JPS63241548A - Organic electronic material - Google Patents

Abstract

PURPOSE:To enable the electrification to bipolarities by using a charge transfer complex of a specified benzoquinone derivative and an electron donative compd. for the titled material. CONSTITUTION:The charge transfer complex of the benzoquinone derivative shown by formula I and the electron donative compd. is used for the titled material. The benzoquinone derivative shown by formula I is exemplified by the compd. having the structural formula shown by formula II. And, the electron donative compd. is exemplified by an aromatic compd. such as benzene, naphthalene, anthracene, pyrene and perylene, etc., p-phenylene diamine and its similar condensed ring type aromatic compd., and a sulfur-contg. electron donative compd., such as tetrathiafulvalene and tetrathiatetracene, etc. Thus, the photosensitive body capable of the electrification to the positive and negative bipolarities is obtd.

Description

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

[Conventional technology]

In recent years, organic electronic materials used for organic semiconductors, electrophotographic materials, organic conductors, thermistors, and the like have attracted attention.

For example, when an organic electronic material is used as an electrophotographic photoreceptor, the organic photoreceptor is a material having charge generation ability (hereinafter referred to as charge generation material) and II! Materials that have charge transport ability (hereinafter referred to as charge transport materials) are used in combination, and a charge generation layer and a charge transport layer are laminated, or a layer in which a charge generation material is dispersed in a charge transport material is used. It is used as The charges to be transported may be holes or electrons, but a 1=1 mixture of polyvinylcarbazole ()'VK) and trinitrofluorenone (TNF') is currently available as a charge transporting material with electron transporting ability. Most of the charge transport materials were those with hole transport properties such as pyrazoline and hydrazone. A conventional photoreceptor using a charge transport material having hole transport ability is used by laminating a substrate, a charge generation layer, and a charge transport layer in this order.
Since the photoreceptor must be charged with negative polarity, it is impossible to avoid the problem that the photoreceptor is chemically altered by negatively charged ozone. It has the disadvantage that printing durability is significantly lower than that of a photoreceptor, and furthermore, it has the disadvantage that a photoreceptor that can be charged to both positive and negative polarities (ambipolar photoreceptor) cannot be obtained. From these points, it is desired to develop a photoreceptor that can be positively charged, that is, that can transport electrons, and furthermore that can be charged to both polarities.

Tetracyanoanthraquinodimethane and its derivatives have been proposed as such organic electronic materials (for example, JP-A-57-149259, JP-A-58-55450, etc.).

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

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

Furthermore, we also proposed a compound in which at least one of the two fused metal rings of tetracyanoanthraquinodimethanes was replaced with another fused heterocyclic ring, and two dicyanomethylene groups were modified into a cyclogroup. has been done (% 17116/1986)
No. 1).

[The shortcomings that the invention attempts to solve]

The present inventors have discovered that lJi order charge transfer complexes of analogues of benzoquinone derivatives, which are raw materials for the above compounds, are useful as organic electronic materials.

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 represents a ring of the following general formula, and when one represents this petero ring, and R3 are independent of each other, H, alkyl, aryl, aryl-substituted alkyl, alkokene, halogen,
Represents a nitro, cyanide or carboxylic acid ester group.

The present invention provides an organic electronic material characterized in that it is used as a charge transfer complex of a benzoquinone enzyme conductor and an electron-donating compound as shown in the following.

A specific example of the benzoquinone derivative represented by the above general formula (I), which is a raw material for the charge transfer complex used in the present invention, is shown in the structural formula below.

(BDTQ) (BTDTQ) (BDTTO) As the electron donor which is the other raw material for the charge transfer complex of the present invention, for example, aromatic compounds such as benzene, naphthalene, anthracene, pyrene, perylene, etc. - fluorinated diamine and similar fused ring type aromatic compounds,
Tetrathiafulvalene (TTF), tetrathiatetracene (TTT) and tetramethylthiafulvalene (TM
Examples include sulfur-containing electron-donating compounds such as TS1i'). It is also possible to use polymers such as polyvinylcarbazole (PVK).

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

萱H3 Such a charge transfer complex of the present invention was developed as follows!
It can be manufactured by a method.

(I1 A method in which a compound represented by general formula (I) and an electron-donating compound are reacted in a solvent in which both are soluble and the resulting complex is insoluble or sparingly soluble to precipitate the product.

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

(3) Similarly, a method in which both raw materials and the product are reacted in a 0T-soluble solvent, and the reaction solvent is distilled off to precipitate the product with or without adding a poor solvent for the product.

〔Effect of the invention〕

A charge transfer complex of a quinone conductor and an electron donor represented by the general formula (I) is useful as an organic electronic material,
Organic electrophotographic materials, capacitor materials, low resistance heat-sensitive elements,
It can be used for sensor materials, etc. For example, when used as a charge transport material for an electron source, it may be used together with a binder resin such as polycarbonate or polyester to form a charge transport layer, or it may be incorporated in a charge generation layer together with a charge generation material. Hiru.

