyamine is a π-electron conjugated unit (for example, a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond). , An amide bond, an imidazole ring, an oxazole ring, a thiazole ring, or the like). The conductive polymer usually contains a unit (repeating unit or crosslinking unit) represented by the following formula (IV-1) or (IV-2).

^(Wherein, A 5 to A ⁷ represents an aromatic ring, X is shows a nitrogen atom, an oxygen atom or a sulfur atom)
Examples of the aromatic ring A ⁵ (the aromatic ring derived from the aromatic polycarbonyl compound) and the aromatic rings A ^{6 to} A ⁷ (the aromatic ring derived from the aromatic polyamine) include the same aromatic rings as the ring A.

In formula (IV-1) or (IV-2), for the sake of convenience, a single bond extending outwardly from ring A ⁵ and each of ring A ⁶ and / or ring A ⁷ is shown. A plurality of bonds extend from at least one ring selected from ring A ⁵ and ring A ⁶ or ring A ⁷ to form a three-dimensional bridge structure.

  A conductive polymer obtained from a composition containing an aromatic aldehyde compound and an aromatic heterocyclic compound is bonded via a π-electron conjugated unit (for example, a carbon-carbon single bond, a carbon-carbon double bond, etc.). And having a structure in which a plurality of aromatic rings are connected. The conductive polymer usually contains a unit (repeating unit or crosslinking unit) represented by the following formula (IV-3) or (IV-4). A preferred repeating unit or crosslinking unit includes at least a unit represented by the formula (IV-4).

(Wherein A ⁵ , Het, X, R ⁵ , r and p2 are the same as above)
As the aromatic ring A ⁵ (aromatic ring derived from an aromatic aldehyde compound), the same aromatic ring as ring A can be exemplified, and as the aromatic heterocyclic ring represented by Het, X is a sulfur atom, oxygen atom or nitrogen Examples thereof include monocyclic, fused ring, and ring assembly heterocycles containing a 5-membered ring that is an atom.

  Similar to the relationship between the compound represented by the formula (IIIc) and the compound represented by the formula (IIId), the compound represented by the formula (IV-3) is subjected to a dehydrogenation reaction to give the formula (IV -4) can be obtained.

  The conductive polymer produced by the crosslinkable composition is a single polymer because the reaction between the carbonyl group-containing group and the amino group and the reaction between the formyl group and the α-carbon moiety of the heterocyclic compound easily proceed. It can be estimated that. For this reason, it is considered that aggregation can occur and recombination of electrons can be suppressed as in the case of a low molecular dye, and electron mobility (hopping) between molecules can be substantially not generated, and electron mobility can be improved.

  The conductive polymer may have any characteristics of an n-type semiconductor, a p-type semiconductor, and an intrinsic semiconductor. Usually, a conductive polymer exhibiting p-type semiconductor characteristics is used in combination with inorganic particles exhibiting n-type semiconductor characteristics.

  The surface resistivity of the conductive polymer is not particularly limited, and is, for example, 10Ω / □ or less (for example, 1 to 10Ω / □), preferably 3 to 9Ω / □, and more preferably about 4 to 8Ω / □. May be. The surface resistivity can be measured using a conventional resistivity meter.

  As described above, the conductive polymer contained in the photoelectric conversion layer functions as a sensitizer and / or a charge transport agent that can photoexcite inorganic particles. Therefore, the photoelectric conversion layer contains other sensitizers [low molecular organic dyes (such as dyes having a complex structure such as ruthenium complex dyes)], other charge transfer agents [electrolyte (iodine and metal iodide salts and Etc.) etc.] may not be substantially contained. That is, a sensitizer composed of a conductive polymer has less exciton binding caused by light absorption than a low-molecular complex dye, and can easily perform charge separation. In addition, charge transport agents composed of conductive polymers have no problems such as volatilization or leakage like electrolytes, and are stable (high reliability) and safe without deterioration in performance over time. Despite its molecular type, it has low resistance and high carrier mobility.

  The band gap of the sensitizer composed of the conductive polymer is not particularly limited, and is, for example, 3.2 eV or less (for example, 0.7 to 3 eV), preferably 1 to 2.9 eV (for example, 1.2). ˜2.7 eV), more preferably about 1.5 to 2.5 eV. The band gap can be measured by a conventional method, for example, a UV-Vis spectrum.

