JPH0337667A - Electrographic sensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity to white light or laser light and repetitive characteristics by forming layers separately contg. titanylphthalocyanine and a specified bisazo pigment as carrier generating materials or a layer contg. a mixture of them as a photosensitive layer. CONSTITUTION:Layers separately contg. titanylphthalocyanine and a bisazo pigment represented by formula I as carrier generating materials or a layer contg. a mixture of them is formed as a photosensitive layer 2 contg. the carrier generating materials and a carrier transferring material on a substrate 1. In the formula, Z is arylene, R3 is alkyl or aryl, R4 is H, alkyl or aryl, Ar is aryl and Y is a group of atoms required to form an arom. carbon ring or a hetero ring. Sensitivity to white light or laser light and repetitive characteristics are improved.

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. It 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 first adapts to the printer function! In particular, it must have high sensitivity in the near-infrared region, and must also be highly sensitive to light in the visible light region in order to be compatible with 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-A12-As) light emitting device has an oscillation wavelength of 750 nm.
n+s or more, and is sensitive in such a long wavelength range, for example, Japanese Patent Publication No. 49-4338
No., JP-A-58-182639, JP-A No. 60-19151
Examples include metal-free 7-ironanine compounds of the Xl rl τ, wa, and η' type described in No.

Furthermore, the a-type titanyl phthalocyanine described in JP-A No. 61-239248, the β-type titanyl-7 thalocyanine described in JP-A No. 62-67094, and the report in Electrophotographic Society Vol. 27, No. 4 (p. 19-24) Examples include m-type titanyl phthalocyanine.

However, such electrophotographic photoreceptors, which have high sensitivity in the long wavelength range, do not have sufficient photosensitivity from the medium wavelength range to the 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 containing phenanthraquinone type instead of 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 provide a photosensitive layer containing titanyl phthalocyanine as a carrier substance and a compound of the following general formula [ This is achieved by an electrophotographic photoreceptor provided with a layer containing a bisazo pigment represented by BA] either separately or in a mixture.

The titanyl phthalocyanine preferably used in the present invention is
In the line diffraction spectrum, the peak position at the Bragg angle 2θ including a measurement error of ±0.2° (the error value of ±0.2° will be omitted in the following description) is (1) 7.5'
, 12.3°, 16.3°, 25.3° and 28.7'
i: α-type titanyl phthalocyanine with a strong peak,
(2) 9.3°, 10.6', 13.2°, 15.1'
, 15.7°, 16.1', 20.8°, 23.3°,
26.3° and 27.1'i: β-type titanyl 7-dironanine with strong peaks, (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, Y
type titanyl phthalocyanine to distinguish it from the former two)
It is.

The peak of titanyl phthalocyanine according to the present invention is
It is a conical projection with an acute angle that is clearly different from noise.

The basic structure of the titanyl phthalonanine of the present invention is represented by the following general formula (P c).

General formula [PC] represents an atom, an alkyl group, or an alkoxy group, and n,
m and Q represent integers 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 dag.

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 with. After the reaction is completed, the mixture is allowed to cool and the precipitate is collected by filtration to obtain titanyl phthalocyanine.

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 phthalocyanine in a crystalline state whose peak intensity at 9.6° is 40% or more of the peak intensity at 27.2° is used. Preferably, and more preferably, in the 7thalocyanine according to the present invention, titanyl phthalocyanine in a crystalline state exhibiting a peak intensity of 60% or more at 9.6° based on the peak intensity at 27° and/or titanyl phthalocyanine at 9.6°. The peak intensity is 50% or more and the peak intensity at 6.7° is 30
% 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 (B A) according to the present invention, the general formula (B A) [wherein R1 and R1 each represent a hydrogen atom, a halogen atom, or an alkyl group].

, Y, , represents.

Z represents an arylene group. R3 represents an alkyl group or an aryl group. R6 represents a hydrogen atom, an alkyl group or an aryl group. Ar represents an aryl group.