〔Example〕

Reference Example 11 Synthesis of a quinone derivative represented by formula (3) Lorani #(I) 12.39 (50 mmoffi)
is suspended in 180° C. DMF and cooled to 10° C. in a water bath. Malonitrile CH2 (CN)2 prepared from carbon disulfide and sodium hydroxide (cN)2C2
S2NI! L2 (J, Org, Chem,, 29.6
60 (I969)] 18.49 (9 pull round 0ffi)
A solution of 50 - dissolved in water was added to the previous DM1i' solution.
After adding dropwise over 0 minutes and stirring at room temperature for 5 hours,
Add 50% of water and cool on ice. The precipitate was separated in a furnace, washed with 100% water, and then recrystallized from THF'-methanol to obtain a hydroquinone derivative represented by the following formula, 10.099% (yield 52%), yellow-green needle crystals (melting point) 384°C). This hydroquinone derivative 2.09 (5,18 mmo
Q) was suspended in 150- of anhydrous TH1' and dicyanodichloro-p-benzoquinone 1.419 (6,22r
rmoQ, 1.2 equivalents) in 20 ml of dry THF is added dropwise over 20 minutes. Stir at room temperature for 4 hours and separate the purple crystals of BDTQ. Collection d1.529 (
76%).

Melting point: 397℃ or higher (decomposition); cBrm 2203c1n-”, ++N Mass:!IIL/e 384 (M, 100%);
Elemental analysis: Calculated value as C14N4S40□: c 43.74 N 14.57 8 3
3.76 actual value: C43,74N 14.68 8 3
3.24 Reference example 2. BDTIQ-DB'rT1i'
(I: 1) complex (2) (
Add (2) to AJ35aJ anhydrous CH2 (384(0)
゜1 mmoffi) To the boiling solution, add 10 d of anhydrous CH2CIL2 to 309 (0,1 mmoffi)
) The dissolved boiling solution was added, and the mixture was heated and stirred for 5 minutes. After cooling, the precipitated crystals are separated from each other to obtain a 1:1 complex 67 cape.

Dark blue crystal. Melting point 255-258°C (decomposed).

KEr.

ν. N, ~2203 an p Elemental analysis” HN calculated value as C28H8N4S802 (%l 48.82 1.17 8.13
Actual value (%) 48.36 0.96 7.98
Reference example 3. BDTIQ-TTMTTF (I: 1
) Complex (2) (2577JP (0,
07mm0fi) into the boiling solution (25 W
(0.07 mmol) was added, and the mixture was heated and stirred until a black precipitate started to precipitate. After cooling, the mixture was separated into 49 parts of a 1:1 complex. Black precipitate. Melting point 184-186°C (decomposed).

K11r.

ν, 2207 beliefs.

CN elemental analysis CHN calculated value (%) as C24H1□N4S1□ 37.28 1.56 7.25
Actual value (%) 37.13 1,25 8.07
Reference example 4. BDTQ-TMTSF (I: 1”)
6 bodies (3) (G) 30tne of anhydrous CH2 ((3) to J2 29”f
(0.08 mmo.

A boiling solution of 34 ``S'' (0.08 mmol) dissolved in 25 m/g of anhydrous CH2Cl12 was added to the boiling solution, heated and stirred for 5 minutes, and cooled to form a 1:1 complex 61 as a black precipitate. ■ Get.

Melting point: 220-230°C (decomposition); υKBr: 2202m.

N Elemental Analysis”C as C24H12N4S4S0402
HN Calculated value 34.63 1.45 6.73 Actual value
35.10 1.30 7.07 Reference example 5. B
TDTQ-TMTTI' (I: 1) complex (4)
(to) 15mj ca2cc, K (43 to 32719 (0
, 1rrmol) of 5-(H2C
A boiling solution of 26 capes (0,1 mmo Q) of 2 mmol was added. After cooling, green ash 1) as color precipitate 1:
55 µ of the 1 complex are obtained. Melting point: 258°C or higher (decomposition).

Elemental analysis 2C□8H12O□S□. Closing CH Calculated value 37.22 2.68 Fresh value 37.04 2.09 Reference example 6. BTDTQ-TTT (I: 1) complex (4) (equal 40 ml (Q C) 12C12K (4) wo 32 '1
17 (0,1 mmoffi) flJ filter using a Soxhlet extractor (H) 35 ■ (0,1 (decomposed)).

Elemental analysis: CH as C26H80□Sio Calculated value 46.4 Q il 1.20 Actual value
47.52 1.46 Reference example 7. DTPQ-TTT (I: 1) complex (
I) (Bo250 txttl') Add 1 to CH2Cl2 from 32~(
0,1 Peng 02) Suspend and use a Soxhlet extractor (
H135q (0.1 mmol) was added to the above suspension for 24 hours.
Extract time. Concentrate to 50 ml to obtain 50 mq of 1:1s product as a brown precipitate. Melting point: 400℃ or higher.

Example 1. Electrical conductivity of charge transfer complexes Regarding charge transfer complexes consisting of a combination of a donor (electron donor) and an acceptor (electron acceptor) shown in Table IK below, the specific resistance value ( The results of calculating ρ/Ω are shown below.

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ One of these is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables etc. showing the heterocycle shown by ▼, and when one side represents this heterocycle, the other one is ▲ mathematical formula, chemical formula,
There is a table etc. ▼ is also acceptable, R_1, R_2 and R_3 are mutually independent, H, alkyl,
Represents aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group. ] An organic electronic material characterized by using a charge transfer complex of a benzoquinone derivative and an electron donating compound.