  Thus, the photoelectric conversion layer is composed of inorganic particles capable of photoelectric conversion and a conductive polymer having a three-dimensional network structure substantially composed entirely of π-conjugated system (in particular, as a sensitizer and / or a charge transport agent). A conductive polymer) and a photoelectric conversion composition.

  A typical photoelectric conversion layer is laminated (or formed) on at least one surface of a porous layer (or inorganic semiconductor layer) containing inorganic particles capable of photoelectric conversion, and substantially entirely. and an organic semiconductor layer (or charge transport layer) containing a conductive polymer having a three-dimensional network structure composed of a π-conjugated system.

  The thickness (average thickness) of the photoelectric conversion layer may be, for example, about 5 to 300 μm, preferably about 10 to 100 μm, and more preferably about 20 to 50 μm.

  The solar cell is not particularly limited as long as it includes a conductive transparent substrate and a photoelectric conversion layer, and an arbitrary layer may be further laminated. Examples of the optional layer include a conductive substrate, an insulating layer, and a protective layer. These arbitrary layers may be laminated alone or in combination of two or more.

  The conductive substrate may be a substrate that exhibits conductivity as a whole (conductive layer alone), and at least one surface is a substrate that exhibits conductivity (the base substrate and the base substrate are laminated on at least one surface of the base substrate). A laminate with a conductive layer) may be used. As the conductive layer, in addition to the transparent conductive layer exemplified in the section of the conductive transparent substrate, metal (platinum, gold, silver, copper, aluminum, etc.), carbon material (graphite, carbon black, carbon nanotube, fullerene, activated carbon, Examples thereof include a conductive layer composed of hard carbon spheres and the like. Examples of the base substrate include the base substrate exemplified in the section of the conductive transparent substrate. In addition, a conductive substrate is normally laminated | stacked on a photoelectric converting layer, and is utilized as a counter electrode (or cathode) of the transparent electrode (or anode) comprised with the conductive transparent substrate.

  The solar cell of the present invention does not necessarily require a sealing material because an electrolytic solution is substantially unnecessary, but the peripheral portion may be sealed with a sealing material. The sealing material may be an organic sealing material (such as ethylene-vinyl acetate copolymer) or an inorganic sealing material (such as glass, metal, or silicon nitride).

  FIG. 2 is a schematic view showing an example of the solar cell of the present invention. In this example, the transparent electrode (anode) in which the transparent substrate 1 and the transparent conductive layer 2 are sequentially stacked, and the inorganic particles 3 and the conductive polymer (which are stacked on the transparent conductive layer 2 of the photoelectrode and can be photoelectrically converted) A photoelectric conversion layer including a sensitizer 4 and a charge transport agent 5) and a counter electrode (cathode) 8 laminated on the photoelectric conversion layer are provided, and a peripheral portion is sealed with a sealant 6. . In such a solar cell, when light is incident, the conductive polymer is in an excited state to generate excitons, and when the excitons reach the interface between the conductive polymer and the inorganic particles 3, charge separation easily occurs and electrons Moves to the transparent electrode through the inorganic particles 3, and holes move to the counter electrode to generate an electromotive force, whereby a current flows.

[Method for manufacturing solar cell]
The solar cell can be produced by a conventional method, for example, by applying a photoelectric conversion composition to at least one surface of a conductive transparent substrate to form a photoelectric conversion layer. This method usually involves applying a paste containing inorganic particles to at least one surface of a conductive transparent substrate, and applying a high conductivity to the coating film (porous layer or inorganic semiconductor layer) obtained in this step. Applying a composition containing molecules (sensitizer and charge transport agent) [or a composition for forming a conductive polymer (sensitizer and charge transport agent)].

  The application process of the paste containing inorganic particles includes metal oxide particles when, for example, (i) the conductive transparent substrate is a laminate of a glass plate and a transparent conductive layer, depending on the type of the conductive transparent substrate. It may be a step of applying paste, drying and firing (high temperature firing method), and (ii) when the conductive transparent substrate is a laminate of a transparent resin film and a transparent conductive layer, metal oxide particles and metal It may be a step of applying a paste containing alkoxide, drying and irradiating with ultraviolet rays (low temperature baking method).

