JPS6059355A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity to the light of a specified long wavelength by using a specified kind of phthalocyanine for an electrostatic charge generating material. CONSTITUTION:A charge generating layer formed on a conductive substrate is allowed to contain chloroindium phthalocyanine represented by the formula shown here or said compd. having at least one H of its benzene ring substd. by Cl. It is synthesized by reacting O-phthalodinitrile with indium chloride under heating, the product is purified by sublimation, and it is vapor deposited on a glass substrate. It has light absorption in >=800nm, and a charge transfer layer contg. polyvinyl carbazol or the like is formed on this charge generating layer contg. this phthalocyanine. The functionally separated photosensitive body thus prepared is adapted to semiconductor laser beams.

Description

Detailed Description of the Invention (Technical Field) The present invention relates to an electrophotographic photoreceptor, particularly
It is an object of the present invention to provide a photoreceptor that is highly sensitive to light with a long wavelength of 00 nm or more and has excellent specific characteristics.

(Prior Art) As shown in FIG. 1, a conventional photoreceptor is one in which a selenium (Se) film 12 is formed on a conductive substrate 1 made of aluminum or the like by vacuum evaporation. The spectral sensitivity of this Se photoreceptor sharply decreases above 50°n+7Z, as shown by curve 21 in FIG. Note that the sensitivity value used was the reciprocal of the exposure amount required to halve the initial potential. The definition of sensitivity is the same below.

There is also a 5e-T"e alloy photoreceptor in which tellurium (Te) is added to Se to extend the spectral sensitivity to long wavelengths. However, as the amount of Te added increases, this 5e-Te photoreceptor retains more surface charge. The characteristics become poor and it cannot be used as a photoconductor in fact. Therefore, as another example, as shown in FIG. There is a two-layer type in which the charge retention property is improved by forming 2 to 3μ7n.When the surface layer is 5e85Te15, as shown by curve 22 in Figure 2, the spectral sensitivity decreases rapidly above 650nm. Shuffle.

In addition, as shown in FIG. 4, a charge generation layer 42 is formed on the soil of the conductive substrate 41 by coating 42 of chlorodia ampule or squaryllic acid derivative, and a charge generation layer 42 of polyvinylcarbazole or pyrazoline having high insulation resistance in the dark is formed on this layer. There is a two-layer functionally separated photoreceptor in which a charge transport layer 43 is formed by coating a mixture of a derivative and a polycarbonate resin. Although these photoreceptors have sufficiently high sensitivity to visible light, they cannot be used as photoreceptors to irradiated light of 650 nm or more.

On the other hand, attempts have been made to use a semiconductor laser as a light source in laser beam printers that use laser light as a light source and an electrophotographic photoreceptor, and the oscillation wavelength of this light source is 8.
00 to 850 nm is common. However, currently 800
Almost no photoreceptor has been found that exhibits high sensitivity to light of nm or more.

Therefore, a photoreceptor is required that has high sensitivity to long wavelength light of 800 nm or more.

Therefore, as shown in FIG. 5, a dispersed photoreceptor is prepared by coating a conductive substrate 51 with a polymer material and X-type metal-free phthalocyanine at a weight ratio of 6:1 to a thickness of 10 to 30 μm. As shown in FIG. 6, it has sensitivity at 800 nm. However, X-type phthalocyanine has an X-type crystal structure, and the manufacturing method is more complicated than that of the widely commercially available α-type and β-type phthalocyanine pigments. There was a drawback that special consideration was required for the processing. (Objective of the Invention) The object of the present invention is to provide an electrophotographic photoreceptor that is sensitive to wavelengths of 800 nm or more and that can be easily produced. It is in.

(Structure of the Invention) The present invention relates to an electrophotographic photoreceptor in which a charge generation layer made of an organic photoconductive substance is formed on a conductive support, or a charge generation layer made of an organic photoconductive substance on a conductive support and charge transport. In the functionally separated electrophotographic photoreceptor in which the layers are formed in this order, the charge generation layer is a chloroindium phthalocyanine Al represented by the general formula, or the benzene ring of the chloroindium phthalocyanine has one or more H atoms and Ct. This invention relates to an electrophotographic photoreceptor characterized by using a substance with a substituted structure, and will be described in detail below. (Example) In the first example of the present invention, orthophthalodinitrile 128g and indium chloride (I n CZ 3 )5
．． 6.9 was reacted for 30 minutes while stirring and mixing in a beaker in a mantle heater at 30 (1'C).
) with In represented by the general formula shown in the formula as the central metal,
This is a phthalocyanine in which Ct is bonded to In, and a portion of the hydrogen in the benzene ring surrounding the phthalocyanine ring is all C4
A phthalocyanine with a substituted structure was synthesized and purified by sublimation. As a result of elemental analysis of this product, the elemental ratio was C32H16,7NB, 0ct1.8In1.0, one of Ct was bonded to the central metal, and the remaining one was
ke is approximately C52H16NBCL2. bonded to the benzene ring surrounding the phthalocyanine ring. It was found to be indium phthalocyanine with an elemental ratio of I n 1. Phthalocyanine (hereinafter referred to as In) synthesized and purified in this way
(abbreviated as CAPcCt) was placed in an aluminum crucible in a vacuum evaporation apparatus, and a thin film of 0.0511 m was formed on a glass substrate at 400° C. r 10 −′ Pa. 600 of this thin film
FIG. 6 shows the results of measuring the optical absorption spectrum for wavelengths of up to 900 nm. Thus, the optical absorption of InC4PcC4 is high in the range of 600 to 900 nm.

