JPS6086551A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve light responsivity, to reduce light fatigue and deterioration, and to enhance stability by using a metal-free phthalocyanine in specified crystal form pretreated with an electrostatic charge transfer agent and/or sensitizing dye. CONSTITUTION:Metal-free phthalocyanine (Pc) of a tau of modified tau type or eta or modified eta type is pretreated with a charge transfer agent and/or at least one kind of sensitizing dye to allow metal-free Pc to strongly adsorb the charge transfer agent on the surface. When such Pc is used for a laminate type electrophotographic sensitive body, the flow of carriers through the interlayer between a charge generating layer and a charge transfer layer can be smoothed and light responsivity can be enhanced by further mixing the charge transfer agent and/or the sensitizing dye with said pretreated Pc. In the case of using a single layer type, since release of carriers from the surface of the metal-free Pc is also smoothed by mixing the charge transfer agent and/or the sensitizing dye, light responsivity can be improved, light fatigue or deterioration due to adsorption of gases, etc., can be reduced, and stability can be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is an electrophotographic method using a metal-free phthalocyanine in a specific crystal form that has been previously treated with one or more of a charge transport agent and/or a dye having a sensitizing effect. Regarding photoreceptors.

Generally, in electrophotography, a photoreceptor is formed by forming a thin film of photoconductor elements such as selenium or cadmium sulfide on a metal drum, such as xerography, which is charged in a dark place and then irradiated with a light image (exposure). After forming an electrostatic latent image, a visible image is created with toner (development), and this is transferred and fixed onto paper, etc., or a photoconductive layer (photosensitive layer) is placed on paper as in the electrofax method. and charges the photosensitive layer.

There is a method of obtaining a permanent visible image on the photoconductive layer by exposure, II imaging and fusing.

Inorganic compounds that are currently widely used as photoconductor materials for electrophotographic photoreceptors include solid selenium, cadmium sulfide, and zinc oxide. Amorphous selenium has good properties as an electrophotographic photoreceptor, but! The L method requires vapor deposition and is difficult to manufacture. Cadmium sulfide also has the drawbacks of being expensive, requiring careful handling as the film is not flexible or highly toxic.

Zinc oxide is used in the form of a binder and a resin dispersed in it, but practical sensitivity cannot be obtained unless the weight ratio of the resin/photoconductor material is small, making it flexible.

Cadmium sulfide has drawbacks in mechanical properties such as smoothness, hardness, tensile strength, and abrasion resistance, and cadmium sulfide also requires consideration of hygiene issues.

On the other hand, polyvinylcarbazole, which is known as an organic photoconductor material, has charge retention properties and transparency.

Although it has advantages such as self-forming ability, its photosensitivity is significantly inferior to that of inorganic photoconductor materials, and sufficient sensitivity cannot be obtained for practical use depending on known sensitizers.

It is also known to use phthalocyanines as photoconductor materials. Although phthalocyanine has sensitivity to light at a comparative lesion wavelength, its sensitivity to semiconductor laser light having an oscillation wavelength of 790 nm or more to guarantee a sufficiently long life for practical use is still insufficient.

The present inventors have already discovered τ, a modified τ, which has sufficient sensitivity to semiconductor laser light of 790 nm or more.

η, invented an electrophotographic photoreceptor using deformable metal-free phthalocyanine as a photoconductor material (patent application 1983-1986).
No. 963, No. 58-). Electrophotographic photoreceptors using these phthalocyanines as photoconductor materials have excellent flexibility, processability, and hygiene.

Although the sensitivity to long wavelength light is good, the stability of the image quality upon repeated use is not necessarily sufficient, and there are also problems with durability.

As a method to solve the above problem, conventionally, a layer using phthalocyanine as a charge generating substance, pyrazolines, hydrazones, oxazoles, trinitroanthracene,
2.4.5.7-tetranitro-9-fluorenone (
It is known to sensitize by stacking layers using polycyclic or heterocyclic nitro compounds such as TENF) as a charge transport material, or by using xanthine dyes, quinoline dyes, etc. as optical sensitizers. There is. However, even with these methods, when put to practical use, there is a slight lack of sensitivity and changes in image quality with repeated use.

There were problems with optical fatigue and longevity. These problems are the result of having to use large amounts of charge transport agents and sensitizing agents in order to improve the sensitizing effect.

