JPH0337674A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity to white light and laser beams and repeated use enduring characteristics by incorporating a specified compound together with titanyl phthalocyanine as a carrier generating material in a photosensitive layer and enhancing the spectral sensitivity of the former at least in a part of wavelength region in the photosensitive body higher than that of the latter. CONSTITUTION:The photosensitive layer 2 formed on a conductive substrate 1 contains a carrier transfer material and as the carrier generating material the compound having spectral sensitivity in the wavelength region of 450 - 600nm and the titanyl phthalocyanine, and the spectral sensitivity of the former in at least one part of the wavelength region of the photosensitive body is higher than that of the latter in the wavelength region, thus permitting sensitivity to white light and laser beams and repeated are 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 that use organic photoconductive materials (OPC) are
They have recently attracted attention because they are generally less toxic than inorganic photoconductive substances and are advantageous in terms of flexibility, lightness, film formability, cost, etc.

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 useful because the range is expanded, and as a result, it is possible to improve the electrophotographic photoreceptor, 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 be compatible with the printer function, 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-arsenide (Ga-AQ-As) light emitting device has an oscillation wavelength of 750 nm.
m or more and is sensitive in such a long wavelength range, for example, Japanese Patent Publication No. 49-4338,
Examples include X+ rt τ , η, η' type metal-free phthalocyanine compounds described in JP-A-58-182639 and JP-A-60-19151.

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 electrophotographic studies reported in Vol. 27, No. 4 (p. 19-24) of the Journal of the Society of Electrophotography. Examples include m-type titanyl phthalocyanine.

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 bisazo 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.

[Objective of the invention J The object of the present invention is to have a highly sensitive spectral sensitivity characteristic ranging from visible light to near-infrared light, and to have 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 that can be applied to an apparatus, has excellent repeatability, and can respond to high-speed copying processes.

[Structure and effects of the invention]

The object of the present invention described above is to provide a photosensitive layer containing a carrier transporting substance and a carrier generating substance on a substrate; in an electrophotographic photoreceptor, titanyl phthalocyanine and a spectral sensitivity in the wavelength range of 450 to 600 nm are used as the carrier generating substance; and wherein the spectral sensitivity of at least a part of the wavelength range expressed in the photoreceptor of the compound is greater than the spectral sensitivity of the corresponding wavelength range expressed by the titanyl 7-lycyanine. It is achieved through the body.

The titanyl 7-lycyanine used in the present invention is
In the X-ray diffraction spectrum for the Cu-Kcr line (wavelength 1.541), the peak position at the Bragg angle 2θ including a measurement error of ±0.2 (in the following description, ±0.
2a error value is omitted) is (1) 7.56.12.3
α-type titanyl phthalocyanine with strong peaks at ', 16.3', 25.3° and 28.7°, (2) 9.3
°, 10.6°, 13.2°, 15.1', 15.7°
, β-type titanyl phthalocyanine with strong peaks at 16°1°, 20.8', 23.3°, 26.3° and 27.1', (3) 6.9°, i5.5° and 23. m-type titanyl phthalocyanine with a strong peak at 4° and (4
) is a titanyl phthalocyanine having strong peaks at 9.6° and 27.2″ (in the present invention, it is referred to as Y-type titanyl phthalocyanine to distinguish it from the former two).

The basic structure of the titanyl phthalocyanine of the present invention is represented by the following general formula (Pc).

- Formation CP c) However, X 1. X! , X3. X 4 represents a hydrogen atom, a norogen atom, an alkyl group, or an alkoxy group, and n, m, and (2) each represent an integer of 0 to 4.

The above X-ray diffraction spectrum is a reflection diffraction spectrum measured under the following conditions. (Using 320 type self-recording spectrophotometer (newly manufactured by Hitachi)) X-ray tube Cu Voltage 40. OKV current
too mA 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 with O. 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.

The peak related to T 1OPc according to the present invention forms a sharp pyramidal projection that is clearly different from noise.

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

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''. Cyyanine is preferred, and more preferably titanyl phthalocyanine and/or 9.6 in a crystalline state exhibiting a peak intensity of 9.66 of 60% or more based on the peak intensity of 27.2'' in the phthalocyanine according to the present invention. By containing titanyl phthalocyanine in a crystalline state in which the peak intensity of ° is 50% or more and the peak intensity of 6.76 is 30% or less, a photoreceptor with high sensitivity and good charging characteristics can be formed. .

