TW200404833A - Dendritic polymer and electronic device element employing the polymer - Google Patents

Abstract

The invention provides a novel dendritic polymer serving as an organic semiconductor material which has high solubility in organic solvent; which is stable (i.e., is not prone to being affected by external inhibitors such as oxygen and water); and which exhibits isotropic, remarkably high carrier conductivity. The invention also provides electronic device elements requiring carrier conductivity and having remarkably high carrier conductivity through a simple production process. The dendritic polymer having a branching structure including a repeating unit having a branch portion, wherein the polymer has an aromatic amine moiety at an end thereof, and the repeating unit is formed of a phenylenevinylene moiety represented by formula (1): which is repeated once or a plurality of times.

Description

200404833 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a novel dendrimer with a carrier conductivity, a dendrimer or a highly branched polymer, and an electronic device using the dendrimer. The dendrimer of the present invention achieves high carrier conductivity with a relatively high efficiency, so it is particularly useful in devices requiring carrier conductivity; for example, switching elements such as electromechanical crystals (organic FETs, organic TFTs, etc.), Solar cells and organic EL devices. [Previous technology] Since the late 1970s, conductive organic polymers have become scientifically and technically interesting. Polymers based on fairly new technologies exhibit the electronic and magnetic properties of metals as well as the physical and mechanical properties of conventional organic polymers. Known conductive organic polymers include poly (p-phenylene) compounds, poly (p-phenylene vinylene) compounds, polyaniline, polythiophene, polyisocyanate, polyacrylidine, polyoctane , Poly (p ο 1 yce η 〇phenes), poly (p-phenylene sulfide) compounds and mixtures thereof, blends thereof with another polymer, and copolymers of monomers of the above polymers. These conductive organic polymers are conjugated system polymers that exhibit conductivity through doping (caused by reactions such as oxidation, reduction, or protonation reactions). In recent years, efforts have been made to produce light-emitting elements of organic electroluminescence devices (organic EL, OLED) and field-effect transistors (organic F E T, organic T F T) from these conductive organic polymers. The current embodiment uses an expensive plasma CVD device to form an insulating layer or a semiconductor layer of amorphous silicon TFT or polycrystalline silicon and an electrode using an expensive sputtering device. In addition, film formation can be performed by CVD at 6 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 up to 2 30 to 3 50 ° C, and maintenance operations must be performed frequently (such as cleaning ) To reduce throughput. In comparison, coating devices or inkjet devices for manufacturing organic FETs or similar devices are cheaper than CVD devices and sputtering devices. In addition, film formation can be performed at a lower temperature, and device maintenance is less troublesome. Therefore, when a display device such as a liquid crystal display and an organic EL is made of an organic FET, a significant cost reduction can be expected. A typical EL device includes a transparent substrate made of, for example, a glass material, a hole injection layer, a hole transmission layer, Light-emitting layer, electron-transport layer, and metal electrode. Three separate layers, namely a hole transport layer, a light emitting layer, and an electron transport layer, can form a single hole transport and light emitting layer or a single electron transport and light emitting layer. Its characteristics are disclosed in Japanese Patent Application Publication No. (kokai) Nos. 7-1 2 6 6 1 6, 8-18125, 1 0 _ 9 2 5 7 6 and the like. However, issues such as lifetime are still unsolved (in the case of organic EL devices), and research on improvements is ongoing. A typical organic T F T s includes a transparent substrate made of, for example, a glass material, a gate substrate, a gate insulating film, a source, a drain, and an organic semiconductor film. By modifying the gate voltage, the charge at the interface between the gate insulating layer and the organic semiconductor film becomes excessive or insufficient. Therefore, the drain current flowing between the source and the drain is changed through the organic semiconductor film to perform switching. Japanese Patent Application Laid-Open (kokai) No. 6 3-0 7 6 3 8 discloses organic TF based on polythiophene or a polythiophene derivative suitable as the organic semiconductor film. Methods for preparing organic TFTs from pentacene are disclosed in Yen-Yi Lin, David J. Gundlach, Shelby F. Nelson 7 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 and Tomas N. Jackson, IEEE Transaction and Electron Device, Volume 44, No. 8, page 1,325 (1997). However, the use of pentacene creates problems. For example, film formation can be performed by a gas deposition method, and the degree of crystallinity must be increased to improve device properties. Another possibility is to use soluble pentacene derivatives to increase the possibilities. However, in this case, these properties are still unsatisfactory. The applicability and development of organic semiconductors formed from polyfluorene, polyfluorene derivatives, or sigmathiophene oligomers are in progress, because organic semiconductors have excellent moldability, such as easy to undergo electrolytic polymerization, Coating or the like is formed into a thin film. However, in this case, these properties are still not satisfactory. At the same time, in recent years, highly branched polymer materials (dendrimers and high branched polymers in a broad sense) have become interesting. The characteristics of dendrimers and highly branched polymers include non-crystallinity, solubility in organic solvents, and the presence of a large number of branched ends that can introduce functional groups. LL Miller et al., J. Am. Chem. Soc. 1997, 119, 1,005 disclose a branched terminal having 1,4, 5, 8-naphthalenetetracarboxylic acid-diamidino group residues (bound to Polyammonium dendrimers with quaternary ammonium salt) have isotropic electron conductivity (also known as "transportability"), and the conductivity is interacted by π-electrons (generated by the spatial overlap of the end portions of the branches) Function provided. Japanese Patent Laid-open Application (kokai) No. 20000-3 3 6 1 7 1 discloses a dendrimer, which contains a dendrite (on a branch end) with a hole conducting portion and no A π-electron conjugate system of a carbonyl group and a benzene ring, and a photoelectric conversion device using the dendrimer is disclosed. 8 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 It has been studied to apply a dendrimer having a high fluorescence yield to a light-emitting element. Publications (Let Halim, Jonathan N. G. Pillow, If or D. WL Burn, Adv. Mater. 1 9 9 9, 11, No. 5, Lupton, Ifor DW Samuel, Richard Beav L. Burn, Heinz Bassler , A d v. Mater. 2 0 0 1 2 5 8; W 0 9 9 2 1 9 3 5; and W 0 1 5 9 0 3 0) Reveal the introduction of phenylene and vinylene-based dendrimers High solubility of dendrimer. These publications disclose that solubility and processability can be provided to the dendrimer through terminal substituents. The introduction of terminal carrier conductive functional groups is not mentioned. Org. Volume 3, No. 17, 2645 (Jose L. Segura, R Nazario Martin, and Dirk M. Guldi) Reveals Groups and Shows Increased Solubility (via Introduction of Long-Chain Burning; i-based Vinyl-Based In the meantime, in addition to polymers, low molecular weight compounds having an arylamine moiety and a vinyl moiety are used organically as shown in Japanese Patent Laid-Open Application (kokai) No. 0 3 -06-271848 No. and Japanese Patent No. 3093796B, etc.) However, in the use of semiconductors or conductive polymers (such as female functional elements, the charge conduction chain of the above organic semiconductors appears oriented and depends on the molecular structure change. In addition, traditional polymers have been The tendency of the influence of oxygen and water makes it easy to do so. The conventional organic FET element has disadvantages, namely, bad 312 / Invention Specification (Supplement) / 92-11 / 92123418 vinyl part 丨 J such as Μ〇unir Samuel, Paul 373; John M. ington, Paul, 1 3, No. 4, with a tertiary tertiary molecule, which is enhanced by the introduction of a suitable polymer, but Lett. 2001, afae 1 Gomez, a terminal dibutylamine k group In the capped phenylene EL element (Jie-296595 and 03 polymer), the properties are along the molecule, and these conjugated systems cause deterioration. Due to its stability and electrical properties, it has a short life span. In addition, semiconductors or conductive polymers (such as conjugated polymers) are often hard and cannot be dissolved or melted. Most of them cannot be dissolved in solvents. To achieve this, derivatives and oligomers introduced into these polymers with side chains are used (see Japanese Patent Laid-Open Application (kokai) No. 4- 1 3 3 3 5 1, 6 3-0 7 6 3 7 8, 5-1 1 0 0 6 9 etc.). However, problems still arise. For example, when a side chain is introduced, a glass transition temperature occurs and induces thermochromism that contributes to micro-Brownian motion, thereby causing a characteristic that depends on temperature changes. The use of agglomerates may reduce reliability. Even when using a polymer introduced with a side chain, satisfactory mobility cannot be achieved. Therefore, the degree of polymerization must be increased, or the degree of orientation of conductive organic compounds can be increased by using an alignment film (for example, Japanese Patent Laid-Open Application (kokai) No. 7-2 0 6 5 9 9). In the case where an alkyl group is not introduced into the end of the dendrimer having the phenylene and vinylidene part, the solution of the dendrimer is not easy due to the poor solubility of these dendrimers in an organic solvent. be made of. Another problem is the difficulty in synthesizing or purifying higher generation dendrimers. At this time, when the long-chain alkyl group is introduced into the end of the dendrimer, a problem similar to that of the above-mentioned polymer derivative with a side chain will be generated, that is, the resulting polymer has a glass transition temperature. When low molecular weight compounds are used, problems with temperature-dependent physical properties arise because their glass transition temperatures are lower than the glass transition temperature of polymers. Furthermore, when these or compounds are used as the organic semiconductor material, the carrier mobility reaches a low level unsuitable for practical use. 10 31W Invention Specification (Supplement) / 92-11 / 92123418 200404833 [Summary of the Invention] In order to solve the problems generated in the conventional techniques described above, the present invention is proposed. Therefore, the object of the present invention is to provide a dendrimer suitable as an organic semiconductor material, which has high solubility in organic solvents; it is stable (that is, it is not easily affected by external inhibitors such as oxygen and water); and Exhibits isotropic, very high carrier conductivity. Another object of the present invention is to provide an electronic device using the dendrimer. The inventors of the present case have conducted extensive research to solve the above problems, and have found that by introducing an aromatic amine moiety to the end of a dendrimer (which is formed by phenylene and vinylidene as a dendritic structure), the polymer is in an organic solvent. Increased solubility; hole conductivity is provided at the end of the polymer; and the main chain of phenylene and vinylene contained in the polymer molecule is protected by the aromatic amine main chain as the molecular surface, making it stable in the air and An organic semiconductor material that exhibits isotropic, very high carrier conductivity. The present invention has been achieved based on this finding. A first aspect of the present invention to solve the above-mentioned problem is a dendrimer having a branched structure, which comprises a repeating unit having a branching portion, which is characterized in that the polymer has an aromatic amine portion at its terminal, and the repeating unit It is formed by a phenylene vinyl group represented by formula (1):

