JPS58140069A - 9-ethylcarboazole-3-carbaldehyde hydrazone compound - Google Patents

Abstract

NEW MATERIAL:The 9-ethylcarbazole-3-carboaldehyde hydrazone compoud of formulaI(R is propyl, butyl, allyl, methylbenzyl, methoxybenzyl, benzoyl, alkoxyethyl, phenoxyethyl, cinnamyl, phenyl or chlorophenyl; X and Y are H or halogen; provided that when R is phenyl, then X is halogen). EXAMPLE:9-Ethyl-6-chlorocarbazole-3-carboaldehyde diphenylhydrazone. USE:A photosensitive material for electrophotography. It has high sensitivity and durability. PROCESS:The compound of formulaIcan be prepared e.g. by reacting hydrazine of formula II or its mineral acid salt with the aldehyde of formula III in a solvent such as methanol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel! -Ethylcarbazole-3-rubaldehyde hydrazo/compound.

Conventionally, selenium has been used in the photosensitive layer of electrophotographic photoreceptors.

Inorganic photoconductive materials such as sulfide silica and zinc oxide were widely used. In recent years, research has advanced on the use of organic photoconductive substances in the photosensitive layer of electrophotographic photoreceptors, and some of these have been put into practical use.

Organic photoconductive substances are compared to inorganic photoconductive substances.

It has advantages such as being lightweight, easy to form a film, easy to manufacture photoreceptors, and depending on the type, transparent photoreceptors can be manufactured.

Many studies have been conducted on photoconductive polymers such as polyvinylcarbazole as organic photoconductive materials, but these polymers do not necessarily have film properties,
It does not have sufficient flexibility or adhesion, and when made into a thin film, it tends to crack and peel off from the substrate. Large amounts of plasticizers, binders, etc. are added to improve these drawbacks, but these tend to cause other problems such as lower sensitivity and increased residual potential than K, so they are not practical photoreceptors. was extremely difficult to obtain.

On the other hand, for organic low-molecular photoconductive compounds, polymers with excellent film properties, removability, adhesive properties, etc. can be selected as binders, making it easy to obtain photoreceptors with excellent mechanical properties. However, it has been difficult to find compounds suitable for making highly sensitive photoreceptors.

Therefore, the present inventors conducted intensive research on organic low-molecular photoconductive compounds that provide electrophotographic photoreceptors with high sensitivity and high durability, and found that a specific new deethylcarbazole-J- The present invention was achieved by discovering that a cycloaldehyde hydrazone compound is suitable.

That is, the gist of the present invention is as follows.

General formula [1] ? ^ engineering (In the formula, 'R is a propyl group, a butyl group, an allyl group.

methoxybenzyl group, benzoyl group, alpoxyethyl group, phenoxyethyl group, cinnamyl group, phenyl group, or chlorophenyl group;
! ,! indicates a hydrogen atom or a halogen atom. However, when R is phenyl.

I represents a halogen atom. ) Two-ethylcarbazole-! - Existing in rubalaldehyde hydrazone compounds.

The present invention will be described below as expressed by the above general formula (1)! Specific examples of dracine compounds (hereinafter referred to as hydrazone compounds of the present invention) in ethylcarbazole-3-rubaldehyde include the compounds shown in Table 1.

The hydrazone compound of the present invention represented by the general formula [I] can be produced, for example, by the method shown below.

One method is to mix drazine or its mineral acid salt represented by the general formula (where R and ! have the same meanings as in the general formula [:I)K] with the general formula ] ?・4 (wherein, X has the same meaning as in general formula (1)) can be reacted with an aldehyde represented by the formula (1) in a solvent to obtain a stone. As a solvent, a wide range of non-reactive organic solvents can be used, but preferred solvents include alcohols such as methanol and ethanol, protic solvents such as acetic acid, ethers such as dioxane in tetrahydrofuran, toluene, Aromatic swelling hydrogen such as benzene can be used alone or in combination.

Another method is to combine hydrazine or its mineral acid salt represented by the general formula (N) (wherein τ has the same meaning as in the general formula [■]) and an aldehyde represented by the general formula (11). is reacted in a solvent, and then the general formula (V)R-Z...
(V) (wherein R has the same meaning as in general formula (1) and 2 represents a negative group such as a halogen atom) and lI$IIφ, preferably.

By reacting under basic conditions, the hydrazone compound of the present invention can be obtained. Also, at this time, it may be effective to use a phase transfer catalyst such as quaternary ammonium chloride. As a solvent, a wide range of non-reactive solvents can be used, including protic solvents such as water, alcohol, aprotic polar solvents such as dimethyl sulfoxide and dimethylformade, and acetate. /, -Ketone steel of one-butanone group, benzene, toluene.

