JPH0337656A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity to white light and laser beams and repeating use enduring characteristics by forming a single layer containing a carrier generating material of titanyl phthalocyanine and a specified bisazo pigment or 2 layers each containing them separately as a photosensitive layer. CONSTITUTION:The photosensitive layer 2 formed on a substrate 1 contains the carrier generating material of titanyl phthalocyanine and a carrier transfer material of the bisazo pigment represented by formula I mixed together in a single layer or separately in 2 layers, and in formula I, A is a group of formula II or III or IV; Ar1 is an aromatic or heterocyclic group; each of Ar2 and Ar3 in an aromatic group; each of R1 and R3 is H, alkyl, or aryl; R2 is alkyl, carboxy, or its ester; and Z is an atomic group necessary to form an aromatic or heterocyclic group, thus permitting sensitivity to white light and laser beams and repeated use enduring characteristics to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photoreceptor, particularly an electrophotographic photoreceptor.

[Prior art]

Photoreceptors using organic photoconductive substances (OPC) are generally less toxic than inorganic photoconductive substances, and are advantageous in terms of flexibility, lightness, film formability, cost, etc. , has been attracting attention recently.

In such electrophotographic photoreceptors, functionally separated photoreceptors, which use materials with separate charge generation and transport functions, allow each of these functions to be designed independently, and the selection can be made in the photoreceptor design. It is advantageous because the width is expanded, and as a result, the electrophotographic characteristics can be improved, and the sensitivity, repeatability,
Excellent in terms of mechanical strength, etc.

Such electrophotographic photoreceptors are generally widely used in electrophotographic copying machines, printers, and the like. For example, in copying machines, photoreceptors that are sensitive to visible light sources have been developed.
On the other hand, a printer using a semiconductor laser as a light source is used at the end of the computer. The electrophotographic photoreceptor incorporated into the printer must have high sensitivity in the near-infrared region.

Further, progress is being made in the development of a printer that uses a semiconductor laser and has a copying function using white light as a light source.

In this case, the photoreceptor must first have high sensitivity in the near-infrared region in order to adapt to the printer function, and high sensitivity to light in the visible light region in order to adapt to the copying function. That is, there is a demand for the development of a composite electrophotographic photoreceptor that can be applied to an apparatus having both the printer function and the copying function using white light as a light source as described above.

For example, JP-A-47-37543, JP-A-55-2283
Photoreceptors containing bisazo compounds, which are already known from No. 4, No. 54-79632, No. 56-116040, exhibit relatively good sensitivity in the short and medium wavelength ranges, but have poor sensitivity in the long wavelength range. Due to its low sensitivity, it could not be used in laser printers that use semiconductor light sources.

The currently widely used gallium-aluminum-arsenic (Ga-Ai2-As) light emitting device has an oscillation wavelength of 750 nm.
As an organic photoreceptor having sensitivity in such a long wavelength region, for example, , τ, τ, η, η' type metal-free 7-thalocyanine compounds.

Furthermore, the σ-type titanyl phthalocyanine described in JP-A No. 61-239248, the β-type titanyl phthalocyanine described in JP-A-62-67094, and the m reported in the Journal of Electrophotography, Vol. 27, No. 4 (p. 19-24). type titanyl phthalocyanine, etc.

However, such electrophotographic photoreceptors, which have high sensitivity in the long wavelength range, do not have sufficient photosensitivity in the medium to short wavelength range, and cannot support copying functions using white light sources as light sources. .

As mentioned above, electrophotographic photoreceptors for visible light and electrophotographic photoreceptors for semiconductor laser light each have relatively good performance when used alone, but they have sensitivity over a wide range from short wavelengths to long wavelengths. Photoreceptors are needed.

In response to this demand, N
- Photoreceptor containing both dimethyldiphenylamine type and anthraquinone type disazo pigments (JP-A-63-2
No. 36048), or a photoreceptor in which a phenanthraquinone type is combined in place of the anthraquinone type in the photoreceptor (
JP-A No. 63-236049) has been proposed, but it has not yet reached a satisfactory stage.