This is thought to be due to the fact that these charge transport agents and sensitizing agents change or decompose under the influence of nitrogen oxides, oxygen, ozone, etc. accompanying strong light irradiation and electrostatic charging.

The present inventors have completed two inventions as a result of intensive research to solve the above problems.

That is, the present invention relates to an electrophotographic photoreceptor using a τ, modified τ, η or modified α type metal-free phthalocyanine which has been previously treated with a charge transport agent and/or a dye having a sensitizing effect of 1vi or more.

The τ, modified τ, η, and modified α-type metal-free phthalocyanine used in the present invention are described in detail in Japanese Patent Application No. 66963/1982 and Japanese Patent Application No. 1983/1983.

The τ-type metal-free phthalocyanine is CuKIx+/Ni 1
．． When using X-rays from 541 people, the Bragg angle (2θ±
0.2 degree) is 7.6.9.2.16.8.1? , 4゜2
It has an X-ray diffraction pattern showing strong lines at 0.4 and 20.9. In particular, the infrared absorption spectrum is 700
Four absorption bands with the strongest strength of 751±'1cs-' were found between ~76 Ga1l-', two absorption bands of approximately the same strength were found between 1320 and 1340 cm-1, and 3288±3 cm
-' is desirable.

A typical method for producing τ-type metal-free phthalocyanine is to prepare α-type metal-free phthalocyanine at 50 to 180°C.

It is characterized in that it is preferably milled at 60 to 130° C. with stirring or mechanical strain for a sufficient time to exhibit the τ type. Note that the X-ray diffraction and infrared absorption spectra are shown with ranges because slight deviations occur due to lattice defects or dislocations in the crystal due to differences in manufacturing conditions.

α-type metal-free phthalocyanine, which is a raw material for τ-type metal-free phthalocyanine, is described in Moser and Thomas's [Phthalocyanine Compound J (Moser and Thomas).
Phthalocyanine Compounds
) and other suitable methods can be used. ! For example, metal-free phthalocyanines include metal phthalocyanines that can be demetalized by sulfuric acid, tx-tonoic acid, such as lithium phthalocyanine, sodium phthalocyanine, and calcium phthalocyanine.

Those synthesized directly from phthalodinitrile, aminoiminoindolenine, alkoxyiminoisoindolenine, etc. by acid treatment such as magnesium phthalocyanine can be used.

α-type metal-free phthalocyanine can be obtained by dissolving this metal-free phthalocyanine in an acid such as sulfuric acid or making it into an acid salt, preferably at a temperature below 5°C, and pouring it into water, preferably ice water, and re-precipitating or hydrolyzing it. . The α-type metal-free phthalocyanine is stirred or milled in a dry state or in an aqueous paste state. The dispersion media at this time are those commonly used for dispersing, emulsifying, and mixing pigments, such as glass beads and steel beads.

Examples include alumina balls and flint stones. However, one distributed medium is not necessarily required. Examples of grinding aids include those commonly used as grinding aids for dispersing pigments, such as common salt, sodium bicarbonate, and sulfur salt. Stir.

If a dispersion medium is required during milling, stir and use one that is liquid at the temperature during milling 2 For example, alcohol solvents such as glycerin, ethylene glycol, diethylene glycol, polyethylene glycol dispersion medium, ethylene glycol monomethyl ether, ethylene glycol mono Cellosolve-based dispersion media such as butyl ether, ketone-based dispersion media.

A dispersion medium such as an ester ketone type can be used.

Examples of stirring and milling equipment used in the crystal transition process include a sand mill and a kneader.

Examples include a homo mixer, an agitator, a Starsea 5 Banbury mixer, a ball mill, and an attritor.

The temperature range in the crystal transition step is 50 to 180°C, preferably 60 to 130°C. It is also an effective method to use crystal nuclei as in the usual crystal transition process.

The rate of crystal transition to τ type depends on the efficiency of stirring and milling.

It depends on various conditions such as strain force, particle size of raw material, and temperature. After the completion of the crystal transition step 1, the grinding aid, dispersion medium, etc. are removed by a conventional purification method, and the desired τ-type metal-free phthalocyanine can be obtained by drying.

The modified τ-type metal-free phthalocyanine has a Bragg angle (2θ
±0.2 degrees) is 7.5.9.1.16.8.1? .