Y represents an atomic group necessary to form an aromatic carbocycle or a heterocycle.

Examples of the alkyl group represented by R1-R1 include methyl group and ethyl group, and examples of the aryl group represented by R1-R, Ar include phenyl group and naphthyl group. may have a substituent.

Examples of the arylene group represented by 2 include a phenylene group and a naphthylene group, and these groups may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, and a hydroxyl group.

Z is particularly preferably a substituted or unsubstituted phenylene group.

The aromatic carbocycle or heterocycle formed by Y is, for example, a benzene ring, a naphthalene ring, a triazole ring, etc.

The compound represented by the general formula [BA] (hereinafter referred to as bisazo (B
It is called A). ) are shown below, but the invention is not limited thereto.

Azo compounds such as No. 23 and above can be easily synthesized, for example, by the method described in JP-A-59-229564.

The bisazo [BA] according to the present invention is 450n+a to 600
It has high sensitivity in the n- region, which compensates for 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 repeatability with respect to charging potential, residual potential, etc. is remarkable. It has the characteristic of being stable.

There is not necessarily a uniform selection method for the combined use of different types of carrier-generating substances, and in the present invention, the combination of Ti0Pc and bisazo [BA] is determined from a large number of compounds through repeated experiments. This is what I did.

With this combination of the present invention, high sensitivity can be maintained in a wide spectral region from long wavelengths to short wavelengths, and the 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 includes, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidazolidine. derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxacilone derivatives,
benzothiazole derivatives, bayzimidazole derivatives,
Examples include one or more selected from quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilhene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc. .

Among these carrier transport substances, in addition to their excellent ability to transport carriers generated during light irradiation to the support side,
Those suitable for combination with TioPc and bisazo (BA) according to the present invention are preferred, and examples of such 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 represent a substituted or unsubstituted aryl group, Ar' represents a substituted or unsubstituted arylene group, and R1 is a hydrogen atom, a substituted or unsubstituted arylene group, and R1 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.

General formula (B) However, R7 is a substituted or unsubstituted aryl group, or a substituted group.

It is an unsubstituted heterocyclic group, and Ra 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.

General formula (C) R' However, R1 is a substituted or unsubstituted aryl group, and RI0
Hydrogen atoms, halogen atoms, substituted and unsubstituted alkyl groups,
Substituted or unsubstituted alkoxy group, i-substituted.

unsubstituted amino group, hydroxy group, R'' is substituted,
Represents an unsubstituted aryl group, a substituted or unsubstituted heterocyclic group.

Synthesis methods and illustrations of these compounds are given in Japanese Patent Publication No. 57-1
It is described in detail in No. 48750, and 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)
Vinyl chloride-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-vinyl carbazole P-18) Polyvinyl butyral P-19) Polyvinyl 7olmar 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 fatigue during repeated use, and the like.

The amount of electron-accepting substance added is carrier-generating substance: 1-child-accepting substance - 100: (0.01 to 200) by weight;
Preferably it is 100:(0.1-100).

The electron-accepting substance may be added to the carrier transport layer. The amount of electron-accepting substance added to this layer is carrier transporting substance:electron-accepting substance-100:(0, old to 100) by weight ratio.
), 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.

■) A solution of a carrier-generating substance dissolved in an appropriate solvent,
Or, if necessary, add a binder resin and apply a mixed solution.

2) Convert the carrier-generating substance into fine particles (preferably particle size of 5 μm or less,
More preferably 1 pLl or less), and if necessary, a binder resin is added and mixed and dispersed, and a dispersion is applied.