312 / Description of the Invention (Supplement) / 92-11 / 92123418 11 200404833 It is repeated one or more times. The second aspect of the present invention relates to a tree-like polymer described in the first aspect, wherein the aromatic amine moiety includes at least one substance represented by formula (2):

Wherein Arx represents a single bond or a divalent aromatic group, and each of 11 and Ar2 represents a monovalent aromatic group. The third aspect of the present invention relates to a dendrimer mentioned in the second aspect, wherein the divalent aromatic group contained in the aromatic amine is a phenylene group or a naphthyl group And the monovalent aromatic group is independently selected from the group represented by formula (3):

Each of 1 ?! and R2 is independently selected from a hydrogen atom, a C1-C4 alkyl group, and a C1-C4 alkoxy group. The fourth aspect of the present invention relates to a dendrimer mentioned in any one of the first to third aspects, wherein the repeating unit suitable as a starting point of the branch structure is further combined with a center suitable as a core. Part 0 12 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 The fifth aspect of the present invention relates to a dendrimer mentioned in the fourth aspect, wherein the core is selected from the group consisting of ) Part:

The sixth aspect of the present invention relates to a dendrimer mentioned in any one of the first to fifth aspects, which is a dendrimer. The seventh aspect of the present invention relates to a tree dendrimer mentioned in the sixth aspect, wherein the dendrimer is a second or higher generation. An eighth aspect of the present invention relates to an electronic device element characterized in that it is used for the dendrimer mentioned in any one of the first to seventh aspects. A ninth aspect of the present invention relates to an electronic device element mentioned in the eighth aspect, which is a charge transfer device element. A tenth aspect of the present invention relates to an electronic device element mentioned in the eighth aspect, which is a switching transistor element. An eleventh aspect of the present invention relates to an electronic device element mentioned in the eighth aspect, which is a light emitting device element. A twelfth aspect of the present invention relates to an electronic device element mentioned in the eighth aspect, which is a photoelectric conversion device element. [Embodiment] A mode for carrying out the present invention will be described in detail below. 13 312 / Description of the Invention (Supplements) / 92-11 / 92123418 200404833 In the present invention, the term "dendrimer" conceptually represents a polymer substance including a generally defined dendrimer and a highly branched polymer. Therefore, a dendrimer encompasses any one of the structures having the structural repeating unit (ie, dendritic structural unit) represented by the above formula (0) repeating one or more times (ie, the dendrimer contains two or more repeating units). molecule. In particular, a structure containing the above-mentioned structural repeating unit represented by the formula (1), that is, a structure containing a repeated repeating monomer to form a branched structure is called a "branched structure". Dendrimers and highly branched polymers are generally represented by the following structural formulas. As shown in the formula, dendrimers have regular repeating branch units, while highly branched polymers have irregular repeating branch units. These polymers may have a structure in which the polymer chain branches from a focal point, or a structure in which the polymer chain radiates from a plurality of focal points linked to a multifunctional molecule as a core. Although other definitions of these substances are also acceptable, in other cases, the dendrimers of the present invention include dendrimers with regular repeating branch structures and those with irregular repeating branch structures, of which these two dendrimers The polymer may have a dendritic branch structure or a radial branch structure. According to the generally accepted definition, when a dendritic structural unit extends from its previous dendritic structural unit to its exact replica, the unit extension represents a continuation "g e n e r a t i ο η". It should be noted that it is within the scope of the present invention that the definition of "dendrimer" according to the present invention encompasses the repeating of the structure having each of the similar similar dendritic units having the same basic structure with each other at least once. The concepts of dendrimers, dendrimers, high-branched polymers 14 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 etc. are disclosed in, for example, Masaaki KA Κ I Μ 0 Τ 0, C hemistry, volume 50, page 608 (1995) and Kobunshi (high polymer, Japan), volume 47, page 804 (19 9 8), and these publications can be referred to and incorporated in this case to for reference. However, the descriptions in these publications should not be construed as limiting the invention. Dendrimer

312 / Description of the Invention (Supplement) / 92-11 / 92123418 15 200404833 The dendrimer of the present invention is structurally characterized in that the dendrimer is formed by a phenylene vinyl group represented by the above formula (1); The dendritic structural unit of a single substance is bound to a benzene ring as a branching part, and the dendritic structural unit is repeated one or more times; and the end of the dendrimer is formed by an aromatic amine moiety. The "structure in which the dendritic structure unit is repeated once" used herein represents the unit represented by the structure within the parentheses of the following formula.

This unit is called the "first generation dendrite". Therefore, the first generation dendrimer is produced when the aromatic amine moiety suitable as the terminal part is bound to the binding hand of the first-generation dendritic branch part, or when the binding hand on the opposite side is also bound to the core. When a repeating unit (ie, a vinyl group) suitable as a focal point of a dendrite is replaced by another part, this structure is represented by the following formula:

Where Y represents a monovalent substituent such as a hydrogen atom, a halogen atom or an aldehyde group. 16 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 In the present invention, this structure is also called "first generation dendrite". The similar structure in which the dendritic units with the same structure are successively linked to the joints of the branches of the first-generation dendrites is called "second-generation dendrites". In a similar manner, n-th generation dendrites are generated. Such dendrites having an aromatic amine moiety at the end or dendrites whose desired substituents are bound to their ends or focal points are referred to as "dendritic or highly branched polymers with dendritic branch structures". When a plurality of dendritic branches or high branching polymers (identical to or different from each other) are bound to a multivalent core by subunits, the resulting dendrimers are called "dendritic branches with radial branches" Molecule or highly branched polymer. " In the present invention, a dendrimer system in which the n-th generation dendrite is linked to an m-valent (m is an integer of 2 or more) core is defined as the n-th generation, m-branched dendrimer. In particular, dendrimers in which the n-th dendrite is linked to a benzene core of m valence (m is an integer of 2 or more) are not only defined as the n-th, m-branched dendrimer but also defined as 1) Generation of dendrimers. Examples of dendrimers in which the first generation of dendrites are linked to the core include a representative of the following formula.