  The paste usually contains a dispersion medium. In the method (i), the dispersion medium may be an aqueous medium such as water, alcohols (methanol, ethanol, isopropyl alcohol, etc.), ethers (dimethyl ether, diethyl ether, etc.), carbitols (methyl carbitol, etc.), Examples include cellosolves (such as methyl cellosolve), ketones (such as acetone), amides (such as dimethylformamide), and mixed solvents thereof. In the method (ii), examples of the dispersion medium include hydrocarbons (such as aromatic hydrocarbons such as toluene), the alcohols, the ketones, the amides, and mixed solvents thereof.

  The ratio of the dispersion medium is, for example, about 50 to 1000 parts by weight, preferably about 100 to 500 parts by weight, and more preferably about 200 to 400 parts by weight with respect to 100 parts by weight of the metal oxide particles.

  The paste may contain any additive as necessary, for example, a dispersant [organic acid (such as acetic acid), inorganic acid (such as hydrochloric acid or nitric acid), acetylacetone, etc.], surfactant [nonionic surfactant (octylphenoxypolyethoxy). Ethanol etc.)], thickeners [polyethylene glycol, polysaccharides (methylcellulose etc.) etc.], antifoaming agents and the like. These additives can be used alone or in combination of two or more.

The coating method is not particularly limited, and examples thereof include a spin coating method, a doctor blade method, a screen printing method, a gravure printing method, and a squeegee method. The coating amount (coating amount after drying) is, for example, 0.5 to 50 g / ^{m 2,} preferably from 1 to 30 g / ^{m 2} approximately.

  In the method (i), drying and firing may be performed in the air or in an inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere. Drying may be performed at the same time as firing at the firing temperature from the viewpoint of reducing the number of steps, and from the point of preventing long-time heat treatment at a high temperature, the drying is performed at a temperature lower than the firing temperature (for example, 50 to 150 ° C., It may be performed prior to firing at preferably 60 to 100 ° C., more preferably about 70 to 90 ° C.). The drying time can be appropriately selected depending on the drying temperature, and is, for example, 10 seconds to 1 hour, preferably 30 seconds to 30 minutes, and more preferably about 1 to 10 minutes. As a calcination temperature, it is about 300-600 degreeC, for example, Preferably it is 350-550 degreeC, More preferably, it is about 400-500 degreeC. The firing time can be appropriately selected according to the firing temperature, and is, for example, 10 seconds to 12 hours, preferably 30 seconds to 5 hours, and more preferably about 1 minute to 2 hours. If the firing time is too short, the connection between the particles will be insufficient and electrons will not flow easily.If the firing time is too long, the particles will be fused together, reducing the effective surface area and reducing the amount of sensitizer adsorbed. Cheap.

  In the method (ii), drying is usually performed at a temperature lower than the glass transition temperature of the transparent resin (for example, about 20 to 100 ° C.) for about 10 seconds to 1 hour (for example, 20 seconds to 30 minutes). Ultraviolet irradiation is performed to remove impurity organic substances from the metal oxide particles, and the ultraviolet irradiation is often performed in an oxygen atmosphere.

Physical properties of the porous layer obtained by coating step of a paste containing inorganic particles is not particularly limited, for example, the specific surface area of the porous layer, for example, 5 to 300 m ² / g, preferably 10 to 200 m ² / g It may be a degree. If the specific surface area is too small, the sensitizer cannot be sufficiently adsorbed, and even if the specific surface area is too large, the pore diameter becomes narrow and the sensitizer cannot be adsorbed. The specific surface area can be measured by a conventional method such as a nitrogen gas adsorption method.

  The surface area of the porous layer may be about 500 to 3000 times (for example, 800 to 2000 times, preferably 1000 to 1500 times) the apparent surface area (area projected in the thickness direction).

  The arithmetic average roughness (Ra) of the porous layer is, for example, about 50 nm to 1 μm, preferably 80 to 800 nm, and more preferably about 100 to 500 nm in accordance with JIS B0601.