Furthermore, as electrophotographic copying machines and printers become faster and more compact, including the reduction in the diameter of photoreceptor drums, the time required for the copying process has been significantly shortened, digitalization has progressed, and the number of copies has increased. A wide variety of demands have been placed on photoreceptors, such as high sensitivity, stable charging characteristics, rapid response to light attenuation, chemical durability, and physical durability.

[Purpose of the invention]

An object of the present invention is to have highly sensitive spectral sensitivity characteristics ranging from visible light to near infrared light, and to be applicable to an apparatus having both a printer function and a copying function using white light as a light source. It is an object of the present invention to provide a photoreceptor having excellent repeatability and capable of responding to high-speed copying processes.

[Structure and effects of the invention]

The object of the present invention is to provide a photosensitive layer containing a carrier-generating substance and a carrier-transporting substance on a substrate, and to add titanyl phthalocyanine and a bisazo pigment represented by the following general formula [:BAl] as a carrier substance to the photosensitive layer. This is achieved by an electrophotographic photoreceptor provided with a layer containing either separately or in a mixture.

The titanyl phthalocyanine preferably used in the present invention has a peak position at a Bragg angle of 2θ (in the following description ± The error value of 0.2' is omitted), but (1) 7.5
°, 12.3°, 16.3°, 25.3° and 28.
σ-type titanyl phthalocyanine with a strong peak at 7°,
(2) 9.3°, 1O16°, 13.2°, 15.1
', 15.7°, 16.1', 20.8°, 23.3°
, (3) m-type titanyl phthalocyanine with strong peaks at 6.9°, 15.5°, and 23.4°, and (4) ) Titanyl phthalocyanine with strong peaks at 9.6° and 27.2° (in the present invention, titanyl phthalocyanine
type titanyl phthalocyanine to distinguish it from the former two)
It is.

The peak of titanyl phthalocyanine according to the present invention is
Al with a cone with an acute angle that is clearly different from the noise. The basic structure of the titanyl phthalocyanine of the present invention is the following general formula (P
c).

The following margin is general formula % formula %) However, X', X'', X3.
, Q represents an integer from 0 to 4.

The above X-ray diffraction spectrum is a reflection diffraction spectrum measured under the following conditions. (320 type self-recording spectrophotometer (
(Newly manufactured by Hitachi)) X-ray tube Cu Voltage 40. OKV current
100 m A start angle
6.00 deg.

Stop angle 35-00 deg.

Step angle 0.020 deg.

Measurement time: 0.50 sec.

The titanyl phthalocyanine according to the present invention (hereinafter referred to as Ti0Pc, limited to the product of the present invention) is produced, for example, by the following production method.

1. Mix 3-diiminoisoindoline and sulfolane, add titanium tetrapropoxide, and heat in a nitrogen atmosphere at 80 to 300°C, preferably 100 to 260°C.
React at ℃. After the reaction is completed, the mixture is allowed to cool and the precipitate is collected by filtration to obtain titanyl-7-talocyanine.

As the apparatus used for the treatment, in addition to a general stirring apparatus, a homomixer, disperser, agitator, ball mill, sand mill, attritor, etc. can be used.

Among the titanyl phthalocyanines described above, the one most preferably used in the present invention is Y-type titanyl phthalocyanine, and furthermore, titanyl 7-thalocyanine in a crystalline state whose peak intensity at 9.6° is 40% or more of the peak intensity at 27 and 2'. is preferable, and more preferably, in the phthalocyanine according to the present invention, titanyl phthalocyanine in a crystalline state exhibiting a peak intensity at 9.6° of 60% or more based on the peak intensity at 27° and/or a titanyl phthalocyanine at 9.6°. The peak intensity is 50% or more and the peak intensity at 6 and 7 degrees is 3
By containing 0% or less of crystalline titanyl phthalocyanine, a photoreceptor with high sensitivity and good charging characteristics can be formed.

