JPH0592943A - Triphenylamine derivative and photosensitive substance using the same derivative - Google Patents

Abstract

PURPOSE:To obtain a new phenylamine derivative having high hole mobility and being excellent also in compatibility with a binding resin capable of forming a photosensitive layer and useful as an electron transfer material, especially as a hole transfer material. CONSTITUTION:A phenylamine derivative of formula I (R<1> to R<4>, R<11>, R<21>, R<31> and R<41> are H, alkyl, alkoxy, aryl or cycloalkyl; (m) is integer of 1-10). The compound of formula I is obtained by e.g. making an aldehyde compound of formula II to react with an amine compound of formula III in the presence of acetic acid, p-toluenesulfonic acid, etc. Since a photosensitive substance using the triphenylamine derivative is excellent in antistatic ability and sensitivity and simultaneously the triphenylamine derivative is rich in compatibility with a binding resin, the photosensitive substance can obtain uniform photosensitive layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel phenylamine derivative and a photoreceptor using the same.

[0002]

2. Description of the Related Art In recent years, as an electrophotographic photosensitive member for an image forming apparatus such as a copying machine, a printer or a facsimile, an organic photosensitive member having excellent processability and economical efficiency and having a large degree of freedom in functional design has been widely used. The Carlson process is widely used to form a copied image using an electrophotographic photoreceptor. The Carlson process
A charging process for uniformly charging the photoconductor by corona discharge, an exposure process for exposing the charged photoconductor to a document image to form an electrostatic latent image corresponding to the document image, and a development process in which the electrostatic latent image contains toner. A developing step of developing with a developer to form a toner image,
It includes a transfer step of transferring the toner image to a base material such as paper, a fixing step of fixing the toner image transferred to the base material, and a cleaning step of removing the toner remaining on the photoconductor after the transfer step. There is. In order to form a high-quality image in the Carlson process, it is required that the electrophotographic photosensitive member has excellent charging characteristics and photosensitive characteristics and that the residual potential after exposure is low.

Conventionally, inorganic photoconductors such as selenium and cadmium sulfide have been known as electrophotographic photosensitive materials.
These have the disadvantages of toxicity and high production costs. Therefore, so-called organic electrophotographic photoconductors using various organic substances instead of these inorganic substances have been proposed. Such an organic electrophotographic photoreceptor has a photosensitive layer composed of a charge generating material that generates a charge upon exposure and a charge transporting material that has a function of transporting the generated charge.

In order to satisfy various conditions desired for such an organic electrophotographic photosensitive member, it is necessary to appropriately select these charge generating material and charge transporting material. Various organic compounds have been proposed as charge transport materials,
For example, a compound N, N, N ', N'-tetraphenyl-1,4-having a phenyl group of triphenylamine represented by the following formula (20) and having a substituent in a para position to a nitrogen atom:
Phenylenediamine (hereinafter referred to as p-phenylenediamine) is known. Formula (20):

[0005]

[Chemical 3]

[0006]

However, p-phenylenediamine has a problem that the sensitivity and repeatability are not sufficient although the diphenylamino group which is a sensitive group is introduced. An object of the present invention is to solve such technical problems and to provide a phenylamine derivative having high sensitivity and excellent repeating characteristics, and a photoreceptor using the same.

[0007]

Means and Actions for Solving the Problems The phenylamine derivative of the present invention for achieving the above object is represented by the general formula (1)

[0008]

[Chemical 4]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ¹¹ ,
R ²¹ , R ³¹ , R ⁴¹ and m are the same as above. ) Is represented. Such a phenylamine derivative of the present invention is a group
(Ten):

[0010]

[Chemical 5]

The double bond represented by the formula (where m is the same as above) forms a long conjugated double bond with the phenyl group to which the double bond is bonded, which is effective as a charge transporting material, especially as a hole transporting material. And has a higher hole mobility than charge transport materials such as conventionally known triphenylamine derivatives and m-phenylenediamine compounds. Furthermore, since the triphenylamine derivative of the present invention has excellent compatibility with the binder resin forming the photosensitive layer, it further contributes to the improvement of sensitivity.