3. It has an X-ray diffraction pattern showing strong lines at 20.3, 20.8, 21.4 and 21.7. In particular, the infrared absorption spectrum is between 700 and 760an-'.
3±'1cm-' is the strongest four absorption bands, 1320
It is desirable to have two absorption bands of approximately equal intensity between ~1340cI11-1 and a characteristic absorption at 3297±3cm-'.

The modified τ-type metal-free phthalocyanine can be obtained by substantially the same manufacturing method as the τ-type metal-free phthalocyanine.

η type metal phthalocyanine is metal-free phthalocyanine,
In particular, 100 ffi parts of α-type metal-free phthalocyanine and one or two types of metal-free phthalocyanine having a substituent on the benzene nucleus, or a phthalocyanine nitrogen isoconstructor or metal phthalocyanine which may have a substituent on the benzene nucleus.
A mixture of at least 50 parts by weight of seeds is heated at 30 to 220°C,
Preferably, it can be produced by stirring or milling in the same manner as when obtaining τ-type metal-free phthalocyanine at 60 to 130°C, and it is not limited to pure metal-free phthalocyanine, but also a mixture with other phthalocyanines. It refers to something. This η-type metal phthalocyanine has an infrared absorption spectrum of 700 to 760 cI.
Between 1320 and 1340cI+1, there are 4 absorption bands with the strongest intensity at 753±ICll-1, and between 1320 and 1340cI+1, there are two absorption bands with almost the same intensity, and at 3285±5c+o-' there is a characteristic absorption. It is something that you have. According to the research conducted by the present inventors, η type metal phthalocyanine has a Bragg angle of 7.6.
．． 9.2. 7.6, which has an X-ray diffraction pattern showing strong peaks at 16°8.17.4 and 28.5;
9.2, 16.8° 17.4, 21.5 and 27.5
Some have xm diffraction patterns showing strong peaks.

Examples of the substituents of the phthalocyanine include an amino group, a nitro group, an alkyl group, an alkoxy group, a cyano group, a mercapto group, and a halogen atom.

Furthermore, sulfone groups, carboxylic acid groups, metal salts thereof, pentammonium groups, amine salts, etc. can be exemplified as relatively simple substituents. Furthermore, there are alkylene groups and sulfonyl groups in the benzene nucleus.

Various substituents can be introduced through carbonyl groups, imino groups, etc., and these are conventionally used as anti-aggregation agents in the technical field of phthalocyanine pigments.

Known crystal growth inhibitors or crystal transition inhibitors (for example, US Pat. No. 4,088,507) or unknown crystal growth inhibitors can be used. Also.

Metal phthalocyanines include copper, nickel, cobalt,
Examples include various metal phthalocyanines such as zinc, tin, and aluminum. Examples of nitrogen isoconstructs include various porphines 2 such as copper tetraviridinovolphyrazine in which one or more of the benzene nuclei of phthalocyanine is replaced with a quinoline nucleus.

The modified η metal-free phthalocyanine can be obtained in substantially the same manner as the η-type metal phthalocyanine.

The infrared absorption spectrum has four absorption bands between 700 and 760 (the strongest at 753 ± 1 cm-' between IJ-' and 13
It has two absorption bands of approximately the same intensity between 20 and 1340cI8-1, and a characteristic absorption at 3297±51-1. According to research by the present inventors.

The modified η-form metal phthalocyanine has a Bragg angle of 7.
5.9.1.16.8. 17.3.20.3.20.
One has an X-ray diffraction pattern showing strong peaks at 8°21.4 and 27.5; , 5, 9.1, 16.8.1
? .

3, 20.3.20.8.21.4.22.1.27.
Some have X-ray diffraction patterns showing strong peaks at 4 and 28.5.

τ and modified τ-type metal-free phthalocyanine have good crystallinity and excellent heat resistance, and η and modified η-type metal phthalocyanine have the feature that their crystals are stable even when they come into contact with aromatic solvents. .

Moreover, since these exhibit maximum sensitivity at 790 to 810 nm, they are suitable as i11!1 photoreceptors for semiconductor lasers.

In the present invention, the method of treating the above phthalocyanine with a charge transport agent and/or a dye having a sensitizing effect is a method of treating the phthalocyanine with a charge transport agent and/or a dye having a sensitizing effect. Group 9 ethers, hydrocarbons, halogenated hydrocarbons, phenols, fatty acids.