More than InCLPcCl-10, j9 and pylon 200
4g of polyester resin and methyl ethyl ketone (ME
Pour 60 ml of 96
Grind and mix for hours. This mixture was coated on an aluminum substrate using a solution coating method to produce a photoreceptor having a dry film thickness of 12 μm and having the structure shown in FIG. ]
The spectral sensitivity of this example is shown in FIG. In this way, 60
Almost flat characteristics from 0 to 850 nm, 85
Sensitivity at 0 nm, reciprocal of half-decrease exposure is 1.2α2
//lJ. The initial charging potential at this time was 800V. Furthermore, Figure 10 shows the results of powder X-ray diffraction after synthesis, and Figure 11 shows the results of polyester resin and InCLPc.
The polyester resin was separated from a mixture of Cl and methyl ethyl ketone, pulverized and mixed in a ball mill for 96 hours, and then evaporated to MF to remove the InCtPcCL powder.
This is the result of line diffraction. In this way, the results were almost the same both after synthesis and after pulverization and mixing in a ball mill. As a result, it can be said that the crystal structure of the InCtPcCA of the photoreceptor of the first example is the same as that after synthesis. In this way, the photoreceptor using InCLPcCL has a stable crystal structure without changing to another structure during the manufacturing process using a solvent and a ball mill, has good reproducibility, and can easily be used for long wavelength light of 800 nm or more. showed high sensitivity.

The second embodiment of the present invention has the same structure as FIG. 8, and the moon in the first embodiment? +[ instead of polyester resin
Polyvinylcarbazole (■) ■K, a cargo-transporting resin
), tetrahydrofura instead of MEK, / (TII
F) Grinding and mixing using a 'JG time rule mill in the same manner as in the first example using a solvent. This mixture was coated onto aluminum substrate using a solution coating method to a dry film thickness of 8.
A film of μ7n was formed to produce a photoreceptor. The initial charging potential of this photoreceptor was 500 ■, and the sensitivity at 850 n7n was as high as 1.6 cm2/μJ. In this way, even if PVK, which is a charge transporting material, was used instead of the polyester resin, a highly sensitive photoreceptor could be obtained as in the first M+i example. It's a trench, THF and InC4.
I after mixing and pulverizing PcC/, and PVK for 96 hours
The powder X-ray diffraction results of nCLPcCl were similar to those of the first example, and were almost the same as the synthesized InC4PcC/, and no change in crystal form was observed due to the pulverization and mixing operation.

In the first and second examples, the case where one Ct is bonded to the benzene ring is described in detail, but depending on the synthesis method, two or more Ct may be bonded, and furthermore, two or more Ct may be bonded to the benzene ring. The use of the above hydrogens replaced by Ct may likewise achieve the object of the invention.

In the third embodiment of the present invention, first, orthophthalodinitrile 128I and indium chloride (I n CZ s ) 5
．． 6g of quinoline in 100ml of flask,
While stirring and mixing, the mixture was heated with a mantle heater and allowed to react for 60 minutes while remaining, to synthesize a phthalocyanine having a structure with In' and H center metals represented by the general formula shown in the claims, and then purified by sublimation. Elemental analysis of this product revealed an elemental ratio of C32H16,5N7.
9C4i, lIn0.9, and 1 Oct is bonded to the central metal. Almost C32H46Na CL, I n
It was found to be indium phthalonanine with an elemental ratio of 1. The thus synthesized and purified phthalocyanine (hereinafter abbreviated as 1nCjPc) was placed in an aluminum crucible in a vacuum evaporation apparatus, and a thin film of 0.04 μm was formed on a glass substrate at 400° C. + 10'Pa. The results of measuring the light absorption spectrum of this thin film in the wavelength range of 600 to 900 nm are shown in FIG.

This InCAPC, 10p, Byron 200 polyester resin 2g, and methyl ethyl ketone 100ml are made of glass + l? - The mixture was ground and mixed in a Lumil for 96 hours.

