JPH08231502A - Maleimide derivative and its production - Google Patents

Abstract

PURPOSE: To obtain a new compound useful as an acceptor compound for electrophotographic photoreceptors. CONSTITUTION: This compound is expressed by formula I [R<1> and R<2> are each H, an alkyl or a (substituted) phenyl; R<3> is a (substituted) alkyl, a (substituted) phenyl or a (substituted) cyclohexyl], which is obtained by reaction between a maleic anhydride derivative of formula II and an amine compound of the formula NH2 -R<3> in the presence of an acidic or basic catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel maleic imide derivative useful as an acceptor compound used in an electrophotographic photoreceptor and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive substances such as selenium, selenium-tellurium alloy, and zinc oxide have been widely used as photoconductive materials for photoconductors used in electrophotography. Research on electrophotographic photoreceptors using photoconductive materials has progressed, and some of them have been put to practical use. The term "electrophotographic method" as used herein generally means that a photoconductive photoconductor is first uniformly charged in a dark place by, for example, corona discharge, and then imagewise exposed to selectively discharge the charge only in the exposed portion. This is one of the image forming methods in which an electrostatic latent image is obtained, and the latent image portion is developed with toner or the like and visualized to form an image.

The basic characteristics required for such an electrophotographic photosensitive member are (1) being able to be charged to an appropriate potential in a dark place, (2) having a small discharge in a dark place,
(3) Immediate discharge by light irradiation may be mentioned. However, the conventional organic photoconductive materials do not always satisfy those requirements.

On the other hand, inorganic photoconductive substances such as selenium and zinc oxide have been known for a long time, and among them, selenium is widely put to practical use. However, recently, from the viewpoint of electrophotographic process, various requirements for a photoreceptor, that is, in addition to the basic electrophotographic characteristics described above as an example, a belt-shaped photoreceptor having a flexible shape is required. Is becoming popular. However, in the case of selenium, it is generally difficult to produce such a shape.

In recent years, in order to eliminate the disadvantages of these inorganic substances, electrophotographic photoreceptors using various organic substances have been proposed and some have been put to practical use. For example, a fluorenylidene methane compound (JP-A-60-69657)
No.), anthraquinodimethane compound (JP-A-61-23)
3750), naphthalene dicarboxylic acid imide compound (JP-A-5-25136), naphthalene tetracarboxylic acid diimide compound (JP-A-5-25174), and the like, but those which have not been sufficiently satisfied have not been obtained yet. It is the actual situation.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel maleic imide derivative which is particularly useful as an acceptor compound for positive charging and used in a single-layer type or multi-layer type electrophotographic photoreceptor, and It is to provide the manufacturing method.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive research to solve the above-mentioned problems, and as a result, found a specific group of compounds and completed the present invention. That is, according to the present invention, a maleimide derivative represented by the following general formula (I) (Formula 1) is provided.

Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.)

According to the present invention, the following general formula (II)
A phthalimide compound represented by Chemical formula 2 is provided.

Embedded image (In the formula, R ³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group.)

According to the present invention, the following general formula (II
I) A maleic acid imide derivative represented by the formula 3 is provided.

Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.)

According to the present invention, the following general formula (I
Maleic anhydride represented by general formula (I), characterized in that a maleic anhydride derivative represented by V) is reacted with an amine compound represented by general formula (V) under an acidic or basic catalyst. A method for producing an imide derivative is provided.

[Chemical 4] (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.)

According to the present invention, the following general formula (V
There is provided a method for producing a phthalimide compound represented by the general formula (II), which comprises reducing the nitrophthalimide derivative represented by I) with iron, zinc, tin or a chloride thereof and an acid. .

Embedded image (In the formula, R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group.)

Furthermore, according to the present invention, a maleic anhydride derivative represented by the following general formula (IV) and a phthalimide compound represented by the general formula (II) are reacted under an acidic or basic catalyst. The general formula (II
A method for producing a maleic acid amide derivative represented by I) is provided.

[Chemical 6] (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.)

