JPH0324059A - Refining of perirene compound - Google Patents

Abstract

PURPOSE: To fractionate and sublime the title compd. useful as a photosensitive image forming member in good yield by heating a specific mixture and a perylene pigment component to separate volatile impurities and a decomposition product.

CONSTITUTION: A mixture of bisbenzimidazo (2,1-a,1',1'-b)anthra(2,1,9-def: 6,5,10-d' e'f')diisoquinoline-6-11-dione and bisbenzimidazo(2,1-a,1',1'-b)anthra(2,1,9-def: 6,5,10-d'e'f')diisoquinoline-10,21-dione and a perylene pigment component selected from N,N'-diphenylperylene-3,4,9,10-tetracarboxylic acid dimides are prepared to be heated to separate impurities and decomposition products more volatile than these components at temp. lower than 350°C to obtain a purified component at about 350-550°C.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to a method for preparing perylene pigments useful in photosensitive images or members, and more particularly, the present invention relates to a method for preparing perylene pigments useful in photosensitive images or members, and more particularly, the present invention relates to a method for preparing perylene pigments useful in photosensitive images or members, and more particularly, the present invention relates to a method for preparing perylene pigments useful in photosensitive images or members, and more particularly, the present invention relates to a method for preparing perylene pigments useful in photosensitive images or members, and more particularly, the present invention relates to a method for preparing perylene pigments useful in photosensitive images or members, and more particularly, the present invention relates to a method for preparing perylene pigments useful in photosensitive images or members. The present invention relates to a multilayered photosensitive member.

More specifically, the purification by sublimation described above involves the fractional condensation of volatile perylene, which is usually a solid material and can be vaporized without chemical or thermal decomposition. That is, the process of the present invention involves the fractional condensation of perylene-3,4,9,10-tetracarboxylic acid bisbenzidazole from its vapor by sublimation under controlled temperature and pressure to minimize impurity absorption. It is particularly suitable for obtaining solid products with Thus, in accordance with the present invention, highly purified bioproducts are obtained in acceptable yields, and the products have improved electrostatographic properties as described below. Thus, in one embodiment B, the present invention includes a sublimation method for preparing purified perylenes useful as organic photoexciter materials in multilayer photosensitive image forming members containing arylamine hole transport molecules. do. The photosensitive image forming member described above can be negatively charged when the purified perylene photoexcitation layer is placed between the hole transport layer and the substrate; and the hole transport layer is placed between the photoexcitation layer and the supporting substrate. When it can be positively charged. Furthermore, it contains a purified perylene pigment photoexciter compound obtained by the method of the present invention,
The photosensitive image-forming member containing the arylamine hole transport layer can also be used in electrophotographic imaging methods, in particular for converting negatively or positively charged images into visible images with a developer material having an appropriate charge. Useful in electrostatography.

Unexplored U.S. Pat. No. 3,871,882 includes certain N, N-
Photoconductive materials are disclosed that include disubstituted perylene-3.4.9.10-tetracarboxylic acid diamide dyes. According to the teachings of that patent, the photoconductive layer is preferably formed by vacuum deposition of the dye. The US patent also discloses a two-layer photoreceptor comprising an N,N-disubstituted perylene-3,4,9.10-tetracarboxylic acid diimide derivative having a spectral response in the wavelength range of 400-600 nm. ing.

Methods for preparing perylene compounds are also known.

For example, perylene compounds of the type exemplified herein include quinoline or 1-perylene-3.4,9.10-tetracarboxylic acid or the corresponding anhydride with a suitable amine.
It can be prepared by reaction in chloronaphthalene, the condensation reaction being carried out in the presence of a catalyst, e.g.
This is carried out by heating at an elevated temperature of 230°C. moreover,
Details regarding these methods can be found in German Patent Publication Nos. 2 and 4.
No. 51,780, No. 2,451,781, No. 2,4
51,7 8 2, No. 2.451,783, No. 2,
No. 451,784, No. 3.016,765; French Patent No. 7723888; British Patent No. 857,130, No. 901.694, No. LO 95,196; and U.S. patents disclosing sublimable perylene pigments. Patent No. 4,43
No. 1,722.

However, the methods of preparing perylene pigments disclosed in the above-mentioned patents give photoconductive materials containing impurities and often lead to undesirable high dark decay values, especially when these pigments are used as dispersions. Produces low photosensitivity and low charge acceptance characteristics.