Among the triphenylamine derivatives of the present invention, those having an alkyl group as a substituent are particularly excellent in compatibility with resins. Further, in the general formula (1), m is preferably 1 to 3. The electrophotographic photoreceptor of the present invention is characterized in that a photosensitive layer containing a triphenylamine derivative represented by the general formula (1) is provided on a conductive substrate, whereby the photoreceptor of the present invention is Excellent sensitivity and chargeability, and high repeatability.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and hexyl group. As the alkoxy group, for example, a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, a hexyloxy group and the like having 1 carbon atom
~ 6 alkoxy groups.

As the aryl group, for example, a phenyl group,
Examples thereof include a naphthyl group, a biphenylyl group, an anthryl group and a phenanthryl group. Examples of the cycloalkyl group include cycloalkyl groups such as cyclopropyl, cyclobutane, cyclopentane, and cyclohexane. Specific examples of the triphenylamine derivative represented by the general formula (1) include the compounds shown in Table 1.

[0015]

[Table 1]

The compound represented by the general formula (1) can be produced, for example, by the following reaction formula [New Experimental Chemistry Course (Publisher: Maruzen Co., Ltd.) 14-III, 1417-].
See page 1427]. Reaction formula:

[0017]

[Chemical 6]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and m are the same as above. ) That is, an aldehyde compound represented by the formula (a) and an amine compound represented by the formula (b) are reacted by adding acetic acid, p-toluenesulfonic acid or the like, and represented by the general formula (1). The compound of the present invention is obtained. This reaction is carried out under reflux in a solvent. As the solvent, for example, benzene, toluene, xylene or the like can be used. The photosensitive layer according to the invention contains one or more compounds represented by the general formula (1).

The photosensitive layer in the present invention includes a charge generating material, a charge transporting material, a compound represented by the general formula (1) and a binder resin in a single layer type, a charge generating layer and a charge transporting layer. The photoconductor of the present invention can be applied to any of them. In order to obtain a laminated type photosensitive layer, a charge generation layer containing a charge generation material is formed on a conductive substrate, and a compound represented by the above general formula, which is a charge transport material, is formed on this charge generation layer. The contained charge transport layer may be formed. The stacking order may be reversed, and the charge generation layer may be provided on the charge transport layer.

As the charge generating material, conventionally used selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salt, azo compounds, disazo compounds, phthalocyanine compounds, anthanthrone compounds, perylene compounds. Examples thereof include compounds, indigo compounds, triphenylmethane compounds, slene compounds, toluidine compounds, pyrazoline compounds, perylene compounds, quinacridone compounds, and pyrrolopyrrole compounds. These charge generating materials can be used alone or in combination of two or more.

The above general formula (1), which is a charge transport material, is also used.
The triphenylamine derivative represented by can be used in combination with other conventionally known charge transport materials.
Examples of conventionally known charge transport materials include oxadiazole-based compounds such as 2,5-di (4-methylaminophenyl) -1,3,4-oxadiazole and 9- (4-
Styryl compounds such as diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazole, triphenylamine compounds, indole compounds, oxazole compounds Compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds,
Examples thereof include nitrogen-containing cyclic compounds such as pyrazole compounds and triazole compounds, and condensed polycyclic compounds. The binder resin is not always necessary when using a charge transporting material having film-forming properties such as polyvinyl carbazole.

As the binder resin, various resins can be used, for example, styrene-based polymers, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers, acrylic copolymers. Coal, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, Thermoplastic resins such as polyarylate, polysulfone, diallyl phthalate resin, ketone resin, poly (vinyl butyral) resin, and polyether resin, silicone resin, epoxy resin, other crosslinkable thermosetting resin, epoxy acrylate, urethane-acrylate How such photocurable resins. These binder resins may be used alone or in combination of two or more.