The X-ray diffraction diagram of Ti0Pc at Bragg angle 2θ is shown in Figure 1.
The absorption spectrum is shown in FIG. Ti0Pc has a large peak of absorption on the long wavelength side and a deep valley on the short wavelength side of the visible region.

In the bisazo pigment represented by the general formula [BA] according to the present invention, the general formula CBA) '°z-'^'2 Here, Ar does not represent an aromatic ring group or a heterocyclic group.

Ar2 and Ar3 each represent an aromatic ring group.

R and R3 each represent a hydrogen atom, an alkyl group or an aryl group. R7 represents an alkyl group, a carboxyl group or an ester group thereof. Z represents an atomic group necessary to form an aromatic ring or a heterocycle.

The aromatic group represented by Ar + r A r 2 or Ar is, for example, a phenyl group, a naphthyl group, etc., and Ar,
The heterocyclic group represented by is, for example, a dibenzofuran ring, a carbazole ring, an indole ring, or the like.

The alkyl group represented by R,, R2 or R1 is, for example, a lower alkyl group such as a methyl group or an ethyl group;
The aryl group represented by 3 is, for example, a phenyl group.

Specific examples of the aromatic ring or heterocycle formed by Z include those similar to the above-mentioned specific examples of Ar and -Ar.

A r+-A rs, Rl-R! Each group represented by and Z may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group,
These include substituted amino groups, acylamino groups, cyano groups, carboxyl groups, sulfonic acid groups, and sulfamoyl groups.

A compound represented by the general formula CBA (hereinafter referred to as bisazoCB
It is called A). ) are shown below, but the invention is not limited thereto.

The above azo compounds are disclosed in, for example, Japanese Patent Application Laid-Open No. 53-1334.
Synthetic leather can be easily formed by the method described in No. 45.

The bisazo [BA] according to the present invention has a wavelength of 450 nm to 600 nm.
It has high sensitivity in the spectral region of m, and complements the sensitivity in the low sensitivity spectral region of Ti0Pc used in the present invention, and when used in combination with Ti0Pc according to the present invention, the cyclic characteristics regarding charging potential, residual potential, etc. are extremely stable. It has the characteristic of being.

There is not necessarily a uniform selection method for the combination of different types of carrier-generating substances, and in the present invention, the combination of T 1OPc and bisazo [:BA) was selected from a large number of compounds through repeated experiments. It has been decided.

With this combination of the present invention, high sensitivity can be maintained in a wide spectral range from long wavelengths to short wavelengths, and potential history can be reduced even during repeated use.

According to this, it is suitable for copying machines that require main spectral sensitivity in the visible range (for example, image signals from fluorescent lamps, halogen lamps, xenon lamps, etc. - analog signals), and is suitable for use in the long wavelength side of the visible light range or in the infrared range. This makes it suitable for printers that require major spectral sensitivity (for example, light emitting diodes, gas lasers such as He-Ne lasers, image signals-digital signals of semiconductor lasers, etc.). In this sense, analog/
Both digital and digital formats can be realized.

Next, the carrier transport substance used in the present invention is not particularly limited, but for example, oquinazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidacilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxacilone derivatives,
benzothiazole derivatives, bayzimidazole derivatives,
One or two types selected from quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilhene derivatives, poly-N-vinylcarbasol, ;F, 1)-1-vinylpyrene, poly-9-vinylanthracene, etc. The above is exemplified.

Among these, carrier transport substances are preferably those that have an excellent ability to transport carriers generated during light irradiation to the support side, and are suitable for combination with TioPc and bisazo [BA] according to the present invention. Examples of charge transport materials include those represented by the following general formulas (A), (B) and (C).