In R ¹ and R ² of the general formulas (I) and (III) of the present invention, the alkyl group represents a methyl group, an ethyl group, a butyl group, etc., and the phenyl group has a chlorine atom as a substituent. Halogen atom such as bromine atom, methyl group,
Alkyl groups such as ethyl group, butyl group and trifluoromethyl group, alkoxy groups such as methoxy group and ethoxy group,
Examples include alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, butoxycarbonyl group, cyano group, and nitro group. Among the substituents, methyl group and phenyl group are particularly preferred as binder resin. It can be preferably used because of its excellent compatibility.

R ^{3 of the} above general formulas (I) (II) and (III)
In the above, the alkyl group represents a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, or the like, and the substituent thereof is a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group, an ethoxy group, or cyclohexyl. Group, a cycloalkyl group such as 4-butoxycarbonylcyclohexyl group, and the like, and as a substituent of the phenyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, Alkyl group such as t-butyl group, n-hexyl group, n-octyl group, trifluoromethyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butoxycarbonyl group Group, iso-butoxycarbonyl group, n-
A hexyloxycarbonyl group, an alkoxycarbonyl group such as an n-octyloxycarbonyl group, an alkoxyalkyl group such as a 2-methoxyethyl group and a 2-ethoxyethyl group, a cyano group, a nitro group and the like, and as a substituent of the cyclohexyl group, Examples thereof include n-butoxycarbonyl group and n-hexyloxycarbonyl group, and among the substituents, hexyl group, n-hexylphenyl group, trifluoromethyl group, n-butoxycarbonyl group, 2-
The methoxyethyl group and the 2-ethoxyethyl group can be preferably used because of their excellent compatibility with the binder resin.

Specific examples of the maleic acid imide derivative represented by the general formulas (I) and (III) and the phthalic acid imide compound represented by the general formula (II) of the present invention are shown in Tables 1 and 2 below. Table-
3, but is not limited to these.

[0016]

[Table 1-1]

[0017]

[Table 1-2]

[0018]

[Table 1-3]

[0019]

[Table 1-4]

[0020]

[Table 1-5]

[0021]

[Table 1-6]

[0022]

[Table 1-7]

[0023]

[Table 2-1]

[0024]

[Table 2-2]

[0025]

[Table 3-1]

[0026]

[Table 3-2]

[0027]

[Table 3-3]

[0028]

[Table 3-4]

[0029]

[Table 3-5]

[0030]

[Table 3-6]

The maleic acid imide derivative represented by the general formula (I) includes a maleic anhydride derivative represented by the general formula (IV) and an amine compound represented by the general formula (V). It can be obtained by reacting under an acidic or basic catalyst. Examples of the acidic catalyst used include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like, and examples of the basic catalyst include quinoline, pyridine and the like. The reaction is usually solvent-free, or aromatic hydrocarbons such as benzene, toluene and xylene, halogenated benzenes such as monochlorobenzene and dichlorobenzene, alcohols such as ethanol, butanol, methoxyethanol and ethoxyethanol, tetrahydrofuran, 1, Four
It can be carried out in a polar solvent such as ethers such as dioxane, N, N-dimethylformamide and N-methylpyrrolidone. The reaction temperature is 50 to 250 ° C., preferably 1
It is carried out at 00 to 160 ° C.

[0032]

[Chemical 4]

The phthalimide compound represented by the general formula (II) is obtained by converting the nitrophthalimide compound represented by the general formula (VI) into iron, zinc, tin or chlorides thereof and an acid (hydrochloric acid, sulfuric acid, It can be obtained by reduction with (p-toluenesulfonic acid, etc.). The solvent used in the reaction includes water, alcohols such as methanol, ethanol and isopropyl alcohol, tetrahydrofuran, 1,4-
It can be performed with ethers such as dioxane, cellosolves such as methyl cellosolve and ethyl cellosolve.
The reaction temperature is room temperature to 150 ° C., preferably 50 to 100
Can be done at ℃

Embedded image

Further, the maleimide derivative represented by the general formula (III) can be obtained by the following reaction.

