JPH02272006A - Styrenic copolymer containing hydrazone group in side chain and production thereof - Google Patents

Abstract

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

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a novel styrenic copolymer having a hydrazone group and a method for producing the same, and more particularly, to a method for producing an electron copolymer using a charge generation material and a charge transfer material. The present invention relates to a styrenic copolymer having a hydrazone group that has an excellent function as a charge transfer material in photographic photoreceptors, and a method for producing the same.

[Prior art and its problems] Conventionally, selenium (Se) and cadmium sulfide (CdS) have been used as photoconductive materials for photoreceptors used in electrophotography.
), zinc oxide (ZnO>, amorphous silicon (a
-3i) and other inorganic substances.

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).
There are two types of photoreceptors: a multilayer structure with a functionally separated type photoreceptor in which charge transfer material (called a 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 concentration of the transfer material (e.g., triphenylamine compounds) in the binder (e.g., polycarbonate) (Takahashi, Mibayashi, Yokoyama, Electrophotography). , 25.
16 (1986)). If the concentration of the mobile material is increased, the mobility will increase, but the physical properties will deteriorate, such as cracking. Furthermore, mechanical wear is increased during the passage of the paper during printing. Therefore, it is difficult to add charge transport materials in binders at high concentrations.

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

[Means for Solving the Problems 1] As a result of continuing research in view of the conventional situation, the present inventors have found that by introducing a charge transfer agent into the side chain of a polymer, the charge transfer agent has a high S. It was found that it showed high mobility.

That is, the present invention provides a compound represented by the following formula: -[I] (wherein, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group) A molecular weight 1 characterized by consisting of a structural unit and a structural unit represented by the formula:
,000 to 500,000 hydrazone groups in the side chain.

In addition, the manufacturing method includes a 4-formylstyrene-based copolymer consisting of a structural unit represented by the symbol [■]; and a structural unit represented by the formula [■]: General formula [IV]: (Formula (wherein, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group). ; ...[V] (wherein R has the same meaning as above) A hydrazone group-containing stylinone compound and a stylinone compound of the formula [
Vl]: It is characterized by avoiding copolymerization with styrene represented by:

The styrenic copolymer having a hydrazone group in its side chain according to the present invention can be produced, for example, as follows.

That is, the first method is to first prepare a Grignard reagent of 4-chlorostyrene, and then add dimethylform 7mide (
DMF) is added to produce 4-formylstyrene (
W, J, Date, L, 5tarrand
C, W, 5trobel, J, Org.
Chem, 26.1965°2225). Next, after protecting the aldehyde group of 4-formylstyrene as an acetal, the compound and styrene are polymerized in the presence of a suitable polymerization initiator, and then hydrolyzed in an acidic solution to remove the acetal group. Said - Throwing coins [n
] and 4- consisting of the structural unit represented by the formula [I [[ ]
Manufacture a formylstyrene copolymer. Next, this copolymer and the above-mentioned coin [! The styrenic copolymer of the present invention can be obtained by reacting with a hydrazine compound represented by V].

The second method is to add a desired 1,1-diarylhydrazine compound to 4-formylstyrene produced in the same manner as above, and to condense it in the presence of an acidic catalyst. , a hydrazone group-containing styrene compound represented by the above-mentioned formula [V] is produced. This monomer and styrene [V! ] The styrenic copolymer of the present invention can also be obtained by polymerizing using a polymerization initiator if necessary.

The copolymer 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] Examples of the present invention will be described in detail below.

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

(In the formula, X and y each represent an integer of 1 or more.) 14.7 g of metallic magnesium, 20 m of ethyl ether, and a small amount of ethyl bromide were added to a 1R flask and heated. to activate magnesium. Furthermore, 81.8 g of 4-chlorostyrene/tetrahydrofuran (THE
>400 d of solution was added over 3 hours. During the reaction, heat was generated and the temperature reached a high temperature, so the reaction solution was kept at 50° C. or lower by cooling in a water bath.