This mixture was coated with aluminum base 4J using a solution coating method.
Coated on top, dry film thickness 08μ? A charge generation layer of n was prepared. On top of this, add 10g of PVK to 100ml of T.
Solution coated with HF solution and dry film thickness 12
A charge transport layer having a thickness of .mu.m was formed to produce a photoreceptor having a two-layer structure as shown in FIG. The initial charging potential of this photoreceptor is 900
When v, the sensitivity at 850 nm is ], 9 CT
The residual potential was as high as n2/μJ and as low as 30V or less. As in the third embodiment, a functionally separated photoreceptor in which InCAPc is dispersed in an insulating polymer material for the charge generation layer is also an excellent photoreceptor. In addition, for InCAPc, the X-ray diffraction results after synthesis and after mixing and pulverization in a ball mill are almost the same as in Figure 10.
Similar to cC4, no change in crystal structure occurred.

The fourth example consists of 10 g of InCtPc, 2 g of polyester resin, and 2 I
50 ml of toluene and 20 ml of MEK were placed in a glass ball mill and pulverized and mixed for 96 hours. This mixture'
Jfyt'f: A charge generation layer with a dry film thickness of 03 μm was prepared by coating on an aluminum substrate using a solution coating method. Add 10g of hydrazone'iloO to this.
A two-layer structure photoreceptor having the same structure as that shown in FIG. 13 was prepared by solution-coating a charge generation layer with a dry film thickness of 10 μm by solution-coating a mixture of MEK dissolved in MEK. The sensitivity at 850 nm is 1.
The residual potential was as high as 5 cm/ltJ, and the residual potential was as low as 40 V or less. In this example, the X-ray diffraction measurement of the InC6Pc after mixing and pulverization using a ball mill showed no change in the crystal structure as in the first to third examples.

(Effects of the Invention) The electrophotographic photoreceptor of the present invention is sensitive to wavelengths of 800 nm or more, can be produced entirely by solution coating method without using any vacuum equipment such as vapor deposition equipment, and can be produced at low cost. It is possible to mass produce stable products. Furthermore, the photoreceptor of the present invention can be applied not only to laser printers but also to facsimile machines or printers using LED light sources, particularly other recording devices and optical sensors using semiconductor radar light sources.

[Brief explanation of the drawing]

Fig. 1 is a cross-sectional view of a conventional Se photoreceptor, Fig. 2 is a spectral sensitivity curve diagram of a conventional electrophotographic photoreceptor, and Fig. 3 is a sectional view of a conventional Se photoreceptor.
, a cross-sectional view of a 5e-Te alloy two-layer type photoreceptor, FIG. 4 is a cross-sectional view of a conventional functionally separated type electrophotographic photoreceptor, and FIG. 5 is a cross-sectional view of a conventional electrophotographic photoreceptor using X-type metal-free phthalocyanine. 6 is a spectral sensitivity curve diagram of a conventional electrophotographic photoreceptor using X-type metal-free phthalocyanine;
FIG. 7 shows the light absorption spectrum of the synthesized InC4PcC4 vapor deposited film, FIG. 8 is a cross-sectional view of the electrophotographic photoreceptor according to the first embodiment, and FIG. 9 is the electrophotographic photoreceptor according to the first embodiment. The spectral sensitivity curve of Fig. 10 is the synthesized InCAPcC.
Figure 11 shows the X-ray diffraction spectrum of the In('tpcct) powder coated in the first example.
Linear diffraction spectrum, Figure 12 shows the synthesized InC/LPc
FIG. 13 is a sectional view of an electrophotographic photoreceptor according to a third embodiment. 21... Spectral sensitivity curve of Se photoreceptor, 22... Se
, 5e-Te alloy two-layer photoconductor, 81,131...aluminum base material, 82...mixture layer of InC4pcC6 and polyester resin, 132...mixture layer of InC2Pc and polyester resin, 133...PVK layer . Patent Applicant: Oki Electric Industry Co., Ltd. Figure 5 Figure 6 Kunami++nml 7th Input lnm1 Figure 8 1 Indication of the incident 1982 Patent Application No. 167536 2 Name of the invention Photoreceptor for electrophotography 3 Amendment Relationship with the patent applicant case Address (〒105) 1-7-12 Toranomon, Minato-ku, Tokyo
No. 6 Contents of the amendment Attachment 14, , /6, Contents of the amendment (1) In the third line of page 8 of the specification, riogJ is amended to read "4g". (2) ``4g'' on page 8, line 4 of the same book is rlO
Correct with &J. (3) In the 8th line of Chapter 11 of the same book, ``InCAPCJ is corrected to r InC/-Pc J.

Claims (2)

[Claims] (1) In an electrophotographic photoreceptor in which a charge generation layer made of an organic photoconductive substance is formed on a conductive support, the charge generation layer is made of chloroindium phthalocyanine represented by the general formula: An electrophotographic photoreceptor characterized by using a substance having a structure in which one or more H atoms in a benzene ring are substituted with Ct. (2) In a function-separated electrophotographic photoreceptor in which a charge generation layer and a charge transport layer made of an organic photoconductive substance are formed in this order on a conductive support, the charge generation layer is a chloroform compound represented by the general formula: An electrophotographic photoreceptor characterized by using indium phthalocyanine or a substance having a structure in which one or more H atoms in the benzene ring of chloroindium phthalocyanine are substituted with Ct.