The first generation of dendritic part Core: Tetravalent anthracene part Core: Trivalent benzene part

First generation, 4-branched dendrimers First generation, 3-branched dendrimers or second-generation dendrimers 17 312 / Description of the Invention (Supplements) / 92-11 / 92123418 200404833 In particular, the first generation Dendrimers with dendrites linked to tetravalent onion cores are defined as first-generation, 4-branched dendrimers, and similar first-generation dendrites are defined with trivalent benzene-dendritic dendrimers. It is a first-generation, 3-branched dendrimer or a second-generation dendrimer. The dendrimer of the present invention is characterized in that the polymer has an aromatic amine moiety at its end and has dendritic repeating units formed from phenylene and ethynyl. As a result, the solubility of polymers in organic solvents increases; hole conductivity is provided at the ends of the polymers; and the phenylene vinylene main chain system contained in the polymer molecules is protected by the aromatic amine main chain as the molecular surface . Therefore, it is possible to supply an organic semiconductor material that is stable in the air and exhibits isotropic and very high carrier conductivity. As described above, the dendrimer of the present invention having a large number of branches provides a large number of branched ends. Through the use of the end, the number of carriers can be increased. Furthermore, because dendrimers provide a large number of pathways for carrier conduction, the carrier mobility can be effectively improved without the need to orient molecules and increase crystallinity (this has been targeted at conventional conjugated polymers and low-molecular organic semiconductor materials get on). Because the non-planar tertiary aromatic amine moiety is introduced into the polymer terminal, the polymer becomes more amorphous than a polymer with only a phenylene and vinylidene moiety, can form a film (no breaks), and is stable ( No crystallization). The structure of the dendrimer of the present invention is not particularly limited, as long as the polymer has a dendritic structure and the dendritic molecules do not necessarily have a completely neat branch structure. However, when the dendrimer of the present invention is a dendrimer, it is preferred that the dendrimer is a second-generation or higher-generation one to achieve high carrier conductivity. The term "dendrimer generation" represents this expression. Generation 18 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 The number of generations of dendrimers with a larger or long central portion is usually 1 to 10. However, from the viewpoints of the carrier conductivity, the space density of the terminal portion, and the ease of synthesis, the number is preferably 2 to 8, more preferably 2 to 7, and most preferably 2 to 5. The structure of the dendrimer of the present invention is not particularly limited, as long as the polymer has a dendritic repeating unit formed of the phenylene vinylene group represented by the above formula (1) and has an aromatic amine moiety at its terminal. As used herein, the term "aromatic amine moiety" refers to a moiety having an aromatic group in place of a hydrogen atom of an amine group or a moiety containing a divalent aromatic group (where this part is bound). The aromatic amine moiety may have a hydrocarbon group on the side attached to the dendritic repeat unit. In this example, for example, the aromatic amine moiety is linked to the dendritic repeat portion through an organic group containing a divalent aromatic group. In particular, two or more of these aromatic amine moieties may be present on the polymer terminal. In this example, the aromatic amine moiety may be directly bonded to the dendritic repeating unit or may be indirectly bonded to the repeating unit through another substituent (preferably an aromatic group). The aromatic amine moiety preferably contains a moiety represented by the above formula (2). In formula (2), Arx represents a single bond or a divalent aromatic group, and each of An * Ar2 represents a monovalent aromatic group. Examples of single bond or divalent aromatic groups include substituted or unsubstituted aromatic hydrocarbon groups, aromatic heterocyclic groups, fused polycyclic aromatic hydrocarbon groups, fused heterocyclic aromatic groups And single bond or divalent aromatic groups which are fused through the ring condensing of these groups. For example, a single bond or a divalent aromatic group preferably has 50 carbon atoms (or less), and may contain heteroatoms such as 0, N, S, P, B, or Si, or in addition to Unsubstituted structure outside 19 312 / Description of the Invention (Supplement) / 92-11 / 92123418 200404833 May have substituents, such as an alkyl group, an alkyl group, a vial group, a weyl group, a fluorenyl group Group, nitro group, cyano group, or halogen (such as fluorine, chlorine, bromine, or iodine) atom. Specific examples include (but are not limited to) benzene, naphthalene, onion, naphthacene, pentacene, hexaphenyl, phenanthrene, phenalene, pyrene, l (chrysene), benzo S, perylene , Bitriphenylene, ca ore nene, cynophthalene, naphtho; I, biphenylene, phenylene, phenanthrene, biphenyl, bitriphenyl, bitetraphenyl, bipentadiene, biphenyl Benzene, diheptabenzene, phenyl shallot, phenyl naphthalene, diphenyl shallot, biphenylene, diphenylene, fluorene, ene, naphthalene, dibenzodine, therapeutics, cyclopentadiene, Zixphene, Gou 7 Dried, Waxian onion, Diquat benzene, Fu, Meng, Huanxin four women, octarene, rubrene, σ stope, squeak, roar, Shi Xi ° each ( si 1 ο 1 e), Jun, 嚷 嗤, Mi 嗤, mouth than Jun, furazane, two 嗤, 嚷 20 sitting, roaring, thio travelan, pyrimidine, roaring, da Till, stilbene, benzopyrene, benzofuran, benzosilrole, indole, benzoxazole, benzothiazole, benzimidazole, phopholine, thioxene, oxazoline, carbazole, two Benzosilrole, dibenzofuran, dibenzothia , Morpholine, acridine, benzoxoline, phenanthrene, phenanthrene, phenanthrene, 0thumb, morphine, σ # drinking mouth, diphenanthrene, triphenylphene, tetraphenylphenanthrene, diphenanthrene Mouth whistle, three squeak whistle, four sigma whistle, two 11:17 each, three roar p each, four roar Luo, two stone xi ρ each, three stone xikou each, four stone xi kou each, two roar. Ding, Ding Ding Ding, Ding Ding Ding, Ping Ding Ding, Phenol Ding, Phenylfuran, Phenylthiophene and Phenyl f-diazole. These groups may be used as monovalent aromatic groups or divalent aromatic groups, and may be substituted or unsubstituted. In the above formula (2), Arx is preferably a phenylene group or a naphthyl group, and each of Ari and A ** 2 of the above formula (3) (may be the same or different from each other) 20 312 / Description of the Invention (Supplement) / 92 · 11/92123418 200404833 is independently selected from the group represented by formula (3). In formula (3), each of R1 and R2 is independently selected from a hydrogen atom, a CM-C4 alkyl group, and a CH-C4 alkoxy group. When an alkyl group is introduced into the terminal, the resulting polymer becomes a glass transition temperature as described above. Therefore, each of Ri and R2 is more preferably a hydrogen atom, a fluorenyl group or an fluorenyl group, among which a hydrogen atom is most preferable. In the present invention, the term "end portion" of a dendrimer is generally used to represent a surface structure in which any number of ends of a dendritic or radial branch structure are bound to form a molecular surface of the dendrimer, ( That is, it does not include dendritic or radial branches (repeating units). However, the aromatic amine moiety of the benzene ring containing the terminal end of the repeating unit of the outermost branched structure is also within the above range. The structure of the terminal portion of the dendrimer of the present invention is not particularly limited as long as these portions have at least one terminal aromatic amine portion. However, it is preferable to have a terminal portion of the structure represented by the formula (2), and to achieve high carrier conductivity. Specific examples of the terminal part include (but are not limited to) the following formula (5). There is no particular limitation on the manner of bonding between these terminal portions and dendritic structural units, and examples thereof include the aforementioned aromatic amine moieties containing a benzene ring suitable as an end point of an outermost branched repeating unit; Bonding; carbon-carbon bonds; carbon-nitrogen bonds; amido groups; ether bonds; ester bonds; and urea bonds. (5)