Aromatic hydrochloride such as xylene, tetrahydrogen w7, ether steel such as dioxane, dichloromethane, /, J-dichloroethane, chlorinated vertical hydrogen, or pyridine, triether, etc. alone. Or it can be used in combination.

Sodium hydride is used. As a phase transfer catalyst, penzyltrimethylammonium chloride is used.

The hydrazone compound of the present invention thus obtained exhibits extremely excellent performance as an organic optical semiconductor. In particular, when used as a charge transfer medium, it provides a photoreceptor with particularly high sensitivity and excellent durability.

Medium Te% Formula Xv, Xa, Im, 1g, Xb, Xl, X
3°xl is preferable because it shows high sensitivity.

The photosensitive layer of the electrophotographic photoreceptor may be of any type. For example, a photosensitive layer containing photoconductive particles that generate charge carriers with extremely high efficiency when absorbing light and a hydrazone compound added to a binder, and a charge transfer layer consisting of a hydrazone compound and a binder that generates charge carriers with extremely high efficiency when absorbing light. Examples include a photosensitive layer in which a charge generation layer made of photoconductive particles or photoconductive particles and a binder is laminated.

When the human 2-sine compound represented by the general formula CI] of the present invention is used as a charge transfer layer of a photosensitive layer consisting of two layers: a charge generation layer and a charge transfer layer.

It is possible to obtain a photoreceptor that has a high k#@廖, a small residual potential, and has excellent durability with little variation in surface potential, decrease in sensitivity, accumulation of residual potential, etc. when used repeatedly.

Such an electrophotographic photoreceptor is manufactured by the general formula [
A coating solution obtained by melting the hydrazone compound formed in step I] in a strong solvent together with a binder, and optionally adding photoconductive particles that generate charge carriers with extremely high efficiency when they absorb light. is applied onto a conductive support and dried.

It can usually be manufactured by forming a photosensitive layer with a thickness of several β to several tens of β. In the case of a photosensitive layer consisting of two layers, a charge generation layer and a charge transfer layer, the above coating liquid is applied on the charge generation layer, or the above coating liquid is applied.・The charge generation layer is formed on the charge transfer layer. It can be manufactured by forming layers.

As a copper immersion for preparing a coating solution, there is a tetra-dolpher y, /-
Examples include solvents for dissolving hydrazone compounds, such as ethers such as dioxane; chotones such as methyl ethyl ketone and cyclohexanone; and aromatic hydrocarbons such as toluene and xylene. Of course, you need to choose a book that dissolves the binder from among these books. Examples of the binder include various polymers that are compatible with hydrazone, such as polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic esters, methacrylic esters, and butadiene, polyester copolymers, and polycarbonate resins. It will be done. The amount of binder used is usually in the range of θ, t-JO times the weight of hydrazone, preferably /-10 times the weight of hydrazone.

As the photoconductive particles to be added to the photosensitive layer, well-known photoconductive particles can be used. Photoconductive particles that generate charge carriers with extremely high efficiency when they absorb light include inorganic photoconductive particles such as selenium and cadmium sulfide, and organic photoconductive particles such as copper phthalocyanine pigments, azo pigments, and perylene pigments. Photoconductive particles may be mentioned.

The photoreceptor formed in this way may also have an adhesive layer, an intermediate layer, and a transparent insulating layer, if necessary, like commercially available electrophotographic photoreceptors. As the conductive support on which the photosensitive layer is formed, any of those used in well-known electrophotographic photoreceptors can be used. Specifically, for example, a metal drum made of aluminum or steel.

Laminated sheet or fin metal foil.

Examples include vapor deposits. Further examples include plastic films, paper, etc. which are coated with a conductive substance such as metal powder, carbon black, copper sulfide, or polymer electrolyte together with a suitable binder to conductivity treatment.

The electrophotographic photoreceptor described above has high sensitivity;
It is necessary that the residual potential that causes fogging is small, that the material is resistant to heat and heat, that there is no accumulation of residual potential due to repeated use, and that there is little fluctuation in surface potential and sensitivity. For this purpose, the performance of the organic photoconductive material used is an important factor.

The hydrazone compound of the present invention is excellent in this respect, and is extremely useful as an organic photoconductive compound in that it provides a photoreceptor with high sensitivity, low residual potential, excellent stability, and poultry durability.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples which do not go beyond the gist of the invention. In the examples, "r parts" indicates "parts by weight."

Production Example 1 Two-ethercarbazole-J-carbaldehyde of G, J t (θ, t not ), ii, a f (
0,/mot) of N-tetrarosuccinic acid indo and J bait oq.
7) (0,00/moj) f) Benzoyl peroxide is reacted in Joy-benzene for one hour under reflux conditions, and after stopping the reaction, the reaction mixture is poured into 100 atm of methanol. A precipitate gradually separated out. When this precipitate was recrystallized using tetrahydrofuran and methanol, white crystals of t-ether-≦-chlorocarbazole-3-carboaldehyde represented by the following formula [VI] were obtained. The melting point of this compound is 1. /-ko, o C, the nine elemental analysis values are as follows.