Solvents or dispersion media used to form the carrier generation layer include butylamine, diethylamine, ethylenediamine, impropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, and toluene. , xylene, chloroform,
1.2-dichloroethane, ■, 2-dichloropropane,
1,1.2-trichloroethane, 1.1.1 trichloroethane, trichlorethylene, tetrachloroethane,
Examples include dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, impropanol, 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 containing an alloy, a metal drum, or a conductive polymer, coated with a thin layer of metal such as aluminum, palladium, or gold containing a conductive compound or alloy such as indium oxide. Examples include paper, plastic film, etc., made conductive by 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 substances (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 hybridized with Ti0Pc and bisazo (B A), and Fig. 3(c)
5 is a carrier generation-transport composite layer (CG) in which either Ti0Pc or bisazo [BA] is mixed with CTM.
TL), and 7 in the same figure (d) is two types of CGM and C
It is CGTL hybridized with TM.

A similar configuration can be provided 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 10 are provided. The same applies to the case of FIG.

In the CGL, the weight ratio of CGM and binder is preferably 100:0-1000. 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 2B is 0.
It is preferable to set it as 0l-10pm (furthermore, 0.05-lpm), and the film thickness of upper CGL2A is 0.01-10pm.
It is preferable to set it as micrometer (furthermore, 0.5-5 micrometer).

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

Further, the thickness of the formed CTL is preferably 5 to 50μ.
-1 Particularly preferably 5 to 30 μm.

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 II 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 can be set to 7 lashes.

〔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 phthalocyanine used for detailed explanation of the present invention will be given.

Synthesis Example 1 1. Mix 29.2 g of 3-diiminoisoindolizine and 200 mQ 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.
- Heating with dichloroethane at 50°C for 10 hours as shown in Figure 1 (
A Y-type Ti0Pc having the X-ray diffraction spectrum shown in a) was used. In this crystal, the peak intensity at Bragg angle 2θ of 9.6° is 102% of that at 27.2°.

Let this be Ti0PcY.

Synthesis Example 2 A sea urchin throat cake obtained in exactly the same manner as in Synthesis Example 1 was stirred in 1,2-dichloroethane at room temperature to obtain Y-type Ti0Pc. This crystal has a Bragg angle of 2θ of 9
, the peak intensity of 6% was 75% of that of 27.2%.

Let this be 7i0PCYz.

Synthesis Example 3 In a nitrogen stream, (i,
Drop 5+n12 of titanium tetrachloride and heat at 200-220°
0 for 5 hours. The precipitate was collected by filtration and washed with σ-chlornaphthalene, followed by chloroform washing and then methanol washing. Next, after completing the hydrolysis by refluxing in ammonia water, washing with water, washing with methanol, and drying, titanyl phthalocyanine; 21.8 g (75,6
%) was obtained.

The product was dissolved in 10 times the amount of concentrated sulfuric acid, poured into 100 times the amount of water, precipitated, and collected by filtration. The wet cake was stirred in layer 2-dichloroethane at room temperature for 1 hour to give the result shown in Figure 1 (b). The Y-type Ti0Pc had the X-ray diffraction spectrum shown below. This crystal has a peak intensity of 27° at a Bragg angle of 2θ of 9.6°.
．． It was 45% of that at 2°.

This is designated as Ti0PcY1.

Synthesis Example 4 A wet cake obtained by the same treatment as in Synthesis Example 3 was stirred in 0-dichlorobenzene at room temperature for 1 hour to obtain Y-type Ti0Pc. In this crystal, the peak intensity at a Bragg angle of 2θ of 9.6° was 35% of that at 27.2°. This is referred to as Ti0PcY.

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

(A) Preparation of photoreceptor constituent layer coating (1) Examples 1 to 20 and comparative examples (1) and (2) a
, Undercoat layer (OCL) paint polyamide resin (CM8000; manufactured by Toshi) 25g
rMethanol 100100O
The mixture was mixed and dissolved and coated on an aluminum substrate to a thickness of 0.5 μm.

b, CGL paint CGM (compounds listed in Table 1) 20g silicone MR resin (KR5240; manufactured by Shin-Etsu Silicon) 20g
risopropyl acetate 1000+nQ
Mix with a sand grinder for 1000 rp + 11.2 hr, and the film thickness is 0.5 μm (however, in the case of two-layer CGL, each layer is 0.5 μm thick).
．． 25 μm).

c, CTL paint CTM (compounds listed in Table 1) 13gr polycarbonate (Nipilon Z-200, manufactured by Mitsubishi Gas Chemical) 22
gr1.2-Dichloroethane 1O00IIla was mixed, dissolved, and applied to a film thickness of 20 μm.