Next, carrier generating substances suitable for complementing the spectral sensitivity in combination with Ti0Pc according to the present invention include:
Generally, it absorbs light in the wavelength range of 450 to 600 nm,
Any W&pigment or organic pigment can be used as long as it generates free carriers and forms a spectral sensitivity higher than T 1OPc in the wavelength range.

Among these, preferable carrier-generating substances that complement the spectral sensitivity of Ti0Pc are bisazo pigments having an anthraquinone skeleton represented by the following formulas (Al), (A2) and [A], or the following - Formation [S
S] A bisazo pigment having a styryl-stilbene structure or a perylene-based pigment, -formation [A1] General formula General formula [A,] In the formula, A is, where n is l or 2, m is 0 .1 or 2. selected from the group consisting of substituted sulfonamide groups, Z is a hydrocarbon aromatic ring such as a benzene ring or a naphthalene ring, a heterocyclic aromatic ring such as a carbazole ring, benzofuran ring or indole ring, or a substituted product thereof; R1 is a hydrogen atom, a substituted or unsubstituted amino group, an alkyl group, a carbamoyl group, a carboxylic acid group, or an ester group thereof, AI is a substituted or unsubstituted aryl group, R, , R are each substituted or unsubstituted Represents an alkyl group, an aralkyl group, or an aryl group.

General Formula [SS] In the formula, A r 11 A r * and Ars each represent a substituted or unsubstituted aromatic carbocyclic residue or a substituted or unsubstituted aromatic heterocyclic residue.

R, , R, , R and R4 each represent a hydrogen atom or an electron-withdrawing group. However, at least one of R, -R,
One is an electron-withdrawing group.

A is N) 150! Rs (where R6 and R7 each represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group);

Y is a halogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted s7-amoyl group, a carboxyl group, or a sulfo group. Z represents an atomic group necessary to constitute a substituted or unsubstituted carbocyclic aromatic ring or a substituted or unsubstituted heterocyclic aromatic ring.

R5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a carboxyl group, or an ester group thereof. A' represents a substituted or unsubstituted aryl group. n represents an integer of 1.2 or 3, and m represents an integer of 0.1 or 2.

Additionally, the following pigments may be used depending on Ti0Pc.

(1) Indigoid pigments such as indigo derivatives and thioindigo derivatives (2) Carbonium pigments such as diphenylmethane pigments, triphenylmethane pigments, xanthine pigments and acridine pigments (3) Quinoneimine pigments such as azine pigments, oxazine pigments and thiazine pigments (4) Methine pigments such as cyanine pigments and azomenthine pigments (5) Quinoline pigments (6) Benzoquinone and naphthoquinone pigments (7) Naphthalimide pigments (8) Perinone pigments such as bisbenzimidazole derivatives This invention The carrier generating material (hereinafter expressed as 100) that complements the spectral sensitivity of Ti0Pc is 450 nm to 60 nm.
Ti0Pc has high sensitivity in the 0 nm region and is used in the present invention.
It supplements the sensitivity in the low sensitivity spectral region of the invention, and when used in combination with the T 1OPc according to the present invention, it has the characteristic that the cyclic characteristics of charging potential, residual potential, etc. are extremely stable.

There is not necessarily a uniform selection method for such a combination of different types of carrier-generating substances, and in the present invention, the combination of Ti0Pc and PcTi was determined from a large number of compounds through repeated experiments. .

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

FIG. 3 shows an example of the sensitivity of the complementary spectra of Ti0Pc and PcTi.

According to this, copy m that requires main spectral sensitivity in the visible range
(e.g., fluorescent lamps, halogen lamps, xenon lamps, etc.; It is suitable as an image signal (digital signal) of a gas laser such as a laser, a semiconductor laser, 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 Ti0Pc and PcTi according to the present invention are preferred, and such charge transport materials include those represented by the following -formations (TI), (Tz) and (T,).

General formula (T1) However, Ar', Ar'', and Ar' each represent a substituted or unsubstituted aryl group, Ar' represents 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.

bar However, R7 is a substituted or unsubstituted aryl group, or a substituted group.

It is an unsubstituted heterocyclic group, and R8 is a hydrogen atom and is substituted.