General formula (A) However, A r', A r'', A r' each represents a substituted or unsubstituted aryl group, Ar' represents a substituted or unsubstituted arylene group, and R6 is a hydrogen atom, a substituted or unsubstituted arylene group, and R6 is a hydrogen atom, a substituted or Represents an unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Specific examples of such compounds are described in detail on pages 3 to 4 of JP-A-58-65440 and pages 3-6 of JP-A-58-198043.

K+ However, R7 is a substituted or unsubstituted aryl group, or a substituted group.

It is an unsubstituted heterocyclic group, R'' is a hydrogen atom, and is substituted.

It represents an unsubstituted alkyl group, a substituted or unsubstituted aryl group, and in detail, JP-A-58-134642 and JP-A-58-1.
It is described in the publication No. 66354.

However, R'' is a substituted or unsubstituted aryl group, and R11
1 Hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substitution.

They are an unsubstituted amino group or a hydroxy group, and R11 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. Synthesis methods and examples of these compounds are given in Japanese Patent Publication No. 57-
148750, which can be incorporated into the present invention.

Other preferred carrier transport materials include JP-A No. 5
No. 7-67940, No. 59-15252, No. 57-1
The hydrazone compounds described in No. 01844 can be mentioned.

Any binder resin can be used to form the carrier generation layer or the carrier transport layer, but it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. is preferred. Examples of such high molecular weight polymers include, but are not limited to, the following.

P-1) Polycarbonate P-2) Polyester P-3) Methacrylic acid resin P-4) Acrylic resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl acetate P- 9) Styrene-butadiene copolymer P-10) Vinylidene chloride-acrylonitrile copolymer P-11) Vinyl chloride-vinyl acetate copolymer P-12)
Hinychloride-vinyl acetate-maleic anhydride copolymer P-13) Silicone resin P-14) Silicone-alkyd resin P-15) Phenol formaldehyde resin P-16) Styrene-alkyd resin P-17) Poly N-vinylcarbazole P- 18) Polyvinyl butyral P-19) Polyvinyl 7-year-old rumal These binder resins can be used alone or as a mixture of two or more.

An antioxidant can be added to the photosensitive layer according to the present invention for the purpose of preventing ozone deterioration. As an antioxidant,
Hindered phenol, hindered amine, paraphenylene diamine, aryl alkane, haodoroquinone, spirochroman, spiroindanone and their derivatives,
Examples include organic sulfur compounds and organic phosphorus compounds.

These specific compounds are disclosed in Japanese Patent Application Laid-Open No. 63-1415.
No. 3, No. 63-18355, No. 63-44662,
No. 63-50848, No. 63-50849, No. 63
-58455, 63-71856, 63-71
It is described in No. 857 and No. 63-146046.

The carrier generation layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.

The amount of electron-accepting substance added is as follows: carrier-generating substance = electron-accepting substance - 100: (0,01-200),
Preferably it is 100:(0,1-100).

The electron-accepting substance may be added to the carrier transport layer. The amount of the electron-accepting substance added to this layer is as follows in weight ratio: carrier transport substance:electron-accepting substance=100:(0,01~
100), preferably 100:(0,1-50).

Specific examples of electron-accepting substances are disclosed in JP-A-63-168656.
It is stated in the number etc.

In addition, the photoreceptor of the present invention may also contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, or a dye for color sensitivity correction.

In the photoreceptor of the present invention, a carrier generation layer, a carrier transport layer, and, if necessary, auxiliary layers such as a protective layer, an intermediate layer, a barrier layer, and an adhesive layer may be laminated on the support.

Regarding the carrier generation layer, the following method may be used as appropriate.

l) A method of applying a solution in which a carrier-generating substance is dissolved in a suitable solvent, or a solution in which a binder resin is mixed and dissolved, if necessary.

2) The carrier-generating substance is made into fine particles (preferably particle size of 5 μm or less, more preferably 1 μm or less) in a dispersion medium using a ball mill, homomixer, etc., and if necessary, a binder resin is added and mixed and dispersed. How to apply.