[Chemical 6]

That is, a maleic anhydride derivative (IV),
The maleic acid imide derivative represented by the general formula (III) can be obtained by reacting the phthalic acid imide compound (II) with an acidic or basic catalyst. Examples of the acidic catalyst used include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like, and examples of the basic catalyst include quinoline, pyridine and the like. The reaction solvent is
Usually without solvent, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated benzenes such as monochlorobenzene and dichlorobenzene, alcohols such as ethanol, butanol, methoxyethanol, ethoxyethanol, tetrahydrofuran, 1,4-dioxane, etc. The polar solvents such as ethers, dimethylformamide and N-methylpyrrolidone are used, and the reaction can be carried out in these. The reaction temperature is 50 to 250 ° C., preferably 10
It is carried out at 0 to 160 ° C.

The maleic acid imide derivative and the phthalic acid imide compound of the present invention can be used not only as an electrophotographic photoreceptor, but also as an electronic device such as a solar cell or an organic EL element in the electronics field.

[0037]

EXAMPLES Next, the present invention will be explained concretely by way of examples and application examples. The parts here are based on weight.

Example 1 (Synthesis of Exemplified Compound No. I-53) 3,4-diphenylmaleic anhydride 2.50 g, p-
1.77 g of n-hexylaniline and 100 m of toluene
25 ml of pyridine was added dropwise with stirring in 1, and the reaction was carried out for 30 hours under reflux while removing water. After the reaction, toluene was distilled off, and the residue was subjected to column chromatography using toluene as a developing solvent, and the obtained crude target product was recrystallized from ethanol to obtain 3.18 g of pure target product (yield). Rate 77.6%). Melting point: 122.0-122.6 [deg.] C. The infrared absorption spectrum of this compound is shown in FIG.

Examples 2 to 5 In the same manner as in Example 1, some of the maleimide derivatives represented by the general formula (I) shown in Table 1 were obtained. The melting points and the elemental analysis results are summarized in Table 4.

Example 6 (Synthesis of Exemplified Compound No. II-15) 27.63 g of N-hexyl-4-nitrophthalimide,
While stirring 100 ml of concentrated hydrochloric acid in 250 ml of 1,4-dioxane, a solution of 75 g of tin (II) chloride dihydrate dissolved in 100 ml of ethanol was added dropwise over 80 minutes. After reacting for 4 hours at room temperature, the reaction mixture was poured onto ice, neutralized with sodium hydrogen carbonate, extracted with chloroform, and washed once with water. After the chloroform solution was dried over anhydrous magnesium sulfate, chloroform was distilled off, and the residue was subjected to column chromatography using 1,2-dichloroethane as a developing solvent, and the obtained crude target product was converted from diisopropyl ether. The crystals were recrystallized to obtain 12.78 g (yield: 51.9%) of pure target product. Melting point: 70.3 to 71.3 ° C. Further, the infrared absorption spectrum of this compound is shown in FIG.

Examples 7 to 10 In the same manner as in Example 6, phthalimide compounds represented by the general formula (II) were obtained. The melting points and elemental analysis results are summarized in Table 5. In addition, infrared absorption spectra of these compounds are shown in FIGS.

Example 11 (Exemplified Compound No. III-34)
Synthesis of 3,4-diphenylmaleic anhydride (2.50 g) and the aniline compound (2.46 g) synthesized in Example 6 were stirred in 100 ml of toluene while stirring in 25 ml of pyridine.
The mixture was added dropwise and the reaction was carried out for 33 hours while removing water under reflux. After the reaction, toluene was distilled off, and 1,2-
Column chromatography was performed using dichloroethane as a developing solvent, and the obtained crude target substance was recrystallized from ethanol to obtain 1.58 g of a pure target substance (yield: 33.0).
%) Was obtained. Melting point: 57.1-80 ° C. The infrared absorption spectrum of this compound is shown in FIG.

Example 12 In the same manner as in Example 11, a compound represented by the general formula (III) shown in Table 3 was obtained. The melting points and the elemental analysis results are summarized in Table 4.

[0044]

[Table 4]

[0045]

[Table 5]

Application Example 1 5 parts of a bisazo dye represented by the following chemical formula (P-1), butyral resin (Denka butyral resin # 3000-2:
Denki Kagaku Kogyo) 2.5 parts, and tetrahydrofuran 9
2.5 parts were dispersed in a ball mill for 12 hours, and then tetrahydrofuran was added so as to have a dispersion liquid concentration of 2% by weight and redispersed to prepare a coating liquid. The prepared dispersion liquid was cast and coated on a polyester film having a thickness of about 100 μm on which aluminum was vapor-deposited by a doctor blade to form a charge generation layer having a thickness of about 1.0 μm after drying.