  The thickness (average thickness) of the porous layer is, for example, about 0.1 to 100 μm (for example, 0.5 to 70 μm), preferably 1 to 50 μm (for example, 5 to 30 μm), and more preferably about 10 to 20 μm. May be.

  A composition containing a conductive polymer (sensitizer and charge transport agent) may be applied to the porous layer, but usually a conductive polymer (sensitizer and charge transport agent) is formed on the porous layer. The composition (the crosslinkable composition or the polymerizable composition) is applied and heat-treated (crosslinked or polymerized). The latter method is excellent in productivity in that the charge transport layer can be formed at the same time as the sensitizer is contained (or adsorbed) in the porous layer.

  Examples of the application method of the composition include conventional application methods such as an air knife coating method, a roll coating method, a gravure coating method, a blade coating method, a dip coating method, a spray method, a spin coating method, and an inkjet printing method. it can. After application, the solvent is usually removed from the coating film by drying. The thickness (thickness after drying) of the coating film (charge transport layer or organic semiconductor layer) is, for example, about 1 to 200 μm, preferably about 10 to 100 μm.

  The heat treatment (polymerization or crosslinking) may be performed in air or in an inert gas (nitrogen gas or the like) atmosphere. The heat treatment temperature may be, for example, 50 to 500 ° C. (for example, 150 to 500 ° C.), preferably 100 to 400 ° C. (for example, 200 to 400 ° C.), and more preferably about 150 to 300 ° C. It may be about 350 ° C. The heat treatment time may be, for example, about 0.1 to 2.5 hours, preferably about 0.2 to 2 hours, and more preferably about 0.3 to 1.5 hours.

  In the case of a composition containing an aromatic aldehyde compound and an aromatic heterocyclic compound, as described above, a unit (or a crosslinking unit) represented by the formula (IV-3) is generated, and this formula (IV The unit represented by -3) can be converted into a unit represented by the formula (IV-4) (or a crosslinking unit) by a dehydrogenation reaction. As the dehydrogenation reaction, for example, a photodehydrogenation method of irradiating actinic rays such as a mercury lamp or a xenon lamp may be used. There are many cases. In addition, when a composition containing an acid catalyst is used, a dehydrogenation reaction can be easily performed.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Conductivity]
After casting the composition for forming the conductive polymer of the example on a glass plate, an organic semiconductor film was produced by heat-treating under a nitrogen atmosphere under the same conditions as in the example. The surface resistivity was measured using “MCP-HT450” manufactured by Kagaku Corporation.

[Absorption spectrum and band gap]
After casting the composition for forming the conductive polymer of the example on the glass plate, an organic semiconductor film was prepared by heat treatment under the same conditions as in the example under a nitrogen atmosphere, and UV-Vis spectrum measurement was performed. (Manufactured by Hitachi High-Technologies Corporation, “Spectrophotometer U-3900H”) was performed to obtain an absorption spectrum. The band gap was calculated from the absorption edge of the absorption spectrum.

[Battery characteristics evaluation]
The dye-sensitized solar cells produced in the examples were evaluated under conditions of AM 1.5, 100 mW / cm ² and 25 ° C. using a solar simulator (“XES-301S + EL-100” manufactured by Mitsunaga Electric Co., Ltd.). did.

Example 1
(1) Production of porous titanium oxide electrode An acetic acid aqueous solution containing 1 g of titanium oxide particles (manufactured by Daicel Corporation, rutile crystal) in an agate mortar and 0.5% by weight of methylcellulose (manufactured by Tokyo Chemical Industry Co., Ltd.) (PH 3) 3 ml was added little by little and mixed for 30 minutes to obtain a titanium oxide paste.

The obtained titanium oxide paste was applied to the ITO layer side of a glass substrate with ITO (Luminescence Technology, size 25 mm × 25 mm, ITO layer thickness 0.14 μm) by a squeegee method and dried at 80 ° C. for several minutes. Thereafter, a heat treatment was performed at 450 ° C. for 1 hour to form a porous layer having a thickness of 10 μm to obtain a porous titanium oxide electrode (apparent area 0.25 cm ² ).