The solvent or dispersion medium used for forming the carrier generation layer includes butylamine, diethylamine, ethylenediamine, impropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1
．． 2-dichloroethane, X, 2-; chloropropane,
1.1.2- IJ Chlor-T-9/, 1,1.1
Examples include trichloroethane, trichlorethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, inglobanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, and the like.

Further, the carrier transport layer can be formed in the same manner as the carrier generation layer described above.

The conductive support used for the photoreceptor may be a metal plate including an alloy, a metal drum or a conductive polymer, a thin layer of metal such as aluminum, palladium or gold including a conductive compound or alloy such as indium oxide. Examples include paper and plastic films made conductive by coating, vapor deposition, or lamination.

As an intermediate layer such as an adhesive layer or a barrier layer, in addition to the polymer used as the binder resin, an organic polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used.

Next, the specific structure of the photoreceptor of the present invention will be described.

FIGS. 3 and 4 are sectional views of photoreceptors according to embodiments of the present invention, respectively.

Figure 3 shows that the carrier transport layer (CTL) is the carrier generating layer (
CGL), which is a preferable embodiment as a negative charging photoreceptor; conversely, FIG. 4 shows an embodiment in which CGL is laminated on a CTL, which is preferable as a positive charging photoreceptor. It is a mode.

Furthermore, in the present invention, since two types of carrier generating material (CGM), Ti0Pc and bisazo [BA], are used, it is possible to form CGL in separate layers.

In FIG. 3(a), l is a support, 2 is a CGL, and consists of two upper and lower layers of CGLs 2A and 2B. 3 is a CTL containing a carrier transport material (CTM). A similar configuration is also possible in the case of FIG. 4, and the same symbols as in FIG. 3 represent layers with the same meaning.

When a two-layer structure is adopted for the CGL, this may be due to the ionization potential or the energy injection barrier of the CTL, but for the negative charging shown in Figure 3, Ti0Pc is applied to CGL 2A in contact with the CTL, and bisazo is applied to CGL 2B in contact with the support.
BA] is preferably allocated. Also, in the case of positive charging as shown in Fig. 4, Ti0Pc is applied to the lower layer CGL2B in contact with the CTL.
When bisazo [BA] is applied to the upper layer CGL2A, the performance becomes better.

The layer structure of the photoreceptor of the present invention is shown in FIGS. 3(a) and 4(a).
Various embodiments are possible, not limited to a).

In Fig. 3, 4 in Fig. 3(b) is a CGL mixed with Ti0Pc and acetic acid (B A);
) is a carrier generation-transport composite layer (C) in which either Ti0Pc or bisazo [BA] is mixed with CTM.
Furthermore, 7 in the same figure (d) is a CGTL which is a hybrid of two types of CGM and CTM.

A similar configuration can be provided also in the case of positive charging shown in FIG.

In the present invention, an auxiliary layer may be used, and FIG. 3 shows an embodiment in which a protective layer 8, a barrier layer (or adhesive layer) 9, and an intermediate layer 1O are provided. The same applies to the case of FIG.

In the CGL, the weight ratio of CGM and binder is preferably 100:0 to 1000. If the content of CGM is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, dark decay and acceptance potential will decrease.

In FIGS. 3 and 4, the film layer of the lower CGL 2 B is 0.01-10p rn (and even 0.0505-1p
It is preferable that the film thickness of the upper CGL2A is 0.01
It is preferable to set it as 10 micrometers (furthermore, 0.5-5 micrometers).

Also, in CTL, CTM is the binder resin 1 in CTL.
It is preferably 20 to 200 wt, particularly preferably 30 to 150 wt per 00 parts by weight (denoted as vt).

Further, the thickness of the formed CTL is preferably 5 to 50μ.
(2) Particularly preferably 5 to 30 μm melon.

FIG. 5 shows an example of an image forming apparatus using the photoreceptor 11 of the present invention. Here, 20 is a charging electrode, 21 is a long-wave light source, 22 is a short-wave (visible light) light source, 23 is a developing device, 25 is a transfer electrode, 26 is a separation electrode, 27 is a cleaning blade, and 28 is a static elimination lamp. It is.