21 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833

R! To Rf hydrogen atom, tn-C4 alkyl group or C1-C4 alkoxy group. In the dendrimer of the present invention, the starting point of the repeating unit as the starting point of the branched structure may be combined with the central portion as the core. Simply put, the core can be linked to any number of starting points of the dendritic branch structure, and represents a part of the structure other than the branch structure. In other words, the core is suitable as the center of the dendrimer and represents a part of the dendrimer except for the repeating unit. Specific examples of the core include a C 1 -C 2 0 alkylene group, a C 6-C 2 0 alkylene group, and a group in which these alkylene groups and an alkylene group are combined. In addition to an unsubstituted alkylene group, the alkylene group may contain heteroatoms therein, such as 0, NN, N (CΗ3), S or S02, or may have a substituent such as A hydroxyl group, a carboxyl group, a fluorenyl group, or a halogen (such as fluorine, chlorine, bromine, or iodine) atom. The core may be a polyvalent group of any of the above-mentioned groups, and the hydrogen atom bonded to the carbon atom is removed; the group in which the heterocyclic group is linked to any of the above-mentioned hydrocarbon groups; < Or mouth 1, phthaloline complex. In addition to the core example with at least two valences, a monovalent core formed by linking hydrogen to a multivalent core can also be used. In particular, the part represented by the above formula (4) is preferably used as the core. In particular, dendrimers without a core are also within the scope of the present invention. In this example, the starting point of the branching structure of the dendrimer of the present invention is 22 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 According to the starting material used to make the repeating unit (for forming the branching structure) And decide. As far as the starting point of the branched structure is concerned, the reactive group of the starting material may be replaced by nitrogen. There is no particular limitation on the method for synthesizing the dendrimer of the present invention, and the polymer can form (ie, synthesize) a monomer (or a precursor thereof) containing an aromatic amine moiety and a polymer containing a suitable vinylidene moiety Monomer of structure. As used herein, the term "monomer" refers to a type of low molecular weight compound that has an aromatic amine skeleton as a partial structure or is suitable as a precursor for a phenylene vinylene moiety, where this compound includes its introduction to form a phenylene vinylene Partially reactive substituent derivatives and their precursors. There is no particular limitation on the synthetic method used to form a dendrimer structure from a monomer, and the available methods include a "divergent method" in which branches successively extend from the focal point, in which the branches extend from the ends of the branches and are thus connected The unit is finally combined with the "convergence method" of the focal point and the polycondensation reaction of polyfunctional monomers of type AB 2 (reactive functional groups between A and B). Among these methods, the "convergence method" is preferably used for efficiently synthesizing a defect-free high-purity dendrimer based on the convenience of not requiring an excessive amount of starting materials and purification products. Examples of the method for forming a phenylene vinylene skeleton include those disclosed in the open literature, see, for example, S. K. Deb et al .; J. Am. C hem · Soc. 1997, 119, 9079, J. NG Pillow et al .; Macromolecules 1999 »Volume 32, No. 19, 5 9 8 5; H. Meier et al .; Angew. Ch e m. In t. Ed. 1 9 9 8, 37, No. 5, 6 4 3, M. Hailm et al .; Adv. Mater. 1999, 11; No. 5, 371; H. Meier et al .; Chem. Eur. J. 2 0 0 0 6, 6, No. 13, 2 4 6 2, J. 23 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 M. Lupton et al .; A d v. Mater. 2 0 0 1, 13, No. 4 JL Segura et al. 0 r g. Lett 2 0 01, Vol. 3, 1 or ED Barra et al .; J. 0 r g. Ch e m. 2 0 0 1, 66. The dendrimer of the present invention can be obtained through 2 disclosed in the above literature. . For example, a dendrimer having a tertiary aromatic amine moiety at its terminal portion and having the structure represented by the formula (1) can be obtained by "Receiving 5, which contains the component represented by the chemical reaction formula (6) Reaction steps:, 2 5 8, 7, 2645 5 6 6 4 〇_Method r by the above method

312 / Invention Specification (Supplement) / 92-11 / 92123418 24 200404833

Where η is an integer of 1 to 5, each of Aim and An represents a monovalent aromatic group, and Arx represents a single bond or a divalent aromatic group. The reaction step represented by the chemical formula (6) includes reaction step 1 in which an ethylene compound (a) having an aromatic amine moiety W for forming a terminal portion is reacted with a compound (b) to form a compound (c); a reaction step 2. The aldehyde group of the formed compound (c) is converted into a vinyl group to form a compound (d); and reaction step 3, wherein the product (d) is reacted with the compound (b) to form a continuum Generations of dendrites (e). In addition, when the dendrite is bound to the core of the benzene ring, reaction step 4 is performed, in which the compound (e) is reacted with the compound (f) having a substituent for forming a vinyl skeleton through a reaction with an aldehyde group, whereby Compound (g) is formed. Among the above compounds, the compound (c) and the compound (d) may be referred to as a first-generation dendrimer or dendrite, and the compound (e) may be referred to as a second-generation dendrimer or dendrite. For the purpose of simple explanation, dendrimers having only the first and second generation numbers are shown in the above reaction steps 1 to 3 of the chemical equation (6). However, further generations of trees can be made by repeating reaction steps 2 and 3 25 312 / Explanation of the Invention (Supplement) / 92-11 / 92123418 200404833 Dendrimers. Compound (g) can be defined as a third-generation dendrimer or a second-generation, 3-branched dendrimer. In the above chemical equation, the second generation dendrimer (e) is bound to the compound (f). However, dendrimers of any generation can be combined with central structure molecules according to similar reaction steps. The reaction for converting the compound (c) into the compound (e) can also be performed as shown in the following formula (7) via reaction step 5 shown in the following chemical equation. In particular, the compound (c) is reacted with a branched source compound (h), followed by a deprotection for forming an acetal group, thereby producing a compound (e). The compound (c) can be prepared from an aromatic amine compound similar to the compound (a) and having a brewing group (instead of a vinyl group) by using a similar reaction. By repeating Step 5 of the reaction, a dendrimer having a higher generation can be obtained.

r (e) In reaction step 1 or 3, the reaction of compound (a) or compound (d) with compound (b) can be prepared via Heck reaction (see, for example, R. F. Heck et al., J · Org. Chem. 1972, 37, 2320; or T. Mizoroki et al., Bull. Chem. Soc. Jpn. 1971, 44, 581) 26 312 / Description of the Invention (Supplement) / 92-11 / 92123418 200404833 Various combinations of palladium catalyst and alkali catalyst are used as H eck reaction catalysts. Examples of palladium catalysts include tetrakis (triphenylphosphine) palladium, palladium acetate, palladium chloride, palladium black, bis (triphenylphosphine) palladium dichloride, bis (dibenzylacetone) palladium, dichloride Bis (tricyclohexylphosphine) palladium, [1,2-bis (diphenylphosphino) butane] palladium dichloride and [1,2-bis (diphenylphosphino) ethane] palladium dichloride . In addition, a combination of a ligand compound and such a palladium catalyst may be effective. Examples of the ligand compound include triphenylphosphine, 1,1′_bis (diphenylphosphino) ferrocene, 1,2-bis (diphenylphosphino) ethane, 1,3_bis (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, sodium diphenylphosphinobenzene-3-sulfonate, tricyclohexylphosphine, tris (2-furyl) phosphine , Tris (2,6-dimethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (3-fluorenylphenyl) phosphine and Tris (2-methylphenyl) phosphine. Instead of a palladium catalyst, a nickel catalyst [1,1'-bis (diphenylphosphino) ferrocene iron] digasified nickel can also be used. Examples of alkali catalysts include potassium acetate, sodium acetate, sodium carbonate, sodium oxide (such as sodium ethoxylate), third butoxy bell, barium hydroxide, triethylamine, potassium phosphate, sodium hydroxide, and potassium carbonate . Examples of the preferred reaction solvent include dimethylamidine, dimethylsulfoxide, dioxane, benzene, toluene, tetrahydrofuran, dimethoxyethane, dimethylacetamide, and dibenzobenzene And propionitrile. The reaction temperature is preferably 25 to 150 ° C, and the reaction time is preferably 30 minutes to 24 hours, and more preferably 1 hour to 12 hours. In step 2, the reaction of converting the aldehyde group of the compound (c) into a vinyl group for forming the compound (d) can be performed via a Wittig reaction. The Wittig reaction is known to be effective in the production of alkenes via the reaction of acid or S with conformation-ylide (see, for example, 0 rg. R eac t. 1 9 6 5, 1 4, 2 7 0). In the chemical reaction formula (6), the reaction of converting the aldehyde 27 312 / Invention (Supplement) / 92-11 / 92123418 200404833 group to a vinyl group through a reaction with phosphorus-Ylide can be used by using Phosphorus-ylide produced by the reaction of a methyl functional compound with triphenylphosphine is carried out to form a phosphonium salt, and the phosphonium salt is deprotonated with a base such as an alkyl lithium or an alkoxide. Solvents such as tetrahydrofuran, diethyl ether and dimethyl sulfoxide can be appropriately used. Since phosphorus-Ylide is highly reactive with water, the solvent used is preferably effectively dehydrated. In reaction step 4, the reaction of the compound (e) with the compound (f) used to produce the compound (g) can be performed via a Horner-Wadsworth-Emmons reaction (see, for example, L. Horner et al., Chem. Ber. 1962, 95, 581; or WS W adsworth et al., J. Am. Chem. Soc. 1961, 8 3, 1 7 3 3). Bases such as sodium hydroxide and alkoxides are suitable as catalysts. Examples of the reaction solvent include methanol, ethanol, benzene, tetrahydrofuran, dimethyl sulfoxide, diethyl ether and dimethoxyethane. In reaction step 5, the reaction of the compound (c) with the compound (h) used to make the compound (e) can be performed via a Horner-Wadsworth-Emmons reaction (see, for example, L. Horner et al., Chem. Ber. 1962, 95, 581; W. S. Wadsworth et al., J. Am. Chem. Soc. 1961, 83, 1 7 3 3; ED Barre et al., J. Org. Chem. 2 0 0 1, 66, 5 6 6 4; or H. Meier et al., Chem. Eur. J. 2000, 6, No. 13, 2 4 6 2). Bases such as sodium hydroxide and alkoxides are suitable as catalysts. Examples of the reaction solvent include methanol, ethanol, benzene, tetrahydrofuran, difluorenyl sulfoxide, diethyl ether and dimethoxyethane. The acid used for deprotecting the acetal group is not particularly limited, and acids such as inorganic acids, organic acids, and ion exchange resins can be used. 28 312 / Invention (Supplement) / 92-11 / 92123418 200404833 There is no particular limitation on the method for synthesizing compound (a). The compound (a) can be easily synthesized by, for example, synthesizing an aromatic amine compound having an aldehyde substituent and converting the aldehyde group to an ethylene group. In this example, the reaction for conversion to an ethanoyl group can be performed via a Wi i 11 i g reaction (see, for example, 0 r g. Re a c t · 1 9 6 5, 1 4, 2 7 0). The aromatic amine compound having an aldehyde substituent can be synthesized through the formazanation of the aromatic amine compound and the Vi i 1 smeier reagent. Another possible method involves a condensation reaction via U 1 1 m a η η (see C h e m.