In a solution dissolved in an amine-based or ester-based solvent, τ
, modified τ, η, and modified η type metal-free phthalocyanine, or a mixture of two or more thereof is added.

An example of a treatment method is to stir or shake for several minutes to several days using a stirrer, a shaking cannon, or the like.

When processing with two or more charge transport agents and/or dyes with a sensitizing effect, there are two methods: simultaneous processing and sequential processing using appropriate solvents for each. If the adsorption sites and adsorption forces are different, it can be treated like a young fruit.

The charge transporting agents used in the present invention include Oxasol MilL styryl dye base, cyanine collecting base,
Various photoconductive compounds can be mentioned, such as oxadiazole derivatives, pyrazoline derivatives, hydrazone derivatives, triphenylamine M conductors, triphenylmethane derivatives, nitrofluorenone derivatives, and poly-N-vinylcarbazole, poly- Polymers having a carbazole ring or anthracene ring in the side chain such as 9-P-vinylphenyltenthracene, or polymers having a pyrazoline ring or dibenzothiophene ring in the side chain can also be used, and these polymers can be used as binders. It also acts as a resin. More specifically, 1 such as 0-chloroanyl, 0-bromoanyl,
Tetracyanoethylene, tetracyanoquinodimethane,
2.4.7. -) dinitro-9-fluorenone, 2
．． 4.5.7-tetranitro-9-fluorenone, 2
．． 4.5.7-Titranitroxanthone, 2.4.8
-) linitrothioxanthone, pyrene.

N-LfJLtcarbazole, N-isopropylcarbazole, 2.5-bis(4-N,N-diethylaminophenyl)-1,3,4-oxadiazole, 1-phenyl-3-(4-N,N-diethylamino Styril)
-5-(4-N,N-diethylaminophenyl)pyrazoline, 1-[pyridyl (2>) -3-(4-N
, N-diethylaminostyryl) -5-(4-N,N
-diethylaminophenyl)pyrazoline, 1-C quinolino-(4)) -3-(4-N,N-diethylaminostyryl)-5-(4-N,N-diethylaminophenyl)pyrazoline, triphenylamine, N-ethyl Carbazole-3-carbaldehyde phenylmethylhydrazone, N-ethylcarbazole-3-carbaldehyde diphenylhydrazone, P-diethylaminobenzaldehyde diphenylhydrazone, α-anthryl-β
-(4-N,N,-diethylaminophenyl)ethylene, poly-tovinylcarbazole, halogenated poly-N-
Vinyl carbazole, polyvinylanthracene, polyvinylacridine. Poly-9-P-vinylphenylanthracene, pyrene-formaldehyde resin.

Ethylcarbazole-formaldehyde [111! Examples include lyacetylene.

Brilliant Green, Victoria Blue B, and Methyl Violet are used as sensitizers.

Triallylmethane dyes such as Crystal Violet, Acid Violet 6B, Rhodamine 6G, Rhodamine B, Rhodamine 6G Extra, Eosin S, Erythrosin, Rose Bengal.

Xanthine dyes such as fluorenine, thiazine dyes such as methylene blue, cyanine dyes such as cyanine, 2-6-diphenyl-4-(N,N-dimethylaminophenyl)thiapyrylium verchlorate, benzobyrylium salts Examples include biryllium dyes such as.

The metal-free phthalocyanine treated in this way.

It can be separated from the solvent and dried and used as a dry powder, but if the solvent is suitable, a binder resin can be further added and used as a paint as it is.

The metal-free phthalocyanine pre-treated in this way is simply metal-free phthalocyanine.

Compared to the case where a solvent, a binder resin, and a charge transport agent and/or a sensitizing agent are simultaneously mixed to form a paint, it exhibits superior effects in terms of electrophotographic photoreceptor properties such as sensitivity and resistance. This is thought to occur because the charge transport agent and/or the sensitizing agent are firmly adsorbed onto the surface of the metal-free phthalocyanine due to the pretreatment.

The electrophotographic photoreceptor according to the present invention includes τ, modified τ, η, or modified η type metal phthalocyanine treated as described above, singly or in a mixture thereof, as well as other phthalocyanine pigments known as charge-generating substances. Azo pigment, anthraquinone pigment.

Used in combination with quinacridone pigments, perinone pigments, methine squaric acid pigments, etc., and polyurethane resins.