(2) Preparation of composition for forming conductive polymer (sensitizer and charge transport agent) Tris (4-formylphenyl) amine 10 mg, 2,2 ′: 5 ′, 2 ″ − in a 6 ml sample bottle Terthiophene (4.4 mg) and p-toluenesulfonic acid monohydrate (7.2 mg) were added and dissolved in 1,4-dioxane (1453.3 mg). Was prepared.

(3) Production of photoelectric conversion layer After casting the composition obtained in (2) to the porous titanium oxide electrode obtained in (1), the conductive layer was subjected to heat treatment at 120 ° C. for 1 hour in a nitrogen atmosphere. A conductive polymer (thickness 10 μm) was formed to form a photoelectric conversion layer. The conductivity of the conductive polymer was 6.6 × 10 ⁴ Ω / □, and the band gap was 1.8 eV.

(4) Production of solar cell A solar cell was obtained by vacuum-depositing an aluminum electrode on the photoelectric conversion layer obtained in (3).

Example 2
(1) Production of porous titanium oxide electrode A porous titanium oxide electrode was obtained in the same manner as in Example 1.

(2) Preparation of composition for forming conductive polymer (sensitizer and charge transfer agent) 1,3,5-triformylbenzene (manufactured by Nard Laboratories) 16.2 mg in a 6 ml sample bottle And 29.0 mg of tris (4-aminophenyl) amine were dissolved in 860 mg of N, N-dimethylacetamide. The solution was filtered through a filter having a pore size of 0.2 μm to prepare a composition.

(3) Production of photoelectric conversion layer After casting the composition obtained in (2) on the porous titanium oxide electrode obtained in (1), the conductive layer was subjected to heat treatment at 300 ° C. for 1 hour in a nitrogen atmosphere. A conductive polymer (thickness 10 μm) was formed to produce a photoelectric conversion layer. The conductivity of the conductive polymer was 8.0 × 10 ¹⁰ Ω / □, and the band gap was 2.7 eV.

(4) Production of solar cell A solar cell was obtained by vacuum-depositing an aluminum electrode on the photoelectric conversion layer obtained in (3).

Example 3
(1) Production of porous titanium oxide electrode A porous titanium oxide electrode was obtained in the same manner as in Example 1.

(2) Preparation of composition for forming conductive polymer (sensitizer and charge transfer agent) 16.5 mg of tris (4-formylphenyl) amine and 2,2′-bis (trifluoro) in a 6 ml sample bottle 16.5 mg of methyl) benzidine was added and dissolved in 1350 mg of cyclohexanone. This liquid was filtered through a filter having a pore size of 0.2 μm to prepare a composition (coating composition).

(3) Production of photoelectric conversion layer After casting the composition obtained in (2) on the porous titanium oxide electrode obtained in (1), the conductive layer was subjected to heat treatment at 300 ° C. for 1 hour in a nitrogen atmosphere. A conductive polymer (thickness 10 μm) was formed to produce a photoelectric conversion layer. The conductivity of the conductive polymer was 4.2 × 10 ⁵ Ω / □, and the band gap was 2.7 eV.

(4) Production of solar cell A solar cell was obtained by vacuum-depositing an aluminum electrode on the photoelectric conversion layer obtained in (3).

  The output characteristics of the solar cells of Examples 1 to 3 are shown in FIG. As can be seen from FIG. 3, in Examples 1 to 3, the photoelectric conversion rate is excellent. Moreover, the absorption spectrum of the conductive polymer of Examples 1-3 is shown in FIG. When an aromatic heterocyclic compound is used as a polymerization component as in Example 1, a conductive polymer having absorption on a relatively long wavelength side can be obtained, so that the photoelectric conversion rate can be improved. In addition, by adding a functional group having a large steric hindrance such as a trifluoromethyl group as in Example 3, the band gap can be increased, and a solar cell having relatively excellent transparency can be obtained. As can be seen from FIG. 4, the absorption spectrum can be appropriately adjusted by changing the type and ratio of the polymerization component of the conductive polymer.