Lett., 1145, (1 9 8 9), Synth. Commu. 3 8 3, (1 9 7 7), etc.) or via the Toso method (disclosed in Japanese Patent Laid-Open Application (kokai) No. 10-3 1 0 5 6 1) Condensing a diarylamine compound with an aryl compound having an aldehyde group (protected in its acetal form) and deprotecting the acetal group. The compound produced in each reaction step is purified, thereby synthesizing a high-purity dendrimer with a small number of defects. The purification method is not particularly limited, and a recrystallization method, a crystallization method, a sublimation method, and a column purification method can be used. According to the above manufacturing method, various kinds of dendrimers having polyaromatic amine portions at the ends can be prepared by selecting the types of the compound (a) for forming the branched end and the compound (f) for forming the central portion. Since the manufacturing method is based on the "convergence method", the purification process in each reaction step can be easily performed on the basis, so a high-purity dendrimer (a dendrimer) with a small number of defects can be produced. The carrier-conductive dendrimer of the present invention can be envisaged to be used in many fields. By selecting its molecular structure or doping or similar method, the dendrimer of the present invention can provide hole transport (p-type), electron transport (η-type) and Xu 29 312 / Invention Specification (Supplement) / 92 -11 / 92123418 200404833 Versatile electronic material. Therefore, these electronic materials can be used for switching elements such as organic transistor elements, organic F E T elements or organic T F T elements, solar cells, photoelectric conversion elements, capacitors, light emitting elements, electroluminescent elements, polymer secondary batteries, and the like. The structure of these elements suitable for each purpose will be described below. An organic transistor element formed of an organic layer having hole-transporting and / or electron-transmitting properties includes a semiconductor layer, a gate electrode formed of a conductive layer, and an insulating layer interposed between the semiconductor layer and the conductive layer. , The source electrode and the drain electrode are bonded to manufacture a transistor element. The above organic layer is formed of the dendrimer of the present invention. The light-emitting device includes a pair of plate-shaped electrodes arranged in parallel and an organic layer containing the material of the present invention between the two electrodes. Generally speaking, this device is formed by a transparent electrode (such as IT 0), a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode. The carrier transmission function and the light emitting function can be combined into a single structure. The above organic layer is formed from the dendrimer of the present invention. A photoelectric conversion element or a solar cell usually includes an organic layer sandwiched by plate electrodes arranged in parallel. An organic layer may be formed on the comb-shaped electrode. There is no particular limitation on the position of the organic layer. There are no particular restrictions on the electrode material. However, when using plate electrodes arranged in parallel, at least one electrode is preferably formed of a transparent electrode (such as an I T 0 electrode or a fluorine-doped tin oxide electrode). The organic layer is formed by two secondary layers, that is, one layer is formed by the dendrimer having P-type semiconductivity or hole transportability according to the present invention, and one layer is formed by the η-type semiconductivity or electron transportability according to the present invention. Dendrimer 30 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833. Furthermore, when a photosensitive dye group is introduced into two dendritic molecules or two molecules or two branches and two molecules are located between the two layers of the special photosensitive dye molecule, the element efficiency is improved, and For example, a solar power efficiency capacity having such a structure is used. In this case, the photosensitive dye molecule part has the HOMO energy level of the HOMO (the highest occupied molecular domain) energy of the dendrimer, and has less than the unoccupied molecular domain of the electron transport dendrimer. ) Higher energy level LUM0. When the photoexcitation conditions of the hole transport layer or the electron transport layer are satisfied, a conductive polymer or a dendrimer is disposed between the hole transport layer and the layer, and an electrochemical photoelectric conversion element can be formed. Introducing optional dye groups into either layer. A capacitor includes a hole transport layer and an electron transport layer, one of which is a conductor layer and the other is a semiconductor layer, and an insulating layer is interposed between the semiconductor layer. In addition, the hole transport layer and the electron transport are formed by a conductive layer, and the ion conductive layer is inserted into the two conductive layers. The R hole transport layer is formed by a p-type semiconductor layer, and the electron transport is formed by an η-type semiconductor layer. And these layers can be stacked, thereby stacking multiple layers. The above semiconductor system is formed from the dendritic electroluminescence element of the present invention, which includes a hole transport layer formed of a polymer layer that can be doped with a p-type dopant and decolorized by an oxygen reaction, an I-doped compound, and oxidized. The electricity formed by the polymer layer decolorized by the reduction reaction and the supporting electrolyte is provided in one layer between the two layers. This element is in a polymer secondary battery, so it can provide one of the high capacity and low internal 312 / Invention Specification (Supplement) / 92-11 / 92123418 layers. The meaning is that it can enter a pool to achieve high specific hole transmission. Lower LUM0 (the most ionic electron transport can use the photosensitizer as a semi-inductive layer. Both are 3. In addition, the transport layer is formed by continuous L polymer. The structure of the reduced quasi-n-type hole-doped transport layer can be used for resistance Two 31 200404833 grade batteries. As mentioned above, by using the above-mentioned materials according to the present invention, a device that requires carrier conductivity and has a significantly high carrier conductivity can be manufactured through a simple process. (Example) Next, the present invention will refer to the relevant tree branches Polymers and functional elements using these dendrimers are described in the examples described below, and the present invention should not be limited to them. The devices used for measurement are described below. NMR: FT-NMR, model JNM -AL400 (400 MHz, product of JE0L), solvent: CDC 13, room temperature, chemical shift reference value (0 ppm): tetramethylsilane (TMS). GPC: HLC-8220 GPC, product of Tosoh Corporation; Column: TSK gel Super ΗZΜ-Μ; Eluent: THF; Detector: UV 24 5 nm; Measurement (weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)) decreased To polystyrene (as a standard product). [Synthesis Example 1] Synthesis of a third generation dendrimer [Synthesis Example 1-1] Diphenylamino styrene (having an aromatic amine moiety represented by the following formula as a terminal Synthesis of vinyl compound (a))

Under nitrogen pressure, dehydrated tetrahydrofuran (160 ml) was added to a mixture of methyltriphenylphosphonium bromide (42.9 g) and potassium tert-butoxide (13.5 g) while stirring at room temperature. mixture. The resulting mixture was allowed to react at room temperature for 2 hours. Next, diphenylaminobenzaldehyde (10.9 g) dissolved in dehydrated tetrahydrofuran (120 ml) 32 312 / Explanation of the Invention (Supplement) / 92-11 / 92123418 200404833 was added dropwise to The resulting mixture was reacted at room temperature for 2 hours. The reaction was stopped by adding acetone (10 ml) to the mixture. The precipitate was removed by filtration and washed with dichloromethane. The washing liquid and the filtrate were combined, and the solvent was filtered off under reduced pressure, thereby producing a crude product. The crude product was separated and purified by column chromatography (packing material: Silicagel 60 (Merck product), eluent: dichloromethane / n-hexane) to produce 10.0 g of the target product (yellow solid, yield : 9 2%). The structure of the product was confirmed by 1 Η-N M R spectrum. The measured data is shown below. NMR (CDC13) δ7.29-7.22 (m, benzene ring, 6H), δ7 · 08 (d, J = 8.4Hz, benzene ring, 4H), 67.03-6.98 (m »benzene ring, 4H), 66.65 (dd , J = 18Hz, 11 Hz, ethylene, 1H), 5 5. 6 3 (d »J = 18Hz, vinyl, 1H), δ5 · 14 (d, J = 11Hz, vinyl, 1H). [Synthesis Examples 1-2] Synthesis of first-generation dendritic aldehyde (represented by the following formula)