As a solvent for dissolving the charge generating material, the charge transporting material and the binder resin to prepare a coating solution, for example, alcohols such as methanol, ethanol, isopropanol and butanol, n-hexane, octane and cyclohexane are used. Aliphatic hydrocarbons such as benzene, toluene, xylene etc., aromatic hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene etc., dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether etc. Ethers, acetone, methyl ethyl ketone, cyclohexanone and other ketones, ethyl acetate, methyl acetate and other esters, dimethylformaldehyde, dimethylformamide, dimethyl Sulfoxide and the like.
These solvents may be used alone or in combination of two or more.

In order to improve the sensitivity of the charge generating layer, known sensitizers such as terphenyl, halonaphthoquinones and acenaphthylene may be used together with the above charge generating material. Further, a surfactant, a leveling agent, etc. may be used in order to improve the dispersibility of the charge transporting material or the charge generating material and the dyeing property.

Examples of the conductive substrate include aluminum, copper, tin, platinum, silver, vanadium, molybdenum,
Chromium, cadmium, titanium, nickel, palladium,
Simple metals such as indium, stainless steel, and brass, and plastic materials in which the above metals are vapor-deposited or laminated,
Examples thereof include glass coated with aluminum iodide, tin oxide, indium oxide and the like.

The conductive substrate may be in the form of a sheet, a drum, or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Also,
The substrate preferably has sufficient mechanical strength when used. In the laminate type photosensitive layer, the charge generating material and the binder resin which constitute the charge generating layer can be used in various ratios, but the charge can be changed with respect to 100 parts of the binder resin (weight part, the same hereinafter). Generating material 5 to 500 parts, especially 10
It is preferably used in a proportion of 250 parts.

The charge generation layer may have an appropriate film thickness, but is 0.01 to 5 μm, particularly 0.1 to 3 μm.
It is preferable that the thickness is about m. The compound (charge-transporting material) represented by the above general formula (1) that constitutes the charge-transporting layer and the binder resin can be used in various proportions, but the charge generated in the charge-generating layer by light irradiation can be used. To 100 parts of the binder resin, the above general formula
10-500 parts, especially 25-
It is preferably used in a ratio of 200 parts.

The charge transport layer is preferably formed to have a thickness of 2 to 100 μm, particularly 5 to 30 μm. In the single-layer type photosensitive layer, the charge generating material is 2 to 20 parts, particularly 3 to 15 parts, and the compound represented by the general formula (charge transporting material) is 40 to 200 parts based on 100 parts of the binder resin. ,
Particularly, it is suitable that the amount is 50 to 150 parts. The thickness of the single layer type photosensitive layer is 10 to 50 μm, especially 15 to 3 μm.
It is preferably about 0 μm.

When a photoreceptor including a charge generating layer and a charge transporting layer is formed by a coating means, the charge generating material or charge transporting material and the binder resin are treated by a conventionally known method such as a roll mill, a ball mill, an attritor, or the like. A coating liquid is prepared using a paint shaker, an ultrasonic disperser or the like.

[0030]

The present invention will be described in detail below with reference to Examples and Comparative Examples. Example 1 <Synthesis of compound represented by No. 3 in Table 1> Formula (11) below
For 2.0 g of the aldehyde compound represented by
2.7 g of the amine compound represented by (12) was reacted in toluene under reflux for 3 hours to obtain a compound represented by No. 3 in Table 1. Elemental analysis: Calculated as _{C 34 H 30 N 2 (%} ) C87.52 H6.48 N6.00 Found (%) C87.46 H6.53 N5.94 formula (11):

[0031]

[Chemical 7]

Formula (12):

[0033]

[Chemical 8]

Example 2 <Compound represented by No. 1 in Table 1> 2.0 g of an aldehyde compound represented by the following general formula (11) and the following general formula (14)
Example 1 using 2.3 g of the amine compound represented by
In the same manner as described above, the compound represented by No. 1 in Table 1 was obtained. Elemental analysis value: calculated value as C ₃₂ H ₂₆ N ₂ (%) C87.64 H5.98 N6.39 measured value (%) C87.64 H6.08 N6.36 Formula (11):

[0035]

[Chemical 9]

Formula (14):

[0037]

[Chemical 10]