  Since the conductive polymer of the present invention can exhibit a function as a sensitizer and / or a charge transport agent, it is suitably used as a material for solar cells [photosensitized solar cells (all solid photosensitized solar cells, etc.)]. Available. In addition, the absorption spectrum can be easily controlled simply by adjusting the type and proportion of the polymer component (or reaction component) of the conductive polymer, so it can be adjusted to the emission spectrum of various light sources (sunlight, fluorescent lamps, etc.). A solar cell that can be optimized and exhibits a high photoelectric conversion rate can be provided.

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 2 ... Transparent conductive layer 3 ... Inorganic particle 4 ... Sensitizing dye (sensitizer)
5 ... Electrolytic solution (charge transport agent)
6 ... Sealing material 7 ... Catalyst layer 8 ... Counter electrode

Claims (17)

  A solar cell comprising a conductive transparent substrate and a photoelectric conversion layer laminated on at least one surface of the conductive transparent substrate, wherein the photoelectric conversion layer is substantially entirely composed of inorganic particles capable of photoelectric conversion. A solar cell comprising a conductive polymer having a three-dimensional network structure composed of a π-conjugated system.   A solar cell comprising a conductive transparent substrate and a photoelectric conversion layer laminated on at least one surface of the conductive transparent substrate, wherein the photoelectric conversion layer photoexcites the inorganic particles capable of photoelectric conversion, and the inorganic particles A sensitizer and a charge transport agent, and the sensitizer and / or the charge transport agent is a conductive polymer having a three-dimensional network structure substantially consisting of a π-conjugated system. Solar cell made up.   The conductive polymer is at least one selected from carbon-carbon single bond, carbon-carbon double bond, carbon-carbon triple bond, carbon-nitrogen double bond, amide bond, imidazole ring, oxazole ring and thiazole ring. The solar cell according to claim 1, wherein the solar cell is a polymer in which a plurality of aromatic rings are three-dimensionally connected through a unit. The conductive polymer is formed of a crosslinkable composition, and the crosslinkable composition comprises an aromatic carbonyl compound having one or more carbonyl groups as a reaction site and a plurality of amino groups as a reaction site. An aromatic polyamine having at least one aromatic reaction component selected from an aromatic heterocyclic compound having a plurality of unmodified α-carbon positions adjacent to the hetero atom of the heterocyclic ring and having a plurality of unmodified α-carbon positions as a reactive site. ,
When the aromatic reaction component is an aromatic polyamine, the aromatic carbonyl compound is an aromatic polycarbonyl compound having a plurality of carbonyl groups as reaction sites, and the aromatic polycarbonyl compound and the aromatic polyamine Among them, at least one component has 3 or more reaction sites,
When the aromatic reaction component is an aromatic heterocyclic compound, the aromatic carbonyl compound is an aromatic aldehyde compound having one or more formyl groups as a reaction site, and formyl of the aromatic aldehyde compound When the number of groups is “T” and the number of unmodified α-carbon positions of the aromatic heterocyclic compound is “U”, T ≧ 2 and / or U ≧ 3 is satisfied,
When the aromatic reaction component is a combination of an aromatic polyamine and an aromatic heterocyclic compound, the aromatic carbonyl compound is an aromatic polyaldehyde compound having a plurality of formyl groups as reaction sites. 4. The solar cell according to any one of 3. The aromatic carbonyl compound is represented by the following formula (Ia)
(In the formula, L represents a linker, A represents an aromatic ring, R ¹ represents a carbonyl group-containing group, R ² represents a non-reactive group, n is 0 or 1, and k1 is 1 or more. An integer, k2 is 0 or an integer of 1 or more, p is 1 when n is 0, and p is an integer of 2 or more when n is 1)
The solar cell according to claim 4, which is a compound represented by the formula: In the formula (Ia), the aromatic carbonyl compound is