Under nitrogen pressure, diphenylaminoacetamide (220 ml) was added to 3,5-dibromobenzaldehyde (5.8 g), and the diphenylaminobenzene prepared in Synthesis Example 1-1 was added. In a mixture of ethylene (1.2 g), palladium acetate (1.0 g), triphenylphosphine (2.3 g) and sodium carbonate hydrate (5.1 g). The resulting mixture was heated to 110 t with stirring overnight. After the reaction was completed, the reaction mixture was cooled to room temperature. With stirring, dichloromethane and water were added to the reaction mixture 33 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833, and the organic layer thus formed was separated. The organic layer thus separated was washed with water, and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure, whereby an oily crude product was formed. The crude product was separated and purified via column chromatography (filler: Silicagel 60 (Merck product), eluent: dichloromethane / n-hexane) to produce 8.9 g of the target product (yellow solid, yield: 63%). The structure of the obtained product was confirmed by 1H-NMR spectrum. The measured data is shown below. ! H NMR (CDCls) δΐθ.1 (s, aldehyde, 1H), 57.85 (d, J = 1.6 Hz, benzene ring, 2H), 5 7.7 9 (t ^ J = 1.6Hz, benzene ring, 1H), 57.41 (d, J = 8. 4 Hz, benzene ring, 4H), 67.2 7 (t, J = 7. 8 Hz, benzene ring, 8H), 57.18 (d, J = 16Hz, vinyl, 2H), S7. 12 (d, J = 8. 4 Hz, benzene ring, 8H), 5 7.0 7-7.0 2 (m, benzene ring, 8H, and vinyl, 2H) °

Under nitrogen pressure, add dehydrated tetrahydrofuran (35 ml) to a mixture of methyltriphenylphosphonium bromide (10.0 g) and potassium tert-butoxide (3.1 g), while at room temperature The mixture was stirred. The resulting mixture was allowed to react at room temperature for 2 hours. Next, the first-generation dendritic aldehyde (4.5 g) prepared in Synthesis Example 1-2 was dissolved in dehydrated tetrahydrofuran (22 ml) 34 312 / Instruction Manual (Supplement) / 92-11 / 92123418 200404833 The solution was added dropwise to the above reaction mixture, and the resulting mixture was allowed to react at room temperature for 2 hours. The reaction was stopped by adding acetone (10 ml) to the mixture. The precipitate was removed by filtration and washed with two gases of methane. The washing liquid and the filtrate were combined, and the solvent was filtered off under reduced pressure, whereby a crude product was formed. The crude product was separated and purified by column chromatography (packing material: Si 1 icage 1 6 0 (Merck product), eluent: dichloromethane / n-hexane) to produce 4.5 g of the target product (yellow solid Product, yield: 99%). The structure of the product obtained was confirmed by 1 Η-N M R spectrum. The measured data is shown below. ! H NMR (CDC 1 3) 5 7. 4 8 (s, benzene ring, 1H), 6 7. 3 9-7. 3 7 (m, benzene it, 6H), 57.48 (t, J = 7.2 Hz, ^ St, 8H), 57.11-6.96 (m, benzene ring, 20H), 5 6.7 3 (dd, J = 18 Hz, 11 Hz, vinyl, 1H), 65.81 (d, J = 18 Hz, vinyl, 1H), 6 5. 2 8 (d, J = 11 H z, ethynyl, 1 H). [Synthesis Examples 1-4] Synthesis of second-generation dendritic aldehyde (represented by the following formula)

Under nitrogen pressure, dehydrated dimethylacetamide (40 ml) was added to 3,5-dibromobenzaldehyde (0.9 g), and the first-generation dendritic ethylene prepared in Synthesis Examples 1-3 Base compound (4.5 g), palladium acetate (0.16 g), triphenylphosphine (0.33 7 35 312 / Invention Note (Supplement) / 92-11 / 92123418 200404833 g) hydrated with sodium carbonate (0.82 g). With stirring overnight, the resulting mixture was heated to 110 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature. With stirring, dichloromethane and water were added to the reaction mixture, and the organic layer thus formed was separated. The organic layer thus separated was washed with water, and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure, whereby an oily crude product was formed. The crude product was separated and purified by column chromatography (packing material: Si 1 icage 1 6 0 (Merck product), eluent: dichloromethane / n-hexane) to produce 2.9 g of the target product (yellow solid Material, yield: 60%). The structure of the product was confirmed by 1 Η-N M R spectrum. The measured data is shown below. The weight-average molecular weight (Mw), number-average molecular weight (Mη), and molecular weight distribution (Mw / Mη) distribution measured by G PC were 1,6 0, 1, 6, 05, and 1.05. These values indicate that the target polymer has high purity and has a unimodal dispersion state. ! H NMR (CDC13) 610.08 (s, aldehyde, 1H), δ 7.94 (d, J = 1.6 Hz, benzene ring, 2H), 57.91 (t, J = 1.6Hz, benzene ring, 1H), 67 54 (s, benzene ring, 6H), δ7.42 (d, J = 8.8 Hz, benzene ring, 8H), δ7 · 3, 7.17 (m, vinyl, 4H, and benzene ring, 16H), δ7 · 14-7 · 11 (m, vinyl, 4H, and benzene ring, 16H), δ 7.08-7.01 (m, benzene ring, 16H, and vinyl, 4H).

[Synthesis Examples 1 to 5] Synthesis of 1,3,5-benzotriphosphonate (represented by the following formula) as a trivalent core 36 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 According to SK The procedure disclosed by Deb et al. (≪ 1.111. () 11611] .800.199.7, 119,9 079) was used to synthesize the target product. In particular, a catalytic amount of phenylhydrazone In the presence of fluorenyl peroxide, mesitylene (1 equivalent) is reacted with N-succinimide (3 equivalents) at 35 ° C methyl acetate to form 1,3,5-tris (bromo Methyl) benzene. Triethyl phosphite (6 equivalents) was added to the product (1 equivalent) and the mixture was heated to 120 ° C. Unreacted triethyl phosphite was removed under reduced pressure, whereby The target product is generated. The structure of the product is confirmed through 1 Η-NMR spectrum, and the product is confirmed to be the target product; that is, 1,3,5-benzotriphosphonate, based on the fact that the spectrum of the product meets the above Disclosed in the literature. The measured data are shown below. 4 NMR (CDC13) δ7 · 14 (s, benzene ring, 3Η), δ4.01 (q, fluorenylene, 12H), 63.12 (d, methylene, 6Η) δ1 · 26 (t, methyl, 18H) [Synthesis Example 1--6]. The third generation dendritic polymer (represented by the following formula (8)) is synthesized