Elemental analysis OHM calculated value (@49.tOta, ?Or, bait experimental value (@
To, or, feed, 1114f- Next, 4. The above aldehyde [η] of 蓼F (ko! group trot) and / of t, t f (J tw!lol),
/-Schiffzx hydrazine hydrochloride was reacted in J1σ-methanol at room temperature for a feeding time. When the generated precipitate was reconsolidated using toluene and methanol, pale yellow deether-4-chloroOcarbazole-J-carbaldehyde diphenylhydrozone represented by the above formula [x1] was obtained. The melting point of this compound is 168-1, FC,
1. Also, it was a general policy to expand the elemental analysis values.

Elemental analysis OHM calculated value (Is) 2t, dabuta, koj
? , Ri/Experimental value (@7t, Kobait!t, Jr.
De, r7 production example Cococo, 9-ethyl of JP (0, /Il/), lucarpazole! - Rubaldehyde and l, tsuf (0,/com
phenylhydrazine (oj) and 80-70% phenylhydrazine in ethanol of good quality using 80% sodium acetate as a catalyst.
Incubate the reaction for 1 hour at °C. When the generated precipitate was reconsolidated using tetrahydrofuran and ethanol, a pale yellow deethylcarbazole-3-
Carbaldehyde phenylhydrazone was obtained. The melting point of this compound was /uO,σ-/lco,OC.

0fTi.

Kiji, 13. θf (θ, Oa# moz) and the above hydrazone [■]? , / 1 (θ, σ!Co-chloro7enethole and rd dimethyl sulfoxide are 4IC in a !0-sodium hydroxide aqueous solution.
The reaction was carried out for 1 hour. The obtained precipitate was recrystallized using tetrahedral furan and methanol and filtered to give a pale yellow-white color to deethyl-carbazole-J-carboalde represented by the above formula [C] and dophenyl-(-monophenoxyethyl). -Hydrazone was obtained. Melting point of this compound/6. t-/1431::, and the elemental analysis values are as follows.9.

Elemental analysis OHN Calculated value <@rθ, 37 g, 2 baits? , 70 Experimental Values (@2De, Day In, 009.JI) The hydrazone compounds shown in Table 7 were obtained in a similar manner. Their melting points are shown in Table 1.

Application Example 1 A bisazo compound having the above structure of OHOH 7,3s and 17 parts of phenoxy tree JJl (manufactured by Union Carbide Co., Ltd., trademark FKH1'!) were dispersed in 10 parts of hexanone, and the mixture was dispersed using a sand grinder. Atomized. This dispersion is 7! A 10p thick aluminum foil coated on a polyester film with a thickness of 0.0 μm after drying. /f/- was coated on birch with a film applicator and dried to form a charge generating layer.

On top of this, add 10 parts of terethylcarbazole-J-:/
J rubaldehyde phenyl-(a-1 toxyphenolmethyl)-hydrazone (Ib) triDO moiety polymethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trademark BR-4S)
of! A solution dissolved in 70 parts of toluene was applied with a film applicator so that the film thickness after drying was 0.1 μm, followed by drying to form a charge transfer layer. In this way, an electrophotographic photoreceptor having a two-layer photosensitive layer was obtained.

Regarding the photoreceptor of
/* ') was measured and the result was 101u-X@m@O.

The half-decrease exposure amount is determined by charging the photoreceptor in a dark place by corona discharge of -NA, then exposing it to white light, and measuring the amount of exposure required for one surface potential to attenuate to half of the initial attenuation surface potential. I asked for it.

Application Example: Two-ethyl-1- is substituted for the hydrazone used in Application Example 1.
A photoreceptor was produced in the same manner as in Application Example I except that mocarpazole-J-rubaldehyde diphenylhydrazone [1h] was used.

When 1 ml t/* was measured in the same manner as in Application Example 1, met t/* W jt, I lux @ @ @ @
Met.

Sender: Mitsubishi Chemical Industries, Ltd. Proxy Physician Bentoushi Haseyo - Others/Names

Claims (1)

[Scope of Claims] (General formula [1) (wherein R is a propyl group, a butyl group, an allyl group, a methylbenzyl group, a methoxybenzyl group, a pensoyl group, an alkoxyethyl group, a phenoxyether group, a cinnabar group) basis,
A deethylcarbazole-3-carbaldehyde hydrazone compound which represents a phenyl group or a chlorophenyl group, and X and Y represent hydrogen 1.