Melamine resin, urea resin, phenol resin, epoxy resin, silicon resin, polyester resin, alkyd resin, acrylic resin, xylene resin, vinyl chloride-vinyl acetate copolymer resin, vinyl acetate-methacrylate copolymer resin, polycarbonate resin , binder resins such as cellulose derivatives.

Alternatively, it is made into a paint by a known method using a photoconductive binder resin such as polyvinylcarbazole, a solvent, and, if necessary, various additives such as an antioxidant. This paint is applied to aluminum plates normally used for electrophotographic photoreceptors.
It is applied onto a conductive support such as conductive treated paper or plastic film.

Form a photosensitive layer. Application methods include adding a solvent to the paint to adjust the viscosity if necessary, and using an air doctor coater, flade coater, rod coater, roll coater, or reverse roll coater.

An electrophotographic photoreceptor can be produced by forming a film using a coating method such as a spray coater, gravure coater, Honto coater, or spray coater, and drying the coated film appropriately after coating.

The electrophotographic photoreceptor according to the present invention can be used as a single layer as described above, but as well known in the technical field of electrophotographic photoreceptors, a laminated electrophotographic photoreceptor in which a charge transport layer is laminated is used. It can also be used as a photoreceptor.

The ratio of binder resin and metal-free phthalocyanine used is 20 to 20 parts by weight of metal-free phthalocyanine per 100 parts by weight of resin.
200 parts by weight is appropriate, but when making a laminated electrophotographic photoreceptor or using a sensitizer etc., 1 part by weight is appropriate.
The amount of metal-free phthalocyanine used can be reduced to about parts by weight. If it is less than 1 part by weight, the characteristics of metal-free phthalocyanine will not appear in the sensitivity or photosensitive wavelength range;
If the amount exceeds 0.00 parts by weight, sufficient mechanical strength and dark charge retention cannot be ensured as an electrophotographic photoreceptor.

The thickness of the photosensitive layer containing these metal-free phthalocyanines is 5~
The appropriate thickness is 50 μm, but in the case of a laminated type, the thickness is 0.0 μm.
It is possible to reduce the film thickness to about 1 μm. The charge transport layer is formed on the layer containing metal-free phthalocyanine and/or
Or layer it on the bottom. As charge transport agents compounds such as those mentioned above can be used, in particular styryl dye bases.

Oxazole derivatives, cyanine dye bases, oxadiazole derivatives, pyrazoline derivatives, hydrazone derivatives,
Triphenylamine derivatives, trinitrofluorenone, etc. are used. These charge transport agents are formed by forming a paint by a known method using the binder resin as described above, applying it, and drying it.

The photosensitivity of the electrophotographic photoreceptor according to the present invention is that the half-exposure sensitivity (light energy required to halve the surface potential) to white light is 1.5 to 2.5 Lux, s even for a single layer type.
ec. On the other hand, if the charge transport agent and/or the sensitizing agent were not pretreated and the same amount of the charge transporting agent and/or the sensitizing agent was added at the time of forming the paint, the amount of the charge transport agent and/or the sensitizing agent was 4 to 5 L.
ux and sec, and a significant difference in effectiveness is observed.

In addition, in the case of a laminated type electrophotographic photoreceptor, a charge transport agent and/or a sensitizing agent may be further mixed with the metal-free phsarocyanine which has been previously treated with a sensitizing agent and/or a sensitizing agent before charge transport.

Since carriers flow smoothly at the interface between the charge generation layer and the charge transport layer, the photoresponse is extremely good. Similarly, in the case of a single layer type, by further mixing a charge transport agent and/or a sensitizing agent, the release from the metal-free phthalocyanine surface into the binder resin becomes smoother, resulting in better photoresponse. , deterioration caused by optical fatigue, gas adsorption, etc. is reduced, and stability is improved.

Hereinafter, the present invention will be specifically explained using Examples, Reference Examples, and Comparative Examples. In the examples, 9 parts indicate parts by weight.

Reference Example 1 20 parts of the grinding aid shown in Table 1 and 8 parts of the solvent were added to IO part of αm gold-free a phthalocyanine in a kneader.

Each was kneaded at 80°C for 7 to 15 hours.

