JPH0797219B2 - Organic electronic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an organic electronic material. More specifically, the present invention relates to an organic electronic material characterized by using a novel charge transfer complex which has not hitherto been known.

[Conventional technology]

In recent years, attention has been paid to organic electronic materials used for organic semiconductors, electrophotographic materials, organic conductors, thermistors and the like.

For example, when an organic electronic material is used as the electrophotographic photosensitive member, the organic photosensitive member has a material having charge generating ability (hereinafter referred to as charge generating material) and a material having charge transporting ability (hereinafter referred to as charge transporting material). Are used in combination, and are used by stacking a charge generation layer and a charge transport layer, or by forming a layer in which a charge generation material is dispersed in a charge transport material. Holes or electrons can be considered as the charge to be transported, but as the charge transport material having an electron transport ability, polyvinylcarbazole (PVK) and trinitrofluorenone (T
Only a 1: 1 mixture of (NF) has been put into practical use,
Most of the charge transport materials were those having a hole transport property such as pyrazoline and hydrazone. A photoreceptor using a conventional charge transport material having a hole transporting ability is used by laminating a substrate, a charge generation layer and a charge transport layer in this order.
The problem that the photoreceptor is chemically deteriorated by the negatively charged ozone cannot be avoided because it is inevitably negative, and printing durability is higher than that of an inorganic photoreceptor such as a-Se or a-Si. Has the drawback of being extremely low in sex,
Further, there is a drawback that a photoconductor that can be charged to both positive and negative polarities (bipolar photoconductor) cannot be obtained. From these points, the advent of a photoconductor which can be positively charged, that is, which can transport electrons, and which can be charged to both polarities is desired.

As such an organic electronic material, tetracyanoanthraquinodimethane and its derivatives have been proposed (for example, JP-A-57-149259 and JP-A-58-55450).

The tetracyanoanthraquinodimethanes are compounds having a basic skeleton represented by the following formula and substituted with various substituents.

These tetracyanoanthraquinodimethanes are compounds synthesized from the corresponding anthraquinones and are useful compounds as organic electronic materials such as organic semiconductors, organic photographic materials, organic conductors and thermistor materials.

Furthermore, compounds in which at least one of the two benzo-condensed rings of tetracyanoanthraquinodimethanes is replaced with another hetero-condensed ring and two dicyanomethylene groups are modified into various groups have also been proposed. (Japanese Patent Application Sho 60-171161
issue).

[Problems to be solved by the invention]

The present inventors have found that a novel charge transfer complex of a compound related to a benzoquinone derivative, which is a raw material of the above compound, is useful as an organic electronic material.

Therefore, an object of the present invention is to provide an organic electronic material using a charge transfer complex of a benzoquinone derivative and an electron donor.

[Means for solving problems]

That is, the present invention has the following general formula [In the formula, One of Represents a heterocycle, and when one represents this heterocycle, the other is However, R ₁ , R ₂ and R ₃ are independent of each other and represent H, alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group. ] The organic electronic material characterized by using the charge transfer complex of the benzoquinone derivative and electron-donating compound shown by these is provided.

Specific examples of the benzoquinone derivative represented by the general formula (I), which is a raw material of the charge transfer complex used in the present invention, are shown by the structural formulas below.

Among the compounds of the above-mentioned specific examples, the compound of the formula (3) is novel, and the structural steps and literatures including it are shown below.

Examples of the electron donor that is the other raw material of the charge transfer complex of the present invention include aromatic compounds such as benzene, naphthalene, anthracene, pyrene and perylene, p-phenylenediamine and similar condensed ring type aromatic compounds. Compound,
Examples thereof include sulfur-containing electron donating compounds such as tetrathiafulvalene (TTF), tetrathiatetracene (TTT) and tetramethylthiafulvalene (TMTSF). Also,
Polymers such as polyvinylcarbazole (PVK) can also be used.

These electron donors and other examples are shown below by structural formulas.

Such a charge transfer complex of the present invention can be produced by the following method.

(1) A method in which a compound represented by the general formula (I) and an electron-donating compound are reacted in a solvent in which both of them are soluble and the complex formed is insoluble or dissolvable to precipitate the product.

(2) A method in which both the raw material of the compound represented by formula (I) and the electron-donating compound and the product are reacted in a soluble solvent, and then a poor solvent for the product is added to precipitate the product.

(3) Similarly, a method in which both raw materials and a product are reacted in a soluble solvent, and the reaction solvent is distilled off with or without adding a poor solvent for the product to precipitate the product.

〔The invention's effect〕

A charge transfer complex of a benzoquinone derivative represented by the general formula (I) and an electron donor is useful as an organic electronic material,
Organic electrophotographic materials, capacitor materials, low resistance thermosensitive elements,
It can be used as a sensor material. For example, when it is used as a charge transporting material for an electrophotographic photoreceptor, it can be used together with a binder resin such as polycarbonate or polyester to form a charge transporting layer, or it can be contained in a charge generating layer together with a charge generating material.