Examples of light sources that can be used as the light sources 21 and 22 include white light, halogen lamp light, tungsten light, fluorescent lamp light, laser light (semiconductor laser, He-Ne laser), LED, and the like.

The developing device 23 may use either a normal forward development method or a reversal development method. The static elimination lamp 28 is effective during both forward development and reverse development.

When forming an image, first of all, when using a white light source,
The photoreceptor charged at 20 is imagewise exposed at 22 and developed at 23. This is transferred onto a transfer paper 24 using 25 transfer electrodes, and the transfer paper is separated using 26 separation electrodes.

The toner remaining on the photoreceptor 11 is scraped off and cleaned at 27.

On the other hand, when a laser light source is used, the photoreceptor charged at 20 is imagewise exposed at 21 and developed at 23. This is transferred onto transfer paper 24 using 25 transfer electrodes, and 2
The transfer paper is separated by the separation electrode 6. 27 toners left
is cleaned with.

In a recording apparatus that uses a drum-shaped photoreceptor like this recording apparatus, image exposure using a laser light source is preferably performed using a laser beam scanner as shown in FIG.

The operation of the laser beam scanner shown in FIG. 6 will now be described.

A laser beam generated by a semiconductor laser 41 is swung left and right within a predetermined amplitude angle by a polygon mirror 43 rotated by a drive motor 42, passes through an f-theta lens 44, and has an optical path bent by a reflecting mirror 45 to reach a photoreceptor. 23 and scans over a line 46.

47 is an index sensor for detecting the start of beam scanning, and 48 and 49 are cylindrical lenses for correcting the inclination angle. Reflecting mirrors 50a, 56b, and 50c form a beam scanning optical path and a beam detection optical path.

When scanning is started, the beam is detected by the index sensor 47, and modulation of the beam by a signal is started by a modulation section (not shown). The modulated beam scans over a photoreceptor that has been uniformly charged in advance by a charger 20. A latent image is formed on the drum surface by main scanning by the laser beam 51 and sub-scanning by the rotation of the photoreceptor.

Further, in a recording apparatus in which the photoreceptor is in a flat state like a belt, the image exposure may be flash exposure.

〔Example〕

Examples 1 to 20 of the present invention are listed below, and Comparative Examples (1) to
Although the description will be made with reference to (3), the embodiments of the present invention are not limited to the following examples.

Next, a synthesis example of Y-type titanyl 7-thalocyanine used for detailed explanation of the present invention will be given.

Synthesis Example 1 1. Mix 29.2 g of 3-diiminoisoindolizine and 200 mL of sulfolane, and add titanium tetraisopropoxide; 17. Og was added, and the mixture was reacted at 140°C for 2 hours under a nitrogen atmosphere. After cooling, the precipitate was collected by filtration, washed with chloroform, washed with 2% hydrochloric acid, washed with water, further washed with methanol, and after drying, 25.5 g (88
, 5%) of titanyl phthalocyanine was obtained.

The product was dissolved in 20 times the amount of concentrated sulfuric acid, poured into 100 times the amount of water, precipitated and collected by filtration, and the wet cake was dissolved in 1.2 times the amount of water.
- Y-type Ti0Pc heated with dichloroethane at 50°C for tO hours and has an X-ray diffraction spectrum shown in Figure 1(a).
And so. In this crystal, the peak intensity at a Bragg angle of 2θ of 9.6° was 102% of that at a Bragg angle of 27.2°.

Let this be Ti0PcY.

Synthesis Example 2 A wet cake obtained by processing in exactly the same manner as in Synthesis Example 1 was stirred in 1.2-dichloroethane at room temperature for 1 hour to obtain Y-type Ti0Pc. This crystal has a Bragg angle of 2θ of 9
．． The peak intensity at 6% was 75% of that at 27.2%.

