JPH02272005A - Polystyrene compound containing hydrazone group in side chain and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject novel compound having excellent mechanical properties and mobility in a case of using as electric charge-transferring material in photosensitizer of electronic photograph dy reacting poly(formylstyrene) with specific hydrazine compound. CONSTITUTION:Poly(4-formylstyrene) composed of structural unit expressed by formula I (R<2> is 1-4C alkyl) is reacted with hydrazine compound expressed by formula II (R<1> is H, 1-4C alkyl, alkoxy or dialkylamino) to afford the aimed compound containing hydrazone group composed of structural unit expressed by formula III having 1000-500000 molecular weight in side chain.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel hydrazone group-containing polystyrene compound and a method for producing the same, and more specifically, to an electrophotographic process using a charge-generating material and a charge-transfer material. The present invention relates to a polystyrene compound having a hydrazone group that has an excellent function as a charge transfer material in the body, and a method for producing an IA thereof.

[Prior art and its problems] Conventionally, selenium (Se) and cadmium Ia chloride (Cd) have been used as photoconductive materials for photoreceptors used in electrophotography.
S), M zinc ide (ZnO), 7-E rufus silicon (
There are inorganic substances such as a-8i).

Although these inorganic photoreceptors have many advantages, they also have various disadvantages, such as being harmful and being expensive. Therefore, in recent years, many organic photoreceptors using organic materials that do not have these drawbacks have been proposed and put into practical use.

The structure of these photoreceptors includes a material that generates charge carriers (hereinafter referred to as charge generation material) and a material that receives and moves the generated charge carriers (hereinafter referred to as charge generation material).
Examples include a multilayer structure with a functionally separated type photoreceptor in which charge transfer material (referred to as charge transfer material) is formed into separate layers, and a single layer structure with a single layer type photoreceptor in which charge carrier generation and charge transfer are performed using the same material. However, multilayer structures are more widely used because they offer a wider range of material selection and higher sensitivity.

In recent years, with the development of non-impact printing technology, research and development of electrophotographic printers using laser light sources have been actively conducted. In these devices, as the device size becomes smaller and the speed increases, it is desired that the photosensitive materials have higher sensitivity in charge generation materials and higher mobility in charge transfer materials.

In the case of charge transfer materials, it is known that the mobility greatly depends on the S degree of the transfer material (e.g., triphenylamine compounds) in the binder (e.g., polycarbonate) (Takahashi, Gobayashi, Tsukiyama, Denshi et al. Photo, 25.
16 (1986)). If the concentration of the mobile material is increased, the mobility will increase or the physical properties will deteriorate, for example, cracks may occur. Mechanical wear increases as paper passes through rough printing. Therefore, it is difficult to add charge transport materials in binders at high concentrations.

The present invention has been made in view of the conventional circumstances as described above, and has excellent mechanical properties that do not cause cracking even when used at high concentrations and have high mobility. The present invention aims to provide a novel compound useful as a charge transfer material and a method for producing the same.

[Means for Solving the Problems] As a result of continuing research under these conventional circumstances, the present inventors have found that by introducing a charge transfer agent into the side chain of a polymer, a high concentration of the charge transfer agent can be obtained. It was found that it exhibits high mobility.

That is, the present invention is based on the general formula [E]; ...[E] (wherein, R1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group, and R2 represents a carbon Molecular weight 1 characterized in that it consists of a lower alkyl group having 1 to 4 atoms and a structural unit shown in Table "Ij)"
, 000 to 500,000 hydrazone groups in the side chain.

In addition, the manufacturing method is to use poly(4-formylstyrene) consisting of a structural unit represented by the following formula: -Isen [■]: (in the formula, R2 represents a lower alkyl group having 1 to 4 carbon atoms); Formula [■]; (wherein, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group); Alternatively, it is characterized by polymerizing a hydrazone group-containing styrene compound represented by the following formula [IVl:[1v1 (in the formula, R1 and R2 have the same meanings as above)].

The polystyrene compound having a hydrazone group in its side chain according to the present invention can be manufactured into a V-forming structure, for example, as follows.

That is, the first method is to first produce a Grignard reagent of 4-chlorostyrene, and then add acyl chloride to produce 4-acylstyrene.

Next, after protecting the carbonyl group of 4-acylstyrene as a ketal, it is polymerized in the presence of a suitable polymerization initiator, and then the ketal group is removed by Jl water decomposition in an acidic solution. Poly(4-acylstyrene) consisting of a structural unit represented by [ff] is produced.

Next, the polystyrene compound of the present invention can be obtained by reacting this polymer with the hydrazine compound represented by the above-mentioned -Isen [II].

In addition, in the second method, after 4-acylstyrene is 'AMed in the same manner as above, the desired 1,1-cyatoolhydrazine compound is added to the 4-acylstyrene, and condensation is carried out in the presence of an acidic catalyst. In this way, the hydrazone group-containing styrene compound represented by IVl is produced. The polystyrene compound of the present invention can also be produced by polymerizing this monomer using a polymerization initiator if necessary.

The polymer of the present invention is easily soluble in solvents such as benzene, chloroform, and methylene chloride, and is insoluble in methanol and ethanol. Furthermore, by casting a solution dissolved in methylene chloride, a hard film can be produced without any cracks, making it extremely useful as a charge transfer agent for electrophotographic photoreceptors. It is.