It represents an unsubstituted alkyl group, a substituted or unsubstituted aryl group, and in detail, it refers to JP-A-58-134642 and JP-A No. 58-5g-1.
It is described in the publication No. 66354.

-Formation (T3) R9 However, R' is a substituted or unsubstituted aryl group, and R' is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted.

It is an unsubstituted amino group or a hydroxy group, and R1+ 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
7-67940'), 1m No. 59-15252, 5
The hydrazone compounds described in No. 7-101844 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-vinylcarbazole P-18) Polyvinyl butyral p-19) Polyvinyl formal These binder resins can be used alone or as a mixture of two or more types.

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, hydroquinone, spirochroman, spirodanone 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 as follows: carrier-generating substance: electron-accepting substance = 100: (0,01 to 200)
), preferably 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), good! L < Hatoo: (0,1~
50) There is a T.

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.

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

2) A method in which a 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 a binder resin is added as necessary to mix and disperse the resulting dispersion, and then the mixture is applied. .

Solvents or dispersion media used to form the carrier generation layer include butylamine, diethylamine, ethylenediamine, ingropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, and toluene. , Kinren, Chloroform, 1
．． 2-dichloroethane, 1,2-dichloropropane, 1
．． 1.2-trichloroethane, 1.1.1 trichloroethane, trichlorethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, impropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve,
Examples include methyl isobutyl ketone.

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. 4 and 5 are sectional views of photoreceptors according to embodiments of the present invention, respectively.

Figure 4 shows that the carrier transport layer (CTL) is the carrier generating layer (
CGL), which is a preferred embodiment as a negative charging photoreceptor; on the contrary, Fig. 5 shows an embodiment in which CGL is laminated on a CTL, which is preferred as a positive charging photoreceptor. It is a mode.

Furthermore, in the present invention, since at least one, ie, at least two, selected from Ti0Pc and PcTi is used as a carrier generating material (CGM), it is possible to form CGL in separate layers for each.

In FIG. 4(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. 5, and the same symbols as in FIG. 4 represent layers with the same meaning.

When a two-layer structure is adopted for the CGL, this is thought to be due to the ionization potential or the energy injection barrier of the CTL, but for negative charging as shown in Figure 4, the CGL in contact with the CTL is used for negative charging.
2 A jl: Place the Ti0Pc in contact with the support 7
\, CG L 2 B i: It is preferable to allocate PcTi.

Also, in the case of positive charging as shown in Fig. 5, the lower layer C in contact with the CTL
Ti0Pc on GL2B, PcT on upper layer CGL2A
If i is assigned, the performance will be good.

The layer structure of the photoreceptor of the present invention is as shown in FIG. 4(a) and FIG. 4, where 4 in FIG.
5 in <c> in the same figure is Ti0P.
Either c or PcTi is a carrier generation-transport composite layer (CGTL) mixed with CTM, and 7 (d) in the same figure is a CGT hybridized with two types of CGM and CTM.
It is L.

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. 4 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 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. 4 and 5, the film layer of the lower CGL 2B is 0.
01-LOp m (further 0.05~Lpm) is preferable, and the film thickness of the upper CGL2A is 0.01" 1
The thickness is preferably 0 μm (more preferably 0.5 to 5 μm).

In CTL, C'TM is preferably 20 to 200 wt, particularly preferably 30 to 15 (ht) per 100 parts by weight (wt) of binder resin in CTL.

Further, the thickness of the formed CTL is preferably 5 to 50μ.
m5 is particularly preferably 5 to 30 Pm.

FIG. 6 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.

In addition, the light source 2122 can be used as a white light source,
Examples include 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 2o is imagewise exposed at 21 and developed at 23. This is transferred to the transfer paper 24 with the pole of 25, and 2
The transfer paper is separated by the separation electrode 6. 27 toners left
is cleaned with.

In a recording device that uses a drum-shaped photoreceptor like this recording device, the image exposure by the laser beam 57 is performed by the seventh laser beam.
Preferably, a laser beam scanner as shown in the figure is used.

The operation of the laser beam scanner shown in FIG. 7 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〕

The present invention will be described below with reference to Examples 1 to 6 and Comparative Example (1), but the embodiments of the present invention are not limited to the following examples.

First, prior to illustrating embodiments, Y-type titanyl phthalocyanine synthetic leather used for detailed explanation of the present invention will be explained.