The CGM and CTM listed in Table 1 with symbols are as follows.

CGMI A...Y type T+0Pc (Y r, Y 1
, Y s and Y4) B...CGM2 C-m type Ti0Pc D...α type Ti0Pc E -...β type Ti0Pc a...Exemplary compound No., 1 a'...Exemplary compound N002 a"・...Exemplary compound No. 3 a'''...Exemplary compound No. 4 CTM (X) (Y'l [Z] (2) Comparative example (3) An ammonia aqueous solution of casein was applied on an aluminum cylinder and dried. Then, a UCL having a film thickness of 0.5 μI was formed.

Next, the carrier-generating substance was mixed with 1 wt of polyvinyl butyral and 3 wt of isopropyl alcohol.
0vt was dispersed for 4 hours using a ball mill disperser. This dispersion was applied by dip coating onto the previously formed UCL and dried to form a CGL.

The film thickness at this time was 0.25 μm.

Next, 1.0 ft of carrier-generating substance B was dispersed for 4 hours using a full ball mill disperser using polyvinyl butyral lvt and 30 wt of isopropyl alcohol, and this dispersion was applied by dip coating onto the previously formed CGL. The film thickness was 0.25 μm.

However, when CGM is mixed to form a mixed CGL (comparative example (
3)) Mix equal amounts of the above two paints and apply film thickness method 1. 1 wt of CTM, which is a hydrazone compound having the following structural formula, 1 wt of polycarbonate resin, and 5 vt of dichloromethane were mixed and dissolved by stirring with a stirrer. This liquid was applied onto the CGL by a dip coating method and dried to form a CTL. The film thickness at this time was 20 μ■0 CB) Lamination order structure of the photoreceptor constituent layers Diagram (a) Type) I
I l; TioPc layer CTI, adjacent ■-2; Bisazo CBA) layer-CTL adjacent configuration ■...C0M2 layer separation system (Fig. 4 (a) type) m l; TioPc layer CT
L adjacent ■-2; Bisazo [BA] layer - CTL adjacent (C) UCL...Dip coating method CGL...Mixed system; Deep coating method two-layer separation system;
Ring Coating Method (D) Characteristic Evaluation A characteristic evaluation test of the thus obtained photoreceptor sample No. 1 was carried out as follows. The results are listed in Table 1.

[Sensitivity test] Electrostatic charging test device E P p, -8100 (Kawaguchi Electric (
((2ux-see)) was measured as the exposure amount E required to reduce the surface potential of the photoreceptor by half from the initial potential.

[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 in charging potential (Δ'-""CV) at the 0th time was measured. (Determined as 1Δv HI.) [Long-wavelength photosensitivity measurement] Using a tungsten lamp as a light source in a measuring meter using the EPA-8100 mentioned above, the wavelength of 780 ± 1 cm of particular concern was measured through a monochromator. E for the light of
'A (V am''/erg) 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]

FIG. 1 is an X-ray diffraction spectrum diagram of Ti0Pc used in the photoreceptor, FIG. 2 is a spectral absorption spectrum diagram of Ti0Pc, and 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 the following general formula [BA
An electrophotographic photoreceptor comprising a layer containing a bisazo pigment represented by the following, either separately or in a mixture. General formula [BA] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 each represent a hydrogen atom, a halogen atom, or an alkyl group. A represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Z represents an arylene group. R_3 represents an alkyl group or an aryl group. R_4 represents a hydrogen atom, an alkyl group, or an aryl group. Ar represents an aryl group. Y represents an atomic group necessary to form an aromatic carbocycle 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.