[Example 1 Examples of the present invention will be described in detail below.

Example 1 In this example, a polystyrene compound represented by formula (3) was produced by a method represented by the following series of reaction formulas.

Example 1 Preparation of Compound (1) Into 12 flasks, 14. J, 20 d of ethyl ether and a small amount of ethyl bromide were added and heated to activate the magnesium. Roughly, 4-chlorostyrene 81.89/tetrahydrofuran (TI-IF
) 400 ml of solution was added over a period of 3 hours. During the reaction, heat was generated and the temperature reached a high temperature, so the reaction solution was cooled in a water bath to maintain the temperature below 50'C. After the dropwise addition was completed, the reaction was continued for another 2 hours at room temperature.

Acetyl chloride (CH3-Coα) 24.0
! 1F was added dropwise over a period of 2 hours. ethyl ether 50
0ml was added to 7JO, and the reaction solution was added to a dilute aqueous hydrochloric acid solution. Extraction was performed, and the ether layer was washed with pure water and then dried over magnesium FA acid. After distilling off the ether, it is distilled to give 4-
Acetyl styrene was produced (boiling point 76°C 10.8m
mHg). The yield was 42 g (61%).

Preparation of Compound (2) Compound (1) produced by the above method 689.1° 92.59° of 1-diphenylhydrazine, 300 d of bempine, and a small amount of para-toluenesulfonic acid were placed in a 500-power flask equipped with a Dean-Starck receiver. It was charged, heated, and fast-flowed for 2 hours. After the reaction was completed, benzene was distilled off and recrystallized from methanol to obtain Compound (2) as a pale yellow solid with a melting point of 79°C.

Production of compound (3) 15 g of compound (2) and 1 benzene in a 50 d flask
5 ml was charged, and 0.5 g of azohisisobutyronitrile (AIBN) was added to the colander. After polymerization was carried out at 60'C for 24 hours, the polymerization solution was poured into a large amount of methanol. The resulting solid was dried at 50°C under reduced pressure. Yield: 13.2 g, weight average molecular weight: 220.000. 1q of compound (3) with a number average molecular weight of 100.000.

Example 2 In this example, a polystyrene compound represented by formula (3) (where n is 2) was prepared by a method represented by the following reaction formula.
(represents an integer greater than or equal to) to (7! Poly(p-acetylstyrene) in the flask
5J, 15 g of 1,1-diphenylhydrazine, and 50 m of tetrahydrofuran (THE) were charged, and the reaction was carried out at the lowest temperature for 12 hours. After the reaction was completed, T' 1-IF was distilled off under reduced pressure, and 50 m of benzene was added. ! was added, and the solution was poured into 500 d of methanol. The obtained solid product was filtered and dried to obtain compound (3). Yield 11.
It was 8g.

Application example 1 A base layer made of nylon is formed on the △j2 substrate, and a butyral film (0.1 μm thick) containing phthalocyanine is coated on the base layer as a charge generation layer!
A compound (3)/methylene chloride (1:1 weight ratio) solution was applied onto the substrate, and baked at 80'C for 130 minutes to give a 15μ
A charge transfer layer having a thickness of m was formed.

After bringing the surface potential to -1100V with a -5kV corona discharge using an electrostatic copying tester, the light was illuminated at an illumination intensity of 5 lux, and the time-opening (seconds) was applied until the surface potential became 1/2. ) was calculated, and the half-reduced exposure ME1i2 (lux/second) was obtained. The results showed a very high mobility of v po = 1000 pol l and E1/2 = 0.54 lux·sec. The mechanical properties were also very good.

Figure 1 is a schematic cross-sectional view of the photoreceptor manufactured in this application example.
In the figure, 1 is an Afl substrate, 2 is a charge generation layer, and 3 is a charge transfer v
J@, 4 is the base layer.

[Effect of the invention 1 As explained above, the novel polystyrene compound according to the present invention has excellent mechanical properties and high mobility when used as a charge transfer material in an electrophotographic photoreceptor. Therefore, its usefulness as a material with excellent functions is expected.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of an electrophotographic photoreceptor using a compound obtained in one example of the present invention. ]...△! Substrate 2... Charge generation layer 3... Center-to-centre transfer layer 4... Base map agent

Claims (3)

[Claims] (1) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group, and R^ 2 represents a lower alkyl group having 1 to 4 carbon atoms) A polystyrene compound having a molecular weight of 1,000 to 500,000 and having a hydrazone group in a side chain. (2) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2 represents a lower alkyl group having 1 to 4 carbon atoms.) Styrene) and general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group) General formula characterized by reacting with a hydrazine compound represented by; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 have the same meanings as above) From the structural unit represented by molecular weight of 1,000 to 500,00
A method for producing a polystyrene compound having 0 hydrazone groups in its side chain. (3) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group, and R^ 2 represents a lower alkyl group having 1 to 4 carbon atoms) A general formula characterized by polymerizing a hydrazone group-containing styrene compound; ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R ^1 and R^2 have the same meanings as above) with a molecular weight of 1,000 to 500,00
A method for producing a polystyrene compound having 0 hydrazone groups in its side chain.