[0047]

[Chemical 7]

On the charge generation layer thus obtained,
6 parts of the exemplified compound (Compound No. I-53), 10 parts of a polycarbonate resin (K-1300: manufactured by Teijin Chemicals), 0.002 part of methylphenylsilicone (KF50-100 cps: manufactured by Shin-Etsu Chemical), and 94 parts of tetrahydrofuran. A coating solution of a formulation is prepared, cast-coated with a doctor blade, and a charge transport layer having a film thickness after drying of about 20.0 μm is formed, which is a laminate including an aluminum electrode / charge generation layer / charge transport layer. Type electrophotographic photoreceptor (photoreceptor No.
1) was created.

Application Examples 2 to 6 In the same manner as in Application Example 1 except that the compound shown in Table 6 was used instead of the exemplified compound (Compound No. I-53) of Application Example 1, the photoreceptor No. 2-6 were created.

Application Example 7 Instead of 5 parts of the bisazo dye represented by the chemical formula (P-1), a trisazo dye 6 represented by the following chemical formula (P-2)
A charge generation layer was formed in the same manner as in Application Example 1 except that part of the charge generation layer was used.

Embedded image

On the charge generation layer thus obtained,
6 parts of the exemplified compound (Compound No. I-53), 10 parts of a polycarbonate resin (K-1300: manufactured by Teijin Chemicals), 0.002 part of methylphenylsilicone (KF50-100 cps: manufactured by Shin-Etsu Chemical), and 94 parts of tetrahydrofuran. A multi-layered electrophotography in which a coating solution is prepared and a charge transport layer having a film thickness after drying of about 20.0 μm is formed by the same method as in Application Example 1 and which is composed of an aluminum electrode / charge generation layer / charge transport layer. A photoconductor (photoconductor No. 7) was created.

Application Examples 8 to 12 In the same manner as in Application Example 7 except that the compound shown in Table 6 was used instead of the exemplified compound (Compound No. I-53) of Application Example 7, the photoreceptor No. 8-12 were created.

Application Example 13 5 parts of X-type metal-free phthalocyanine (P-3), polyvinyl butyral resin (S-Rex BLS: Sekisui Chemical Co., Ltd.) 5
Parts and 90 parts of tetrahydrofuran in a ball mill 1
Dispersion was carried out for 2 hours, and then tetrahydrofuran was added so as to have a dispersion liquid concentration of 2% by weight and redispersed to prepare a coating liquid. The dispersion liquid thus prepared was cast-coated with a doctor blade on a polyester film having a thickness of about 100 μm on which aluminum was vapor-deposited, and the film thickness after drying was about 0.5.
A charge generation layer of μm was formed. On the charge generation layer thus obtained, the exemplified compound (Compound No. I-53)
A coating solution having a formulation of 6 parts, 10 parts of a polycarbonate resin (K-1300: manufactured by Teijin Chemicals), and 94 parts of tetrahydrofuran was prepared, cast-coated with a doctor blade, and the film thickness after drying was about 20.0 μm. The charge transporting layer of No. 13 was formed, and a laminated electrophotographic photoreceptor (photoreceptor No. 13) formed of aluminum electrode / charge generating layer / charge transporting layer was prepared.

Application Examples 14 to 18 Instead of Application Example 13 (Exemplified Compound No. I-53),
Photoreceptor No. 1 was prepared in the same manner as in Application Example 13 except that the compounds shown in Table 6 were used. 14-18 were created.

The electrophotographic photoconductors (photoconductor Nos. 1 to 18) obtained as described above were subjected to +6 KV using an electrostatic copying paper test apparatus (SP-428: Kawaguchi Denki Seisakusho).
After corona charging and positively charging, leave it in the dark for 20 seconds, measure the surface potential Vo at that time, and then irradiate it with a tungsten lamp so that the surface illuminance becomes 40 lux, and halve it. Exposure amount E1 / 2 (lux · sec)
Was measured. Table 6 summarizes the results.