Although the perylene preparation methods described above are suitable for their intended purposes, there is a need for improved methods, particularly methods for obtaining purified perylene that can be used in multilayered components containing arylamine hole transport compounds. It also contains an arylamine charge transport compound and a purified perylene pigment as a photoexcitable material, has acceptable visible light sensitivity, low dark decay properties and high charge acceptance values, and is suitable for multiple applications in electrostatographic imaging or reproduction equipment. There is a need for a multilayer statue or member that can be used in the statue cycle. There is also a need for a process that allows the preparation of perylene by a simple and economical fractional sublimation process, thereby removing undesirable impurities from the perylene. Additionally, there continues to be an important need for disposable imaging members containing non-toxic perylene organic pigments obtained by fractional sublimation. Also, for example, a light emitting diode (
LED), and electrostatographic imaging methods using helium cadmium or helium neon lasers; ,
Thus, there is a need for non-toxic perylene organic pigments obtained by fractional sublimation that are particularly sensitive from about 400 to about 800 nm (nanometers).

SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved process for the preparation of perylenes useful in photosensitive materials that are substantially non-hazardous to the user.

The above and other objects of the present invention are accomplished by providing an improved method for preparing purified perylene useful as a photoactivatable pigment in multilayer image-shaped bottom members. The methods of the following group; Ding. Formula: cistrans (wherein, Idazoldiyl, 5,6-
cis and tris isomers with divalent aromatic hydrocarbon groups such as penzimidazolediyl and 6,7-quinolinedyl; or divalent heterocyclic groups or their corresponding methyl, nitro, chloro and methoxy substituted derivatives. body mixture; and ■. 2: (wherein A is hydrogen, an alkyl group having 1 to about 4 carbon atoms, ryoryl, substituted aryl, ryaryl alkyl,
alkoxyalkyl, carboxylate, heterocyclic group, alkoxyaryl, specific examples of which are methyl, ethyl, phenyl, methoxy, ethoxy, propoxy, pyrrole, furan, imidazole, ester and quinoline); This includes preparing a known perylene pigment compound by subjecting it to fractional sublimation treatment. The fractional sublimation of perylene pigments described above involves first heating the pigment at a first position to a temperature T1 to evaporate the pigment and volatile impurities therein, and then pseudo-condensing the obtained perylene pigment vapor to obtain purified perylene at T1. , at a second position maintained at a lower temperature T2, followed by condensation of vapors of volatile impurities at a third position maintained at a lower temperature T3 to form deposits. Thus, the undesired unsublimated impurities remain in the first position of the starting material, yielding a purified perylene pigment separated from volatile and unsublimed impurities.

Furthermore, in the method of the invention, the temperature T1 is about 350
to about 650°C and iTz is about 350 to about 500°C; T3 is about 20 to about 350°C, but each temperature used is as described above, i.e., in a particular process embodiment. , temperature T2 is lower than temperature T1, and temperature T3 is lower than temperature T8. Additionally, the fractional sublimation of the perylene pigments of the present invention may be carried out in vacuum or in a low pressure continuous flow of inert gas, which transports the perylene and impurity vapors to the aforementioned desired locations where they separately condense and remove the deposits. This can be done by flowing a In one embodiment of the invention, the process includes known purification methods such as train sublimation, carrier gas sublimation, entrainer sublimation or zone purification.
Generally, train sublimation uses a cylindrical tube, such as glass, stainless steel, quartz, etc., as the main device. When refining perylene (sublimation temperature 4
00-550°C), Pyrex glass is commonly used as this type of glass has a softening point of about 580'C. The tube is placed inside a furnace that creates a temperature gradient of about 550 to about 20"C along the length of the tube, and the furnace is either a commercial three-zone furnace or a heater band placed around one end of the copper tube at the other end. The temperature profile along the cylindrical tube is measured with thermocouples, and the perylene to be purified is heated to a specific temperature in the tube, raising the temperature to about 550°C. A rotary vane pump is also used to maintain the flow of purification inert gas (nitrogen, argon or helium, etc.) inside the tube, the purpose of which is to improve the heating flow inside the glass tube and sublimation. This is to facilitate the transfer of steam to the condenser end of the tube.The Pirani gauge indicates the gas pressure;
In addition, the flow rate is monitored with a flow meter. A liquid nitrogen cold trap prevents contamination of the rotary pump by volatile impurities and dispersed products released during the purification process. Purification tubes can be made of glass, stainless steel, aluminum, etc. The diameter of the tube is 25-1. OO0mm
The length can also vary from 300 to 1,000n. Heating of the pigment to be purified can be thermal, radiant or dielectric.