After the dropwise addition was completed, the reaction was continued at room temperature for approximately 2 hours.

43.8 g of dimethylformamide (DMF) was added dropwise over 2 hours, and the mixture was left overnight at room temperature.

500 ml of ethyl ether was added, 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 sulfate. After distilling the ether, I want to distill it to produce 4-formylstyrene, which has a boiling point of 70℃/
0.8mmHg>. The yield was 42g (63%).

66 g of compound (1) produced by the above method, 92.5 g of 1゜1-diphenylhydrazine, 300 g of benzene
, and a small amount of para-toluenesulfonic acid was charged into a 500 d flask equipped with a Dean-Starck receiver and heated to reflux for 2 hours. After the reaction was completed, benzene was removed and recrystallized from methanol to obtain Compound (2) as a pale yellow solid with a melting point of 79°C.

The compound (2>15g, styrene 5g, and benzene 15d) was placed in a Kyukekko J1 Mommedo 50 WIR flask, and azobisisobutyronitrile (AIBN>0.5g) was added to a colander.60
After polymerization was carried out at ℃ for 24 hours, the polymerization solution was poured into a large amount of methanol. The obtained solid was dried at 50°C under reduced pressure. Yield 17.5 g, weight average molecular weight 180.0
Compound (3) with a number average molecular weight of 84.000 and a number average molecular weight of 84.000 was obtained.

Example 2 In this example, a styrenic copolymer represented by formula (3) was produced by a method represented by the following reaction formula.

(In the formula, X and y each represent an integer of 1 or more) 100ai! 5 g of poly(p-formylstyrene styrene), 1 1,1-diphenylhydrazine in a flask
59. Prepare 50 d of tetrahydrofuran (THF),
The reaction was carried out at the lowest temperature for 4 hours. After the reaction was completed, THE was distilled off under reduced pressure, 50 d of benzene was added, and the solution was poured into 500 d of methanol. The obtained solid product was filtered and then dried to produce compound (3). Collection 1
It was 12.3 g.

Application example 1 A2 in which a base layer made of nylon is formed on a substrate, and a butyral film containing phthalocyanine (<0.1g thickness) is coated on the base layer as a charge generation layer.
A solution of the compound (3)/methylene chloride (1:1 weight ratio) was applied onto the substrate and baked at 80'C for 130 minutes to form a charge transfer layer with a thickness of 15 cm.

After bringing the surface potential to -1054V with a 15kV corona discharge using an electrostatic copying tester, irradiation with light at an illuminance of 5 lux, time (seconds) until the surface potential becomes 1/2. was calculated, and the half-reduced exposure i1E,/2 (lux·sec) was obtained. The result is V. = 1000 volts and E1/2 = 0.96 lux·sec, which showed very high mobility. 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 diagram, 1 is hehe! 2 is a charge generation layer, 3 is a charge transfer layer, and 4 is an underlayer.

[Effects of the Invention] As explained above, the novel styrenic copolymer of the present invention can be used as a charge transfer material in electrophotographic photoreceptors.
When used as a material, it has excellent mechanical properties and high mobility, and is expected to be useful as a material with excellent functions.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of an electrophotographic photoreceptor using a copolymer obtained in one example of the present invention. 1... Aj7 substrate 2... Charge generation layer 3... Charge transfer layer 4... Base layer

Claims (3)

[Claims] (1) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group) Molecular weight 1 characterized by being composed of structural units shown by the unit and formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼
,000 to 500,000 hydrazone groups in the side chain. (2) A 4-formylstyrene copolymer consisting of a structural unit represented by the formula; , general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group) General formulas characterized by the reaction of Molecular weight consisting of the structural unit shown by ▼ 1,000-500
,000 hydrazone group in the side chain. (3) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a dialkylamino group) Hydrazone represented by A general formula characterized by the copolymerization of a group-containing styrene compound and styrene represented by the formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R has the same meaning as above) and the formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Molecular weight 1,000 to 500
,000 hydrazone group in the side chain.