(A1) Ring A is a monocyclic or condensed bi- to heptacyclic aromatic hydrocarbon ring, monocyclic or condensed bi- to heptacyclic aromatic heterocycle, porphyrin ring or phthalocyanine ring, n is 0, k1 Or a compound in which p is 1, or (a2) ring A is monocyclic or condensed bi- to heptacyclic aromatic hydrocarbon ring, or monocyclic or condensed bi- to heptacyclic aromatic heterocycle The linker L is a direct bond, a nitrogen atom, an oxygen atom, a sulfur atom, a vinylene group, a 2- to 4-valent aromatic ring group, a 2- to 4-valent aromatic ring assembly group, or a combination thereof; The solar cell according to claim 5, wherein k 1 is 1 or 2, and p is 2 to 4. The aromatic polyamine has the following formula (IIa)
(Wherein R ³ represents an amino group, R ⁴ represents a hydrogen atom, an amino group, a mercapto group or a hydroxyl group, k3 is an integer of 1 or more, and L, n, A, R ² , k2 and p Is the same as above, except that when n is 0, k3 is an integer of 2 or more.)
The solar cell according to claim 4, wherein the solar cell is a compound represented by the formula: Aromatic polyamines in formula (IIa)
(B1) Ring A is a monocyclic or condensed bi to heptacyclic aromatic hydrocarbon ring, monocyclic or condensed bi to heptacyclic aromatic heterocycle, porphyrin ring or phthalocyanine ring, n is 0, k3 Or a compound in which p is 1, or (b2) ring A is a monocyclic or condensed bi- to heptacyclic aromatic hydrocarbon ring, and linker L is a direct bond, nitrogen atom, oxygen atom, A compound having a sulfur atom, a diazo group, a disulfide group, a vinylene group, a divalent to tetravalent aromatic ring group, or a combination thereof, n is 1, k3 is 1 or 2, and p is 2 to 4. The solar cell according to claim 7.   The aromatic heterocyclic compound is at least one selected from a monocyclic compound, a condensed cyclic compound and a ring assembly compound, and as a hetero atom of the heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom or an imino group, The solar cell according to any one of claims 4 to 8, comprising a 5- to 8-membered aromatic heterocycle having at least one heteroatom selected from selenium atoms. The aromatic heterocyclic compound is represented by the following formula (III)
(In the formula, Het represents an aromatic heterocyclic ring, X represents a hetero atom, R ⁵ represents a non-reactive group, r represents an integer of 0 to 3, and L, n and p are the same as above. )
The solar cell according to claim 4, wherein the solar cell is a compound represented by the formula: A crosslinkable composition comprises an aromatic polyaldehyde compound having 2 to 4 formyl groups as a reactive site in one molecule and an aromatic polyamine having 2 to 4 amino groups as a reactive site in one molecule. The aromatic polyaldehyde compound and the aromatic polyamine at least one component is a composition having 3 or more reactive sites, or an aromatic having 2 to 4 formyl groups as reactive sites in one molecule Composition comprising an aromatic polyaldehyde compound and an aromatic heterocyclic compound adjacent to a heteroatom of a heterocyclic ring and having 2 to 8 unmodified α-carbon positions as a reaction site in one molecule The solar cell in any one of Claims 4-10.   The inorganic particles are composed of at least one metal oxide selected from calcium titanate, strontium titanate, barium titanate, titanium oxide, zirconium oxide, niobium oxide, tantalum oxide, tungsten oxide, zinc oxide, and tin oxide. The solar cell according to claim 1.   The solar cell according to any one of claims 1 to 12, wherein the inorganic particles are composed of titanium oxide.   A sensitizer for photoexciting photoelectrically convertible inorganic particles, which is composed of a conductive polymer having a three-dimensional network structure substantially entirely composed of a π-conjugated system.   A photoelectric conversion composition comprising photoelectrically convertible inorganic particles and a conductive polymer having a three-dimensional network structure substantially entirely composed of a π-conjugated system.   A photoelectric conversion composition comprising photoelectrically convertible inorganic particles, a sensitizer for photoexciting the inorganic particles, and a charge transport agent, wherein the sensitizer and / or the charge transport agent is substantially A photoelectric conversion composition comprising a conductive polymer having a three-dimensional network structure entirely composed of a π-conjugated system.   The process of apply | coating the paste containing the inorganic particle which can be photoelectrically converted to at least one surface of an electroconductive transparent substrate, and the crosslinkable composition in any one of Claims 4-11 to the coating film obtained at this process The manufacturing method of the solar cell including the process of apply | coating and heat-treating.