The carrier gas is typically nitrogen, helium, argon, etc. Purified perylene pigments are more thermally stable than the crude starting material due to the reduction of impurities that induce or catalyze thermal decomposition.

The perylene pigment is then heated to about 550° C. and the resulting vapor is blown toward the cold end of the tube by a flow of a low pressure inert carrier gas such as nitrogen, helium, argon, or mixtures thereof. Impurities and decomposition products that are more volatile than the perylene are transferred to the cold end of the tube below 300°C and condensed. The purified perylene is preferably collected in a temperature range between about 360°C and about 460°C, leaving non-sublimable residue where the starting material was placed.

As a result, separation of the product perylene pigment from both the more volatile components and the non-sublimated residue is achieved. Compared to the original combined pigment used, the resulting train sublimation purified perylene exhibits superior electrostatographic performance when incorporated into the multilayered image forms or components described above. Furthermore, train-sublimated perylene exhibits a substantial reduction in impurity content compared to the as-sublimated material. Changes in impurity content were determined by multi-element analysis, sulfur analysis, thermogravimetric analysis, and perylene 3.4, 9.
Extractable perylenes such as 10-tetracarboxylic acid were tested by optical absorption spectroscopy. In particular, perylenes generally contain four chemical elements: carbon, hydrogen, oxygen and nitrogen, as well as the presence of other elemental impurities. Therefore, multi-element analysis and sulfur analysis will indicate the extent of impurity contamination in the perylene. Thermogravimetric analysis (TGA) is 25-400℃
Perylene pigments show a weight loss when heated to , and this weight loss occurs when impurities that are more volatile than perylene are evaporated by heating. The greater the TGA weight loss, the greater the amount of volatile impurities present in the perylene.

Another harmful impurity is perylene-3,4.9.10-tetracarboxylic acid (PTCDA) impurity, a precursor material used to form perylene pigments, the unreacted acid precursor of which is occluded within perylene pigments. can be done. After washing the perylene pigment for a long time with an alkaline alcohol solution, the extractability P T C D , A. The amount of perylene is measured optically to indicate its presence in the perylene product.

Although the precise reasons for the improvement in the electrostatographic electrical properties of perylene-containing imaging members prepared by the method of the present invention are not fully understood, in general it is believed that it has an unfavorable effect on the electrical properties of perylene. It is believed that this is in part related to the removal of certain impurities. This electrostatographic performance is typically determined by measuring the dark decay, initial charge acceptance and photosensitivity of a multilayered image-forming bottom member containing perylene pigments obtained by the method of the present invention (see Example 3). ). The image forming element can be suitably charged to a particular operating surface potential and retains much of that potential in the dark prior to exposure in the image form. After the light image form, the member:′! ,
The potential of the resulting latent image must be maintained for a period of time before it is developed with ink or toner and transferred to a suitable medium, such as paper or a plastic sheet. Low dark decay is required to maintain the initial charging potential and subsequent latent image potential. A high initial charge acceptance provides greater width for creating contrast potentials of the latent image. High photosensitivity also supports the use of low intensity and cost saving illumination sources as well as improvements in imaging speed by reducing imaging time.

The photosensitivity is usually expressed as the EA value, ie the exposure energy required to discharge the surface potential to half its initial B,11 value. Small E% values include high photosensitivity. Although other additional conditions exist, the electrostatographic performance of sublimation-purified perylene can be well explained in dark decay, charge acceptance, and photosensitivity.

Specific specific examples of purified perylene pigments obtained by the method of the present invention and which can be used for inclusion in image-forming members include those having the following formula: ■. perylene 3.4,9
．． 10-Tetracarboxylic acid bisbenzimidazole and rV: N,N'-diphenylperylene-3.4 of the following formula
, 9. 10-Tetracarboxylic acid diimide Furthermore, in perylene of formula l, the cis isomer is bisbenzimidazo(2,1-a-1'.1'b) anthra(2,1.9-def :6,510-d 'e'f
') diisoquinoline-6,11 dione, and the trans isomer has the chemical notation bisbenzimidazo(2,1a-1', l'-b) anthra(2
, 1,9def:6.5.10-d'e'f') diisoquinoline-10.21-dione.