(Composition of TiOPc) Example 1 Mix 29.2 g of 1.3-diiminoisoindolizine and 200 ra (l) of sulfolane, add 17.0 g of titanium tetraisogropoxide, and add The reaction was carried out at 140°C for 2 hours.After cooling, the precipitate was collected by filtration, washed with chloroform, washed with 2% hydrochloric acid, washed with water, further washed with methanol, and dried.
, 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 a Bragg angle of 2θ of 9.6° was 102% of that at a Bragg angle of 27.2°.

Let this be Ti0PcY.

Synthetic Bait 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 T 1OPc. In this crystal, the peak intensity at a Bragg angle of 2θ of 9.6° was 75% of that at 27.2°. Ti0Pc Y! shall be.

Synthetic bait 3 Phthalodinitrile; 25.6 g and σ-chlornaphthalene; 6.5 m in a nitrogen stream in a mixture of 150 m12
Titanium tetrachloride (Q) was added dropwise and reacted at 200 to 220°C for 5 hours. The precipitate was collected by filtration and washed with σ-chlornaphthalene, followed by chloroform washing and then 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 phthalocyanine.

The product was dissolved in 10 times the amount of concentrated sulfuric acid, poured into 00 times the amount of water, precipitated and 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 T 1OPc having the X-ray diffraction spectrum shown in FIG. 1(b). In this crystal, the peak intensity at a Bragg angle of 2θ of 9.6° was 45% of that at 27.2°.

This is designated as Ti0Pc Y3.

Synthetic Bait 4 A wet cake obtained by processing in exactly the same manner as Synthetic Bait 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 35% of that at 27.2'. This is referred to as Ti0Pc Y.

(Preparation of photoreceptor) A. The substrate for forming the photoreceptor layer is an aluminum drum or a sheet of polyethylene terephthalate film on which aluminum is vapor-deposited.
Each paint was coated and laminated on the substrate in the following layer configuration. The numbers in parentheses indicate layer thicknesses (μm).

Example 1, Substrate-UCL(0,2)-CGL(0,6)-CG
L(0,4)-CTL(20)(PcTi)
(TiOPc)2, substrate -〇 〇 L(0,2)-
CG L(0,6)-CG L(0,4)-CT L(
20) (TiOPc) (PcTi) 3゜Substrate-UCL(0,2)-CGL(0,5)-CT
L(20)(Ti0Pc, PcTi) 4, Substrate-CTL(16)-CGL(0,3)-CGT
L(3) (TiOPc) (PcTi, CTM)
5. Substrate-CTL(16)-CGL(0,4)-CGT
L(1) (PcT i) (T 1OPc,
CTM)6, substrate-CTL(16)-CGTL(
3) (TiOPc, PcTi, CTM) (CGM
, CGM') B. CGM used, CTM CGM: T 1OPc-Y + + Y 1Y s and Y4GM
-1 CGM-2 CGM-3 aM-4 ccM-(1) ccM-(2) 07M-1 07M-3 CTM-(1) C1 paint CGL, CTL and CGTL paints are processed using a sand grinder and ball mill. , mix and stir to dissolve or uniformly disperse.

Furthermore, in CGTL paint, the CGM content and the additive content such as CTM and antioxidants are prepared separately and uniformly mixed to form a paint.