Hereinafter, each compound was produced in the same manner as in Example 1 using appropriate starting materials. The obtained compounds are as follows. Example 3 <Compound represented by No. 2 in Table 1> Elemental analysis value: calculated value as C ₃₂ H ₃₀ N ₂ (%) C87.52 H6.48 N6.00 measured value (%) C87.57 H6.43 N5.99 Example 4 <Compound represented by No. 4 in Table 1> Elemental analysis value: Calculated value (%) as C ₃₆ H ₃₄ N ₂ C87.41 H6.93 N5.66 Measured value (%) C87.39 H6.97 N5.70 example 5 <in Table 1, No compound represented by 5.> elemental analysis: calculated _{C 37 H 36 N 2 (%} ) C87.36 H7. 13 N5.51 Actual measurement value (%) C87.35 H7.18 N5.53 Example 6 <Compound represented by No. 6 in Table 1> Elemental analysis value: Calculated value as C ₃₆ H ₃₄ N ₃ (% ) C87.41 H6.93 N5.66 measured value (%) C87.40 H6.93 N5.62 <In Table 1, No compound represented by 7.> Example 7 Elemental analysis: Calculated _{C 34 H 30 N 2 (%} ) C87.52 H6.48 N6.00 Found (%) C87.49 H6.51 N5.99 <in Table 1, No 8 represented by compounds.> example 8 elemental analysis: C ₃₈ H ₃₆ N ₂ calculated (%) C87.65 H6.97 N5.38 Found ( %) C87.64 H6.99 N5.36 <in Table 1, No compound represented by 9.> example 9 elemental analysis: calculated as _{C 36 H 34 N 2 (%} ) C87.41 H6.93 N5.66 Found (%) C87.41 H6.92 N5.61 example 10 <in Table 1, No 10 represented by compounds.> elemental _{analysis: C 36 H 34 N 2 O} 2 calculated (% ) C87.41 H6.93 N5.66 measured value (%) C87.42 H6.95 N5. <In Table 1, No compounds represented by 11.> 1 Example 11 Elemental Analysis: Calculated as _{C 38 H 36 N 2 (%} ) C87.65 H6.97 N5.38 Found (%) C87. 60 H6.95 N5.41 example 12 <in Table 1, No compounds represented by 12.> elemental analysis: calculated _{C 38 H 36 N 2 (%} ) C87.65 H6.97 N5.38 Found <in Table 1, No compounds represented by 13.> value (%) C87.64 H6.99 N5.40 eXAMPLE 13 elemental analysis: C ₄₀ H ₃₈ N ₂ calculated (%) C87.87 H7 .01 N5.12 actual measurement value (%) C87.93 H7.02 N5.09 Example 14 <Compound represented by No. 14 in Table 1> Elemental analysis value: Calculated value as C ₄₀ H ₃₈ N ₂ ( %) C87.87 H7.01 N5.12 Measured value (%) C87.85 7.05 N5.08 <In Table 1, No compounds represented by 15.> Example 15 Elemental Analysis: Calculated as _{C 36 H 34 N 2 (%} ) C87.41 H6.93 N5.66 Found (%) C87.38 H6.96 N5.64 <in Table 1, No compounds represented by 16.> example 16 elemental analysis: calculated as _{C 36 H 34 N 2 (%} ) C87.41 H6. 93 N5.66 Measured value (%) C87.40 H6.90 N5.69 Example 17 <Compound represented by No. 17 in Table 1> Elemental analysis value: Calculated value as C ₄₁ H ₄₄ N ₂ (% ) C87.19 H7.85 N4.96 <in Table 1, No compounds represented by 18.> Found (%) C87.19 H7.89 N4.93 eXAMPLE 18 elemental analysis: C ₄₂ H ₄₆ N calculated ₂ (%) C87.15 H8.01 N4.84 Found (% C87.18 H8.07 N4.84 <In Table 1, No compounds represented by 19.> Example 19 Elemental analysis: C ₃₇ H ₃₆ N ₂ Calculated (%) C87.36 H7.13 N5. 51 Found (%) C87.32 H7.15 N5.49 eXAMPLE 20 <in Table 1, No compounds represented by 20.> elemental analysis: calculated _{C 37 H 36 N 2 O 4} (%) C77.40 H6.13 N5.01 Measured value (%) C77.32 H6.14 N5.05 Examples 21-40 and Comparative Examples 1-2 (multilayer photosensitive layer) Charge represented by the following formula (A) 2 parts of the generating material, 1 part of polyvinyl butyral resin, and 120 parts of dichloromethane were dispersed in a paint shaker using stainless beads for 2 hours. The obtained dispersion liquid was applied onto an aluminum sheet using a wire bar, dried at 60 ° C. for 1 hour, and then dried.
A charge generation layer of 5 μm was obtained.