312 / Invention (Supplement) / 92-11 / 92123418 37 200404833 Under nitrogen waste, (1.20 g) obtained in Synthesis Examples 1 to 4 and 1 produced in Synthesis Examples 1 to 5, 3.5 mg) was dissolved in anhydrous tetrahydrofuran (28 ml) in paraffin solution, and 71 mg was added thereto, and reacted for 1 hour. Next, in a paraffin solution at intervals of 30 minutes, 71 mg) three times, and after the reaction was completed, a small amount of water was added to the solvent. The residue was dissolved in digas methane, and the resulting organic layer was dried over magnesium sulfate, and the agent was thereby formed into a crude product. The crude product was isolated and filled with Silicagel 60 (Merck product), n-hexane) to produce 859 mg of the target product (72%). 1H-NMR spectrum and 13C-NMR structure. The measured data is shown below. Via GPC amount (Mw), number average molecular weight (Μη), and molecular weight distribution 4,636, 4,431, and 1.046. These values represent purity and present a unimodal dispersion. In addition, it was confirmed that the dendrimer can be easily dissolved in organic alkane, toluene, N-fluorenylsalrolidone or γ-butyrolactone g / l at room temperature. NMR (CDCls) δ7 · 55 (s, aldehyde, 3Η), 6Η), 67.43 (s, benzene it, 3H), 57.35 (s, (s, benzene ring, 6H), δ7 · 23 (d, J = 8 4 Hz, benzene ring (m, vinyl, 12H, and benzene ring, 48H), δ7 · 31 According to the specification of the invention (Supplement) / 92-11 / 92123418 Second generation dendritic aldehyde product-benzotriphosphonic acid Ester (150). Sodium hydride (60%, and the mixture at room temperature, sodium hydride (60%) was added, and the mixture was reacted for 2 hours. And removed under reduced pressure and the solution was washed with water. Removal under reduced pressure column chromatography for purification (filling and dissolving solution: dichloromethane (yellow solid, yield spectrum confirmed product). The measured weight-average molecular (Mw / Mn) distribution is high for the target polymer. The third-generation tree solvent (such as dichloromethane) prepared, at least to the content of 1 δ 7 · 5 2 (s, benzene ring, benzene ring, 1 2 Η), δ 7 · 2 6, 24Η), δ7. 16-7. 12 05-6.89 (m, ethylene 38 200404833, 18H, and benzene ring, 96H), 56.80 (d, J 2 16 Hz, vinyl, 1 2H). 13C NMR (CDCls) 6 1 4 7.4, 1 4 7. 1, 1 3 8.0, 137.7, 137.3, 131.2, 129.2, 128. 3, 127.4, 126.6, 124. 4, 123.4, 122.9 ° [Synthesis Example 2-1] 3,5-bis (diethoxyphosphoranylmethyl) benzaldehyde dimethylacetal (below) (Expression)

According to the procedure disclosed by E. D. Barra et al. (J. Org. Chem. 2 0 01, 6 6, 5 6 6 4), the target product was synthesized through five reaction steps. Specifically, in reaction step 1, by using lithium aluminum hydride, trimethyl-1,3,5-tricarboxylic acid ester is reduced in tetrahydrofuran, thereby generating 1,3,5-tris (hydroxymethyl) benzene. . In reaction step 2, by using carbon tetrabromide and triphenylphosphine, the hydroxyfluorenyl group is brominated in acetonitrile to generate 3,5-bis (bromomethyl) benzyl alcohol. In reaction step 3, 3,5-bis (dibromomethyl) benzaldehyde is formed by oxidizing the methylol group with manganese dioxide (in dichloromethane). In reaction step 4, the dibromomethyl group is phosphorylated using triethylphosphonate to form 3,5-bis (diethoxyphosphofluorenylfluorenyl) benzaldehyde. In reaction step 39 312 / Invention specification (Supplement) / 92-11 / 92123418 200404833 5, the use of orthoacetate and montmorillonite K-1 0 (trade name) (in carbon tetrachloride) The aldehyde group is acetalized to produce a target product of 3, 5-bis (diethoxyphosphoniummethyl) benzaldehyde dimethylacetal. Through l-NMR and based on the fact that the spectrum of the product conforms to those disclosed in the above literature, the product obtained is confirmed to be the target product, that is, 3,5-bis (diethoxyphosphatinofluorenyl) phenylcarbaldehyde Fluorenyl acetal. The measured data is shown below. ^ NMR (CDC1 3) δ7.28 (brs, benzene ring, 2H), δ7.21 (brs, benzene ring, 1H), 55.37 (s »Takigawa, 1H), 64.05-3.98 (m, methylene, 8H), S3.31 (s, methyl, 6H), 53.15 (d, methylene, 4H), δΐ · 25 (t, methyl, 1 2H) ° [Synthesis Example 2-2] The third generation tree Synthesis of aldehyde (represented by the following formula)

40 312 / Instruction of the Invention (Supplement) / 92-11 / 92123418 200404833 Under nitrogen pressure, the second-generation dendritic aldehyde (6 2 8 mg) prepared in Synthesis Examples 1-4 and Synthesis Example 2-1 The obtained 3,5-bis (diethoxyphosphatinofluorenyl) benzaldehyde dimethylacetal (102 mg) was dissolved in dehydrated tetrahydrofuran (10 ml). Potassium tert-butoxide (61 mg) was added thereto, and the mixture was reacted at room temperature for 2 hours. Next, concentrated hydrogen acid (1 ml) was added thereto, and the resulting mixture was allowed to react at room temperature for 18 hours. After the reaction was completed, the reaction mixture was neutralized with a saturated aqueous sodium bicarbonate solution. The formed organic layer was washed with saturated brine, and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure, thereby generating a crude product. The crude product was separated and purified by column chromatography (packing material: Si 1 icage 1 6 0 (Merck product), eluent: dichloromethane / n-hexane) to produce 532 mg of the target product (yellow solid, Yield: 82%). The structure of the obtained product was confirmed by 1H-NMR spectrum. The measured data is shown below. The weight-average molecular weight (Mw), number-average molecular weight (Mη), and molecular weight distribution (Mw / Mn) distribution measured by GPC were 3,547, 3,422, and 1.036. These values indicate that the target polymer has high purity and has a unimodal dispersion state. NMR (CDC 1 3) 5 9.9 6 (s, aldehyde, 1H), 5 7. 8 2 (brs, benzene ring, 3 Η), 6 7. 5 5-7. 5 4 (m, benzene ring, 6 Η ), 5 7.4 5 (s, benzene ring, 8H), 5 7.4 0 (s »benzene ring, 4H), 5 7.3 3 (d» J = 8.8Hz, benzene ring, 16H), δ7 · 24-6 · 97 (πm, vinyl and benzene ring, 116Η), 5 6.9 2 (d »J = 16 Hz, vinyl, 8H). [Synthesis Example 2-3] Synthesis of the fourth generation dendrimer (represented by the following formula) 41 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833