This is designated as Ti0PcY2.

Synthesis Example 3 Acrodinitrile; 25.6 g and α-chlornaphthalene; 5.5 m in a mixture of 150 m12 in a nitrogen stream
12 of titanium tetrachloride was added dropwise and heated at 200 to 220°C for 50 minutes.
Allowed time to react. The precipitate was collected by filtration and σ-chlorna? After washing with talene, chloroform washing was performed, followed by methanol washing. The mixture was then refluxed in aqueous ammonia to complete hydrolysis, washed with water, washed with methanol, and dried to obtain 21.8 g (75.6%) of titanyl 7-talocyanine.

The product was dissolved in 10 times the amount of concentrated sulfuric acid, poured into 100 times the amount of water, precipitated, collected by filtration, and the wet cake was dissolved in 1.2-
The mixture was stirred in dichloroethane at room temperature for 1 hour to obtain Y-type Ti0Pc having the X-ray diffraction spectrum shown in FIG. 1(b).

This crystal has a peak intensity of 9.6° with a Bragg angle of 2θ of 2
It was 45% of that at 7.2°.

This is designated as Ti0PcYs.

Synthesis Example 4 A wet cake obtained by processing in exactly the same manner as in Synthesis Example 3 was stirred in 0-dichlorobenzene at room temperature for 1 hour to obtain Y-type Ti0Pc. This crystal has a Bragg angle of 2θ of 9
．． The peak intensity at 6° was 27.35% of that at 2°. This is referred to as Ti0PcY.

The requirements for preparing the photoreceptor sample are as follows, and the requirements are summarized in Table 1.

CA) Preparation of photoreceptor constituent layer coating (1) Examples 1 to 20 and comparative examples (1) and (2)a
, Undercoat layer (OCL) paint polyamide resin (CM 8000; manufactured by Toshi) 25
gr methanol 1000II
IQ mixed and dissolved, film thickness 0.5μm on aluminum substrate
It was applied to.

b, CGL paint CGM (compounds listed in Table 1) 20g silicone resin (KR5240, manufactured by Shin-Etsu Silicon) 20g
rIsopropylene acetate Mixed with 1000+Q sand grinder at 11000 rpm for 2 hours, film thickness 0.5mm (however, in the case of two-layer CGL, each layer is 0.25μ
(addressed to m).

c, CTL paint CTM (compounds listed in Table 1) 13gr polycarbonate (Nipilon Z-200, manufactured by Mitsubishi Gas Chemical) 22
gr1.2-dichloroethane 100
0+O4 was mixed, dissolved, and applied to a film thickness of 20 μm.

The symbols I:cGM and CTM shown in Table 1 are as follows.

CGMI A/Y type Ti0Pc (Y Is Y!
, Y, and layer 4) B... ''m-type Ti0Pc...σ-type Ti0Pc CGM2 E...β-type Ti0Pc a...Exemplary compound No., 5 a'...Exemplary compound No., 7 a “...Exemplified Compound No. 8 a″'...Exemplified Compound No. 9 b... CTM [X] (Y) [z] (2) Comparative Example (3) Ammonia aqueous solution of casein on an aluminum cylinder was applied and dried to form a UCL with a film thickness of 0.5 μm.

Next, the carrier generating substance is added to 1. Qwt1 polyvinyl butyral 1wt and isopropyl alcohol 30w [
was dispersed for 4 hours using a ball mill disperser. This dispersion was applied onto the previously formed UCL using a dip coating method,
Dry to form CGL.

The film thickness at this time was 0.25 μm.

Next, add carrier generating substance B to 1. 1 wt of Qwtl polyvinyl butyral was dispersed for 4 hours using a 3Q ball mill dispersion machine, and this dispersion was mixed with the previously formed C
It was applied onto GL by a dip coating method, and the film thickness at this time was 0.25μ.