After sampling and confirming that it has transformed to the τ type using an X-ray diffraction diagram, it is taken out from the kneader, and after washing off the grinding aid and solvent with water and methanol, it is stirred in a 2% dilute sulfuric acid aqueous solution. Purified, filtered and washed.

After drying, blue crystals with a clear hue were obtained. These crystals were also confirmed to be τ-type metal-free phthalocyanine by measurement of infrared absorption spectra.

Table 1 Reference Example 2 10 parts of α-type metal phthalocyanate, 200 parts of common salt, and 300 parts of ethylene glycol as a solvent were placed in a sand mill and milled at 100° C. for 20 hours. After sampling and confirming that the sample had transformed to the deformed τ type using an X-ray diffraction diagram, it was taken out from the kneader, and blue crystals were obtained in the same manner as in Reference Example 1. This crystal was also confirmed to be a modified τ-type metal-free phthalocyanine by measurement of an infrared absorption spectrum.

Reference Example 3 100 parts of metal-free phthalocyanine 2 10 parts of each of the various phthalocyanine derivatives shown in Table 2 were dissolved in ice-cooled 98% sulfuric acid, and this solution was poured into water.

A homogeneous mixture was obtained by filtering the precipitate, washing with water, and drying. 100 parts of this mixture, 200 parts of ground common salt and 80 parts of polyethylene glycol were placed in a kneader,
Each was kneaded at 90°C for 7 to 20 hours. After sampling and confirming that it had transformed into the η type using an X-ray diffraction diagram, it was taken out from the kneader and added with water and methanol as a grinding aid.

After washing and removing the solvent, the product was stirred and purified in a 2% dilute sulfuric acid aqueous solution, and blue crystals were obtained in the same manner as in Reference Example 1.

This crystal was also confirmed to be an η-type metal phthalocyanine by measurement of an infrared absorption spectrum.

Table 2 In Table 2, CuPc represents copper phthalocyanine residue, Pc
represents a phthalocyanine residue. Furthermore, an average of 1.1 diethylaminomethyl groups and an average of 2.2 piperidinomethyl groups were introduced.

Reference Example 4 100 parts of α-type metal-free phthalocyanine, 15 parts of the following phthalocyanine derivative, 200 parts of ground common salt, and 80 parts of polyethylene glycol were placed in a kneader, and kneaded at 100° C. for 8 hours. After sampling and confirming that the sample had transformed to the modified η type using an X-ray diffraction diagram, it was taken out from the kneader and a blue crystal was obtained in the same manner as in Reference Example 1. This crystal was also confirmed to be a modified η-type metal-free phthalocyanine by measurement of an infrared absorption spectrum.

P C−+−COCHz N HC&HIT ) z,
J Example 1 Various sensitizing agents and charge transport agents (hereinafter also referred to as additives) were dissolved in saturated amounts in 100 parts of the solvent shown in Table 3, and 1 part of metal-free phthalocyanine was added to 100 parts of this saturated solution. After putting it in a reciprocating shaker for 4 hours, filter it.
The treated metal-free phthalocyanine was obtained by drying at 60-80°C under reduced pressure.

Next, this treatment and 1 part of metal phthalocyanine, acrylic polyol (Takeda Pharmaceutical Co., Ltd. 91. Takelac A-7,02
) 3.6 parts, epoxy resin (manufactured by Shell Chemical Co., Ltd., Epon 1
007) A composition consisting of 0.5 parts of methyl ethyl ketone, 1.2 parts of methyl ethyl ketone, and 1.2 parts of cellosolve acetate is milled in a porcelain ball mill for 48 hours to obtain a photoconductive composition.

This photoconductive composition was roll coated onto the aluminum foil of a laminate film of a 5 μm thick aluminum foil and a 75 μm polyester film to a dry film thickness of 8 μm, and then placed in an oven uniformly heated to 110°C. An electrophotographic photoreceptor was obtained by leaving the mixture in a container for 1 hour.

+5 to these electrophotographic photoreceptors. OKV, corona discharge is applied at a charging speed of 10 m/min with a corona gap of 10 m, and 10 seconds after the discharge is stopped, exposure is performed at an illuminance of 10 Lux using a tungsten light source at 2854°. At this time, the irradiation amount (L
u, sec,) was taken as the sensitivity.

The measurement results are shown in Table 3.

The following additives were used in Table 1 and in the following examples.

- Pyrazoline derivative A; 1-phenyl-3-(4-N.