〔Example〕

Reference example 1. Formula (3) Synthesis of benzoquinone derivative represented by: 12.3 g (50 mmol) of chloranil (I) is suspended in 180 ml of DMF and cooled to 10 ° C. in an ice bath. Malon nitrile CH
₂ (CN) ₂ , (CN) ₂ C ₂ S ₂ Na ₂ prepared from carbon disulfide and sodium hydroxide [see J. Org. Chem., 29 , 660 (1969)] 1
A solution prepared by dissolving 8.4 g (99 mmol) in 50 ml of water was added dropwise to the above DMF solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours, then 50 ml of water was added and ice-cooled. The precipitate was separated, washed with 100 ml of water, and recrystallized from THF-methanol to give the following compound. 10.09 g (yield 52%) of the hydroquinone derivative represented by
Obtained as yellow-green needles (melting point> 384 ° C). 2.0 g (5.18 mmol) of this hydroquinone derivative was suspended in 150 ml of anhydrous THF, and 1.41 g (6.2% of dicyanodichloro-p-benzoquinone).
A solution of 2 mmol (1.2 eq) in 20 ml dry THF is added dropwise over 20 minutes. Stir for 4 hours at room temperature and separate BDTQ purple crystals. Yield 1.52g (76%).

Melting point: 397 ℃ or higher (decomposition); Mass: m / e 384 (M ⁺ , 100%); Elemental analysis: Calculated as C ₁₄ N ₄ S ₄ O ₂ : C 43.74 N 14.57 S 33.76 Measured value: C 43.74 N 14.68 S 33.24 Reference example 2.BDTIQ- DBTTF (1: 1) complex To a boiling solution of 38 mg (0.1 mmol) of (2) in 35 ml of anhydrous CH ₂ Cl ₂ , add 30 mg (0.1 mmo) of (A) in 10 ml of anhydrous CH ₂ Cl _2.
l) The dissolved boiling solution was added, and the mixture was heated and stirred for 5 minutes. The crystals precipitated after cooling were separated to obtain 67 mg of 1: 1 complex.

Navy blue crystal. Melting point 255-258 ° C (decomposition).

Elemental analysis: C HN calculated as C ₂₈ H ₈ N ₄ S ₈ O ₂ (%) 48.82 1.17 8.13 Measured value (%) 48.36 0.96 7.98 Reference example 3. BDTIQ-TTMTTF (1: 1) complex 25 mg (0.07 mmol) of (B) was added to a boiling solution prepared by dissolving 25 mg (0.07 mmol) of (2) in 20 ml of CH ₂ Cl ₂ free, and the mixture was heated and stirred until a black precipitate began to precipitate. Separate after cooling down 1:
49 mg of one complex are obtained. Black precipitate. Melting point 184-186 ° C (decomposition).

Elemental analysis: C HN calculated as C ₂₄ H ₁₂ N ₄ S ₁₂ (%) 37.28 1.56 7.25 Measured value (%) 37.13 1.25 8.07 Reference example 4. BDTQ-TMTSF (1: 1) complex To a boiling solution of 29 mg (0.08 mmol) of (3) in 30 ml of anhydrous CH ₂ Cl ₂ , add 34 mg (0.08 mm) of (G) in 25 ml of anhydrous CH ₂ Cl _2.
ol) Add the dissolved boiling solution, heat and stir for 5 minutes, then cool to obtain 61 mg of 1: 1 complex as a black precipitate.

Melting point 220-230 ° C (decomposition); Elemental analysis: C H N calculated as C ₂₄ H ₁₂ N ₄ S ₄ Se ₄ O ₂ (%) 34.63 1.45 6.73 Measured value (%) 35.10 1.30 7.07 Reference example 5. BTDTQ-TMTTF (1: 1) complex A boiling solution of 26 mg (0.1 mmol) of (D) in 5 ml of CH ₂ Cl ₂ was added to a boiling solution of 32 mg (0.1 mmol) of (4) in 15 ml of CH ₂ Cl ₂ . After cooling, 55 mg of 1: 1 complex was obtained as a greenish gray precipitate. Melting point 258 ℃ or higher (decomposition).

Elemental analysis: C H calculated as C ₁₈ H ₁₂ O ₂ S ₁₀ (%) 37.22 2.08 Measured value (%) 37.04 2.09 Reference example 6. BTDTQ-TTT (1: 1) complex 32 mg (0.1 mmol) of (4) is dissolved in 40 ml of CH ₂ Cl ₂ and 35 mg (0.1 mmol) of (H) is extracted with the above solution for 24 hours using a Soxhlet extractor. 1: 1 complex 4 as black precipitate after cooling
You get 0 mg. Melting point 400 ℃ or more (decomposition).

Elemental analysis: C ₂₆ calculated as C ₂₆ H ₈ O ₂ S ₁₀ (%) 46.40 1.20 Measured value (%) 47.52 1.46 Reference example 7. DTPQ-TTT (1: 1) complex 32 mg (0.1 mmol) of 1 was suspended in 250 ml of CH ₂ Cl ₂ , and 35 mg (0.1 mmol) of (H) was extracted with the above suspension for 24 hours using a Soxhlet extractor. Concentrate to 50 ml to give 50 mg of 1: 1 complex as a brown precipitate. Melting point 400 ° C or higher.

Example 1 Conductivity of Charge Transfer Complex A charge transfer complex composed of a combination of a donor (electron donor) and an acceptor (electron acceptor) shown in Table 1 below was compared as a pellet by a two-terminal method or a four-terminal method. The result of obtaining the resistance value (ρ / Ωcm) is shown below.

Claims (1)

[Claims] 1. The following general formula (I): [In the formula, One of Represents a heterocycle, and when one represents this heterocycle, the other is However, R ₁ , R ₂ and R ₃ are independent of each other and represent H, alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group. ] The organic electronic material characterized by using the charge transfer complex of the benzoquinone derivative and electron donating compound shown by these.