Example I UCL paint (wt) methanol 90 butanol
lO polyamide resin
2 (Laccamite 5003; manufactured by Dainippon Ink) CGL (lower layer) paint (vt
) 1,2-dichloroethane (denoted as E D C) 100
Polycarbonate resin (Panlite L-1250, manufactured by Teijin Chemicals) l PVC/vinyl acetate/maleic anhydride copolymer (Niretsuku MF-10; manufactured by Hosui Kagaku) 0.0
15GM-12 CGL (upper layer) Paint (, L) Isopropyl acetate 100TiOPc
Y r 2 polyvinyl butyral resin (Elex B H-3; manufactured by Ukisui Kagaku) 2CTL
Paint (wt) E D C1
00 Polycarbonate 20 (Nipilon Z-200; manufactured by Mitsubishi Gas Chemical) CTM-115 Example 2 UCL paint...Same CGL (lower layer) paint as in Example 1 Methyl ethyl ketone (represented as MEK) Polyvinyl butyral resin (S-LEC BH-3) α-type Ti0Pc CGL (upper layer) paint DC Polycarbonate (Panlite L-1250) GM-2 CTL paint DC Polycarbonate (Nipilon Z-200) GM-2 Example 3 UCL paint...Same CGL paint as Example 1 (wt ) 00 (wt) 00 00 0 5 (wt) MEK Silicone resin (K R-5240; manufactured by Shin-Etsu Chemical) CGM-3 TiOPcY= CTL paint...Example 4 same as Example 1 CTL paint DC Polycarbonate (Panlite) L-1,250) 07M-3 CGL paint isopropyl alcohol polyvinyl butyral resin (ELEX B H-3) 7i0PcYs CGTL paint DC polycarbonate 00 0.2 (wl) 00 2 6 2 (vt) 00 (it) 00 (Niepilon Z -200, Mitsubishi Gas Chemical) CGM-
24 07M-16 Antioxidant 0.4 (IRGA
NOXIOIO; manufactured by Ciba Gaiki) Example 5 CTL paint...CGL paint same as Example 4 (it)M
E K 100 Butyral Resin l (S-LEC BMS
, Sekisui Chemical) CGM-12 CGTL paint (wt) Isopropyl acetate 100 Silicone resin (K R-5240) 6TiOPcY4
2TM-12 Antioxidant (lI? GANOX 1010)
0.3 Example 6 CTL paint...Same CGTL paint as Example 4 MEK Silicone resin (K R-5240) TiOPc Y 3 CGM-1 07M-2 Antioxidant (IRGANOX 1010) Comparative example (1
) UCL paint Casein ammonia water (28%) Water CGL paint CGM-(1) CGM-(2) Polyvinyl butyral resin (S-LEC BM-2, manufactured by Sekisui Chemical) Isopropyl alcohol CTL paint CTM-(1') (wt) 00 0.3 0.5 11.2g 1g 22mQ (vt) 0.5 0.5 (Wt) Polysulfone (P-1700; manufactured by U CC) i
Monochlorobenzene 6 [Characteristics Evaluation] Characteristics evaluation tests of the thus obtained photoreceptor samples were conducted as follows. The results are listed in Table 1.

[Sensitivity test]

Using an electrostatic charging tester EP A-8100 (manufactured by Kawaguchi Electric Co., Ltd.), the exposure amount of 8% (2ux-sec) required to reduce the photoreceptor surface potential by half from the initial potential was measured.

However, Examples 1 to 3 and Comparative Example (1) had an initial potential of -60
0V, and +600V in Examples 4 to 6.

[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 at the 0th time Δ0→1110 (V) was measured. (Determined as 1ΔVHI.) [Long-wavelength photosensitivity measurement] A tungsten lamp light source was used in the above-mentioned EPA-8100 measuring meter, and light with a wavelength of 780n+*±In11 of particular concern was measured through a monochromator. Measure the E 3A (V cm”/erg) for the sample.

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.

[Brief explanation of the drawings] Figure 1 is an X-ray diffraction spectrum diagram of T1OPc in Synthesis Example 1 (Fig. Spectral absorption spectrum diagram, 3rd
The figure is a diagram showing the spectral sensitivity (Example 3) complemented by Ti0Pc and PcTi. 4 and 5 are cross-sectional views of embodiments of the photoreceptor of the present invention. FIG. 6 is a schematic diagram of an example of an image forming apparatus using the photoreceptor of the present invention, and FIG. 7 is an explanatory diagram of the operation of a laser beam scanner.

Claims (3)

[Claims] (1) In an electrophotographic photoreceptor in which a photosensitive layer containing a carrier-transporting substance and a carrier-generating substance is provided on a substrate, titanyl phthalocyanine and 450-
Contains at least one compound having spectral sensitivity in a wavelength range of 600 nm, and the spectral sensitivity of at least a part of the wavelength range expressed in the photoreceptor of the compound is higher than the spectral sensitivity of the corresponding wavelength range expressed by the titanyl phthalocyanine. A large electrophotographic photoreceptor. (2) Cu-Kα rays of the titanyl phthalocyanine (
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
．． The electrophotographic photoreceptor according to claim 1, which is titanyl phthalocyanine having a peak at 0±0.2°. (3) A claim characterized in that the titanyl phthalocyanine is in a crystalline state, and the peak intensity at 9.6±0.2° of the Bragg angle 2θ is 40% or more of the peak intensity at 27.2±0.2°. Item 2. The electrophotographic photoreceptor according to item 1 or 2.