Under nitrogen pressure, the third-generation dendritic aldehyde product (3 18 mg) obtained in Synthesis 2-2 and the 1,3,5-benzotriphosphonic acid ester (1 20 mg) was dissolved in anhydrous tetrahydrofuran (5 ml). Potassium tert-butoxide (14 mg) was added thereto, and the mixture was reacted at room temperature for 2 hours 42 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833. After the reaction was completed, concentrated hydrochloric acid (1 ml) was added thereto. Diethyl ether was added thereto, and the formed organic layer was separated. The formed organic layer was successively washed with a saturated aqueous sodium bicarbonate solution and saturated brine, and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to produce a crude product. The crude product was isolated and purified by column chromatography (packing material: Silicagel 60 (Merck product), eluent: dichloromethane / n-hexane) to produce 224 mg of the target product (yellow solid, yield: 70%). By 1H-NMR, a broad peak was observed in a region of 6 to 8 ppm. The weight-average molecular weight (Mw), number-average molecular weight (Mη), and molecular weight distribution (Mw / Mn) distribution measured by GPC were 7, 679, 7, 161, and 1.072. These values indicate that the target polymer has high purity and is in a unimodal dispersion state. <Example 1> Organic switching transistor element An organic switching transistor element containing a reversible staggered structure of the dendrimer of the present invention was prepared. Fig. 1 schematically shows a cross section of the transistor. As shown in FIG. 1, the organic thin film switch transistor containing the reversible staggered structure of the dendrimer of the present invention includes an electrically insulating substrate 1 (usually formed of glass), a gate electrode 2 (provided on the substrate), and gate insulation. A layer 3 (formed on the gate electrode 2), a drain electrode 4 and a source electrode 5 (formed on the gate insulating layer), and an organic semiconductor layer 6 (covering these thin films). The gate electrode 2 is formed of Ta, and the non-electrode electrode 4 and the source electrode 5 are formed of Au. The organic semiconductor layer 6 is formed from a third-generation dendrimer (synthesized in Synthesis Examples 1 to 6 and having hole-transport and electron-transmission conductivity) (represented by the formula (8)). An organic thin film switching transistor was prepared as follows. First, T a is deposited on an electrically insulating substrate 1 through a mask gas to form a gate electrode 2. The surface of the gate electrode 2 is oxidized to form the gate insulating layer 3 by oxidizing 43 312 / Invention (Supplement) / 92-11 / 92123418 200404833. Then, Au is deposited on the gate insulating layer through a mask gas to form a drain electrode 4 and a source electrode 5. The dendrimer (formula (8)) synthesized in Examples 1 to 6 was applied thereon by an inkjet coating method to form an organic semiconductor layer 6. The channel length is 12 microns. The carrier mobility of the organic thin film switching transistor (measured by the time-of-flight method) was found to be 6xl0-1 c m2 V_ 1 s_ 1. The on / off current ratio (obtained by evaluating the current-voltage characteristics) was found to be at a level of 1.06. The obtained carrier mobility and the on / off current ratio are also equivalent to similar transistors containing a-S i currently used. The results related to the transistor of Comparative Example 1 shown below show that the performance of the organic thin film switching transistor can be completely improved by using the dendrimer of the present invention. <Comparative Example 1> The procedure of Example 1 was repeated except that an organic semiconductor layer was formed using oligothiophene to manufacture an organic thin film switching transistor using a semiconductor layer formed from oligothiophene. The carrier mobility of the organic thin film switching transistor was found to be 8.5 X 1 0_3 cm 2 V _1 s_ 1 and the on / off current ratio was found to be a level of 103. <Example 2> Light-emitting element A light-emitting element containing the dendrimer of the present invention was prepared. Figure 2 shows this element schematically. As shown in FIG. 2, the light-emitting element containing the dendrimer of the present invention includes a transparent glass substrate 11 (for manufacturing a light-emitting element), an electrode 12 (formed in 44 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 atop), hole injection layer 13 and dendritic polymer layer (hole transport, electron transport, light emission) 14 and electrode 15, of which layers 1 3 and 1 4 are arranged on electrodes 1 2 and 1 5 between. A light-emitting element was prepared in the following manner. First, I T 0 (indium tin oxide) is formed on a glass substrate 11 for manufacturing a light-emitting element, thereby forming an electrode 12 serving as a positive electrode. The hole injection layer 13 is provided in the form of a thin film through a spin coating method at room temperature, and is provided from a mixture of poly (ethylene dioxythiophene) and poly (styrene sulfonate) sodium. The thickness of the film is 50 nm. The dendrimer layer (hole transport, electron transport, light emission) 14 is a dendrimer synthesized in Examples 1 to 6 in a thin film form through a spin coating method at room temperature (Example ( 8)) solution in tetrahydrofuran. The thickness of the film is 50 nm. Next, an aluminum / lithium (9: 1) alloy gas is deposited to form an electrode 15 as a negative electrode. Thus, a light-emitting element was prepared. The light-emitting element was activated by applying a predetermined voltage, and the initial brightness of the emitted light was measured to be 1,500 c d / m2. The time required to reduce the initial brightness to half the value was determined to be 3,000 hours or more. The emitted light has a peak wavelength of 450 nm. The results related to the transistor of Comparative Example 2 shown below show that the device performance can be thoroughly improved by using the dendrimer of the present invention. <Comparative Example 2> The procedure of Example 2 was repeated except that the light-emitting layer was formed using poly (hexylthiophene) to manufacture a light-emitting element having the same structure. The light-emitting element was activated by applying a predetermined voltage, and the initial brightness of the emitted light was measured to be 8 0 c d / m2. The time required to reduce the initial brightness to half the value 45 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 was measured as 800 hours. <Example 3> Organic solar cell element An organic solar cell element containing the dendrimer of the present invention was prepared. Figure 3 shows this element schematically. As shown in FIG. 3, the organic solar cell element containing the dendrimer of the present invention includes a transparent glass substrate 21, an electrode 2 2 (formed on the substrate), an electrode 24, and an electrode disposed between the electrodes 2 2 and 24. 2. Dendritic polymer layer 2 3. An organic solar cell element was prepared as follows. First, I TO is formed on a glass substrate 21. The dendrimer layer (hole transport, electron transport, light emission) 2 3 is a thin film, which is prepared by spin coating at room temperature. It contains copper phthalocyanine and has been synthesized in Examples 1-6 (Formula (8 )) The dendrimer (hole conduction, electron conduction) is provided in a liquid mixture of a solution of tetrahydrofuran. The thickness of the film is 50 nm. Next, silver gas is deposited to form electrodes 24. Thus, an organic solar cell element as shown in FIG. 3 was prepared. The organic solar cell element is illuminated with light (provided from a tungsten lamp and a 400 nm or lower beam is cut). The initial density conversion efficiency was measured to be unsatisfactory from 2.1 to 2.7%. The results relating to the device of Comparative Example 3 shown below show that the device characteristics can be thoroughly improved by using the dendrimer of the present invention. <Comparative Example 3> An organic solar cell element having a structure schematically shown in Fig. 4 was prepared. As shown in FIG. 4, the organic solar cell element of Comparative Example 3 includes a transparent glass substrate 1 (Π, electrodes 102 (formed on the substrate), a power generation layer 103 (formed from copper phthalocyanine), and a conductive layer. 1 0 4 (hexaacryl triphenylene derivative), hole pass 46 312 / invention specification (supplement) / 92-11 / 92123418 200404833 transport layer 1 0 5 (by poly (ethylene dioxythiophene) Provided with a mixture of sodium poly (styrene sulfonate) and electrodes 106, these elements are in this order. Light (provided from a tungsten lamp, and a cut beam of 400 nm or lower) Organic solar cell elements were irradiated. The initial density conversion efficiency was measured to be 1.7 to 2.0%. As described above, according to the present invention, a novel dendrimer suitable for use as an organic semiconductor material can be provided in an organic solvent. It has high solubility; it is stable, that is, it is not susceptible to foreign inhibitors (such as oxygen and water); and exhibits isotropic and very high carrier conductivity. In addition, it can be made by a simple process that requires carrier conductivity and Electronic device components with significantly high carrier conductivity [Brief description of the drawings] Fig. 1 schematically shows a cross-sectional view of an organic thin film switch transistor according to Embodiment 1 of the present invention. Fig. 2 is a schematic diagram showing a light-emitting element according to Embodiment 2 of the present invention. Schematic diagram of an organic solar cell element according to Inventive Example 3. Fig. 4 is a schematic diagram showing an organic solar cell element according to Comparative Example 3. (Element Symbol Description) 1 Electrically insulating substrate 2 Gate electrode 3 Gate insulating layer 4 Drain electrode 47 312 / Inventory (Supplement) / 92-11 / 92123418 200404833 5 Source electrode 6 Organic semiconductor layer 11 Transparent glass substrate 12 Electrode 13 Hole injection layer 14 Dendrimer layer 15 Electrode 2 1 Transparent glass substrate 2 2 Electrode 23 Dendrimer layer 2 4 Electrode 10 1 Transparent glass substrate 10 2 Electrode 103 Power generation layer 104 Conductive layer 10 5 Hole transport layer 10 6 Electrode 48

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Claims (1)

200404833 The scope of patent application: 1. A branched polymer having a branched structure, the branched structure comprising a repeating unit with a branched portion, characterized in that the polymer has an aromatic amine portion at its end, and the repeating unit is Formed by a phenylene vinyl group represented by formula (1): Phantom% It is repeated one or more times. 2. The dendrimer according to item 1 of the application, wherein the aromatic amine moiety comprises at least one substance represented by formula (2): —Αι ^ —NM (2) Where Arx represents a single bond or a divalent aromatic group, and each of Ar! And Ar2 represents a monovalent aromatic group. 3. The dendrimer according to item 2 of the application, wherein the divalent aromatic group contained in the aromatic amine is a phenylene group or a naphthyl group, and the monovalent aromatic group is The group is independently selected from the group represented by formula (3): Each of R 1 and R 2 is independently selected from a hydrogen atom, a C1-C4 alkyl group, and a C1-C4 alkoxy group. 49 312 / Invention Specification (Supplement) / 92-11 / 92123418 200404833 4. If the dendrimer in the first scope of the patent application, the repeating unit suitable as the starting point of the branch structure is further combined with suitable as The central part of the core. 5. The dendrimer according to item 4 of the application, wherein the core is selected from the group represented by formula (4): 6. The dendrimer according to item 1 of the patent application scope, which is a dendrimer. 7. The dendrimer according to item 6 of the application, wherein the dendrimer is a second or higher generation. 8. An electronic device component characterized by using a dendrimer as described in claims 1 to 7 of the scope of patent application. 9. An electronic device element according to item 8 of the scope of patent application, which is a charge transfer device element. 10. The electronic device element according to item 8 of the patent application scope is a switching transistor element. 1 1 · The electronic device element according to item 8 of the patent application scope is a light emitting device element. 1 2. The electronic device element according to item 8 of the scope of patent application is a photoelectric conversion device element. 50 312 / Inventory Supplement) / 92-11 / 92123418