However, when CGM is mixed to form a mixed CGL (comparative example (
3)) Mix equal amounts of the above two paints and form a film with a film thickness of 1.5 μm.
It was set as CGL.

Next, lv CTM, which is a hydrazone compound with the following structural formula,
t, 1 wt of polycarbonate resin, and 6 wt of dichloromethane were mixed, and the mixture was stirred and dissolved using a stirrer. This solution was applied onto CGL by dip coating and dried to form CTL. The film thickness at this time was 20 μm.

CB) Lamination order configuration of photoreceptor constituent layers I... CGM hybrid system (Figure 3 (b) type) configuration ■... CGM two-layer separated system (Figure 3 (a) type) If
- l; TioPc layer CTL, adjacent ■-2; Bisazo [BA] layer-CTL adjacent structure configuration... CGM two-layer separation system (C) (Fig. 4 (a) type) ml l; TioPc layer CTL adjacent ■ -2; Bisazo [BA] layer - CTL adjacent coating method UCL...Dip coating method CGL...Mixed system; Deep coating method two-layer separation system;
Ring Coating Method CD) Characteristic Evaluation Tests for evaluating the characteristics of the photoreceptor samples No. 1 thus obtained were carried out as follows. Post the results in Group 1.
.

[Sensitivity test]

Using an electrostatic charging tester EP A-8100 (manufactured by Kawaguchi Electric Co., Ltd.), the exposure amount EIA ((2ux-sec) required for reducing the photoreceptor surface potential by half from the initial potential was measured.

[Repetitive characteristic test]

Using the electrostatic charging test device EP A-8100,
1st and 10th time when charging → exposure → static elimination is repeated 100 times
The amount of change Δo, +oo(y) in the charging potential at the 0th time was measured. (Determined as 1Δv o l.) [Long-wavelength photosensitivity measurement] Using a tungsten lamp as a light source in the above-mentioned EPA-8100 measuring instrument, the wavelength of 780 nm ± 1n111 of particular concern was measured through a monochromator. E'A (V cm"/erg) with respect to light was measured. The larger the value, the better the sensitivity.

〔Effect of the invention〕

As is clear from the results in Table 1, the examples of the present invention are superior to the comparative examples in all respects such as sensitivity to white light and laser light, and repeatability. Also, it can be seen that it is preferable in the present invention to be adjacent to the two-layer CGL.

[Brief explanation of drawings]

Figure 1 is an X-ray diffraction spectrum diagram of Ti0Pc with a photoreceptor l diagonal, Figure 2 is a spectral absorption spectrum diagram of Ti0Pe,
FIGS. 3 and 4 are cross-sectional views of embodiments of the photoreceptor of the present invention. FIG. 5 is a schematic diagram of an example of an image forming apparatus using the photoreceptor of the present invention, and FIG. 6 is an explanatory diagram of the operation of a laser beam scanner.

Claims (2)

[Claims] (1) A photosensitive layer containing a carrier-generating substance and a carrier-transporting substance is provided on a substrate, and titanyl phthalocyanine and a bisazo pigment represented by [BA] are separately or mixed as carrier-generating substances in the photosensitive layer. An electrophotographic photoreceptor provided with a layer containing General formula [BA] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas, tables, etc. There is ▼. Ar_2 and Ar_3 each represent an aromatic ring group. R_1 and R_3 each represent a hydrogen atom, an alkyl group, or an aryl group. R_2 represents an alkyl group, a carboxyl group, or an ester group thereof. Z represents an atomic group necessary to form an aromatic ring or a heterocycle. ] (2) The titanyl phthalocyanine has a Cu-Kα ray (
In the X-ray diffraction spectrum for a wavelength of 1.541 Å), the Bragg angle 2θ is at least 9.6 ± 0.2° and 27
．． It has a peak at 2 ± 0.2°, and the peak intensity at 9.6 ± 0.2° is 40% of the peak intensity at 27.2 ± 0.2°.
% or more of titanyl phthalocyanine in a crystalline state.