N-diethylaminostyryl) -5-(4-N,N-
diethylaminophenyl) pyrazoline oxadiazole derivative B, 2,5-bis(4-
N,N-diethylaminophenyl) -1,3,4-oxadiazole hydrazone derivative C1P-diethylaminobenzaldehyde diphenylhydrazone d! ')-N-vinylcarbazole D; Anan Sangyo Ql
Tubicol 210 ・Oxazole derivative E; 2.4-bis(4-N,
N-diethylaminophenyl)-5-(o-//lorophenyl)oxazole styryl dye base F; - Cyanine dye base G; blank below Example 2 Same as Example 1 1 100 parts of the solvent shown in Table 4 and various One part of metal-free phthalocyanine was treated with the additive.

Two parts of these medium-free metal phthalocyanine and 80 parts of tetrahydrofuran were shaken for 4 hours using a reciprocating shaker to prepare a dispersed coating liquid, and this coating liquid was applied onto a 100 μm aluminum plate using an applicator. It was coated and dried at 90° C. for 30 minutes to form a charge generation layer with a dry thickness of 1 μm.

Next, 2 parts of the charge transport agent shown in Table 1, polyester resin (
Bayone 200. 2 parts of Toyobo tJI (Iall>) and 30 parts of tetrahydrofuran were mixed and dissolved.

Using an applicator on the above charge transport layer, a dry film thickness of 1
It was coated to a thickness of 0 μm and dried at 90° C. for 30 minutes to obtain a laminated electrophotographic photoreceptor.

Table 4 shows the sensitivities measured in the same manner as in Example 1 except that these electrophotographic photoreceptors were charged at -5.0 KV.

Below margin Example 3 Solvents (■) shown in Table 5 as in Example 1.

100 parts each of (II) and additives (1) and (■) in Table 1
1 part of metal-free phthalocyanine was treated in numerical order using

Example 1 using these treated metal-free phthalocyanines
An electrophotographic photoreceptor was prepared in the same manner.

Table 5 shows the results of sensitivity measurements.

The following margin is Example 4 Same as Example 2 using each metal-free phthalocyanine treated in the numerical order of additives (1) and (n) in Table 1 and charge transport agent shown in Table 6 as in Example 3. A laminated electrophotographic photoreceptor was prepared using the following methods, and the sensitivity was measured. Table 6 shows the results. Note that in Example g14-f, the same electrophotographic photoreceptor as Example 4-e was used at +5. These are the measurement results under OKV charging conditions.

Below are blank spaces Example 5 As in Example 1, various additives and 40 parts of metal-free phthalocyanine were added to 100 parts of the solvent shown in Table 7 in a ball mill, and the mixture was milled for 48 hours.

Furthermore, the resin shown in Table 7 was added and milled for 48 hours to obtain a photoconductive composition, which was coated on a 100 μm aluminum plate using a bar coater to a dry film thickness of 1077 m. An electrophotographic photoreceptor was prepared in the same manner, and the sensitivity was measured. Table 7 shows the results.

Below is a blank space Example 6 Similar to Example 5, a photoconductive composition obtained from various additives and 40 parts of metal-free phthalocyanine was laminated in 100 parts of the solvent shown in Table 8 in the same manner as in Example 2. An electrophotographic photoreceptor was prepared and the sensitivity was measured. Table 8 shows the results.

Below is a margin Comparative Example 1 A photoconductive composition obtained in Example 5-a by not processing the τ-type metal-free phthalocyanine in advance, using the same amounts of additives, solvents, and resins, and milling them in a ball mill at the same time for 96 hours. The initial charge amount of an electrophotographic photoreceptor obtained in the same manner using a photoreceptor was 820V.

The sensitivity was 2.3.

Comparative Example 2 In Example 5-b, an electrophotographic photoreceptor obtained in the same manner as Comparative Example 2 without being treated with η-type metal phthalocyanine in advance had an initial charge amount of 580 V and a sensitivity of 4.5. .

patent applicant Toyo Ink Manufacturing Co., Ltd. Hitachi, Ltd.

Claims (1)

[Claims] 1. An electrophotographic photoreceptor characterized by using a τ, modified τ, η, or modified η type metal-free phthalocyanine that has been previously treated with one or more of a charge transport agent and/or a dye having a sensitizing effect.