On this charge generation layer, 1 part of a charge transport material,
A solution prepared by dissolving 1 part of a polycarbonate resin in 9 parts of benzene was applied with a wire bar and dried at 150 ° C. for 1 hour to obtain a 22 μm charge transport layer. In addition, Examples 21 to
The charge transport material used in Example 40 was obtained in Examples 1 to 20 above, and the charge transport materials used in Comparative Example 1 and Comparative Example 2 were respectively represented by the following formula (21) and formula (22). It is represented. Formula (A):

[0040]

[Chemical 11]

Formula (21):

[0042]

[Chemical formula 12]

Expression (22):

[0044]

[Chemical 13]

Examples 41 to 60 and Comparative Example 2 (single layer type photosensitive layer) 1 part of the charge generating agent represented by the above formula (A) and 60 parts of dichloromethane were used for 2 hours on a paint shaker using stainless beads. Dispersed. To the obtained dispersion liquid, 50 parts of a dichloromethane solution of a polycarbonate resin having a solid content of 20% by weight and 10 parts of a charge transport material were added, and the dispersion was further continued for 1 hour. The obtained dispersion was applied onto an aluminum sheet with a wire bar and dried at 60 ° C. for 1 hour to obtain a photosensitive layer of 20 μm. In addition, Example 41-
The charge-transporting material used in 60 was obtained in Examples 1 to 20 above, and the charge-transporting materials used in Comparative Examples 3 and 4 were represented by the above formulas (21) and (22), respectively. It is a thing.

(Evaluation Test) The surface potentials, half-exposure doses (E _1/2 ) and residual potentials of the photoconductors obtained in Examples 21 to 60 and Comparative Examples 1 to 4 were evaluated by an evaluation tester (Kawaguchi Electric Co., Ltd. EPA8100 "). The measurement conditions are as follows.

Light intensity: 50 lux Exposure time: 1/15 seconds Surface potential: (±) The inflow current value was adjusted to be near 700 V. Light source: Tungsten lamp Static elimination: 200 lux Residual potential measurement: Measurement started 0.2 seconds after the start of exposure.

The test results of Examples 21-40 and Comparative Examples 1-2 are shown in Table 2, and Examples 41-60 and Comparative Examples 3-4.
The test results of are shown in Table 3, respectively.

[0049]

[Table 2]

[0050]

[Table 3]

From these test results, the surface potentials of the photoconductors of the respective examples are almost the same as those of the conventional photoconductor (comparative example), but the half-exposure amount and the residual potential are excellent and the sensitivity is remarkably high. You can see that it has been improved.

[0052]

As described above, the photoconductor using the triphenylamine derivative of the present invention is excellent in charging ability and sensitivity, and the triphenylamine derivative is highly compatible with the binder resin. Therefore, there is an effect that a uniform photosensitive layer can be obtained.

Claims (2)

[Claims] 1. General formula (1): (Wherein R ¹ , R ² , R ³ , R ⁴ , R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cycloalkyl group. , M represents an integer of 1 to 10). 2. A photosensitive member comprising a conductive layer and a photosensitive layer containing a phenylamine derivative represented by the following general formula (1) provided on the conductive substrate. General formula (1): (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are the same or different and each is a hydrogen atom, an alkyl group,
It represents an alkoxy group, an aryl group or a cycloalkyl group, and m represents an integer of 1 to 3. )