[0056]

[Table 6]

Application Example 19 0.08 g of the compound (P-1), 10 g of a 10 wt% tetrahydrofuran solution of a polycarbonate resin (PC-Z: manufactured by Teijin Chemicals), 0.6 g of the following compound (D-1), an exemplary compound (compound No. I-53) 0.32 g and a 1 wt% tetrahydrofuran solution 0.3 g of silicone oil (KF50: manufactured by Shin-Etsu Chemical Co., Ltd.) were weighed in a ball mill pot and ball-milled for 24 hours to prepare a coating solution. About 100 μm of the prepared coating liquid deposited with aluminum
Cast coating was performed on a thick polyester film with a doctor blade to prepare a single-layer type electrophotographic photosensitive member (photosensitive member No. 19) having a film thickness after drying of about 15 μm.

[Chemical 9]

Application Examples 20 to 25 Instead of Application Example 19 (Exemplified Compound No. I-53),
The same procedure as in Application Example 22 was performed except that the compounds shown in Table 7 were used. 20-25 were created.

With respect to the electrophotographic photoconductors (photoconductors Nos. 19 to 25) obtained as described above, an electrostatic copying paper test apparatus (SP-428: Kawaguchi Denki Seisakusho) was used for +6.
After performing KV corona charging and positively charging, it was left in a dark place for 20 seconds, the surface potential V ₀ at that time was measured, and then light irradiation was performed using a tungsten lamp so that the surface illuminance was 40 lux, Half exposure E1 / 2 (lux · se
c) and the surface potential Vr after 30 seconds of light irradiation were measured.
Next, after repeating the above operation 5000 times, V ₀ , E1 /
2, Vr was measured. The results are summarized in Table 7.

[0060]

[Table 7]

[0061]

INDUSTRIAL APPLICABILITY The maleic imide derivative of the present invention (including a phthalic acid imide compound, the same applies hereinafter) can be produced in a high yield by a simple method and has excellent solubility and phase in a binder resin. It has solubility. In addition, the maleic acid imide derivative of the present invention has a high charge retention ability when a laminated type photoreceptor containing this maleic acid imide derivative as a charge transporting substance that accepts and transports the charge generated by the charge generating substance is prepared. It has high sensitivity, and also has high sensitivity and high durability when a single-layer type photoreceptor is prepared.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the compound obtained in Example 1.

FIG. 2 is an infrared absorption spectrum diagram of the compound obtained in Example 6.

FIG. 3 is an infrared absorption spectrum diagram of the compound obtained in Example 7.

4 is an infrared absorption spectrum diagram of the compound obtained in Example 8. FIG.

5 is an infrared absorption spectrum diagram of the compound obtained in Example 9. FIG.

6 is an infrared absorption spectrum diagram of the compound obtained in Example 10. FIG.

7 is an infrared absorption spectrum diagram of the compound obtained in Example 11. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03G 5/06 316 G03G 5/06 318Z 318 C07D 209/48 Z // (C07D 403/04 207: 448)

Claims (6)

[Claims] 1. A maleic acid imide derivative represented by the following general formula (I) (formula 1). Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.) 2. A phthalimide compound represented by the following general formula (II) (chemical formula 2). Embedded image (In the formula, R ³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group.) 3. A maleimide derivative represented by the following general formula (III) (formula 3). Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.) 4. A maleic anhydride derivative represented by the following general formula (IV) and an amine compound represented by the general formula (V) are reacted under an acidic or basic catalyst. A method for producing a maleic acid imide derivative represented by the formula (I). [Chemical 4] (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.) 5. A phthalate represented by the general formula (II), which comprises reducing a nitrophthalimide compound represented by the following general formula (VI) with iron, zinc, tin or their chlorides and an acid. A method for producing an acid imide compound. Embedded image (In the formula, R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group.) 6. A maleic anhydride derivative represented by the following general formula (IV) and a maleic acid imide derivative represented by the general formula (II) are reacted under acidic or basic catalysts. A method for producing a maleic acid amide derivative represented by the formula (III). [Chemical 6] (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group. Represents a cyclohexyl group.)