In the following Table 1, P P 4. compared with the sample obtained by the train sublimation method of the present invention. 7 9, PP
The results of impurity analysis of perylene-3.4.9.10 = bisbenzimidazole tetracarboxylic acid pigments of 3-basochi group designated as 520 and PP571 are shown. Thermogravimetric analysis (TGA) shows that the sublimation-purified penzimidazole perylene showed a weight loss of 0.06%, whereas each as-synthesized pigment showed a higher weight loss of 0.10-0.15%. Each sample of Gakai Shitama\ contains a larger amount of impurities removed by heating from 25°C to 400°C. Also, extractable perylene-3, 4, 9,
The amount of IO-tetracarboxylic acid (PTCDA) was below the detection limit of the instrument. In each of the pigments, PTCDA ranged from 25 to 559 ppm.

Table I N. D. = not detectable In addition, the yellow sulfur content was negligible in the sublimated sample, whereas it was 337 to 504 ppm in the as-merited pigment.

The purity values of the pigments varied between bunches, but
After train sublimation, all perylene pigments are slightly below 0.
The removal of impurities was achieved showing a weight loss at 400° C. of less than 0.6%, undetectable amounts of PTODA and S, thereby yielding a pigment of high purity.

The results of multi-element analysis (Table 2) of each batch of as-combined perylene-3.4,9.10 tetracarboxylic acid bisbenzimidazole pigment show that iron (
≧250ppm), sodium (≧100p
pm), and calcium (≧19 ppm). Purification of the same pigments by the train sublimation method of the present invention reduces metal impurities to negligible or below detectable amounts. These results demonstrate the effectiveness of the purification method of the present invention in producing high quality materials. Table 2 Multi-element microanalysis of perylene-3.4,9.10-tetracarboxylic acid bishenzimidazole pigment
-diphenyl-N,N'bis(3-methylphenyl)-
Thickness I overcoated with a 20 micron thick hole transport layer of bisphenol A polycarbonate containing (1,1'-biphenyl)-4,4'-diamine
Polyvinyl strength in micron 80 in rubazol binder
Perylene prepared by the train sublimation method of the present invention compared with as-synthesized perylene of the prior art as binder exciter layer with wt% content -3.4.9.10-
Tetracarboxylic acid bisbenzimidazole pigment and N
, N'-diphenylperylene-3.4,9.10-tetracarboxylic acid diimide pigments. These results clearly demonstrate the improvement in charge acceptance, dark decay and photosensitivity in train sublimation purification of crude pigments.

-Eni:L2L1 Table 4 Conventional sublimation as disclosed in U.S. Pat. No. 4,431,722, as in the method of the present invention,
Does not allow for fractionation of volatiles from the desired product. Conventional sublimation results in pigment contamination and thus less than desired electrostatographic performance. To demonstrate the differences between the two methods, as-combined perylene-34.9,to-tetracarboxylic acid bisbenzimidazole pigment, batch number PP571, was purified by conventional sublimation and fractional sublimation methods. Fractional sublimation of the as-merited perylene was carried out according to the train sublimation method described in Example 2 of the present invention. Do you own the US? No. 4,431
, 722 and Example 1 thereof. More specifically, the freshly synthesized perylene PP571 was loaded into a tantalum evaporation board installed in a Varian 3117 vacuum coater, sublimated at 530 °C, and deposited onto a glass substrate placed 15 cm from the evaporation boat. Ta. The electrostatographic properties of both the sublimated material and the starting crude material were tested in the same two-layer photoreceptor structure. The electrostatographic results are shown in Table 5.

As shown by the results in Table 5, the benzid ξdazole perylene obtained by conventional sublimation methods as described in the prior art did not show any improvement in electrostatographic electrical properties over the as-synthesized pigment. Their charging properties, including dark decay, charge acceptance and photosensitivity, are comparable. However, train sublimation purified perylenes prepared by the method of the present invention exhibit significant improvements in charging properties; higher charge acceptance and lower dark decay than conventional materials. A substantial improvement in photosensitivity was also achieved as evidenced by the low El/■ values measured.

TABLE 5 Many different multilayered photosensitive imaging bottom members can be made containing the purified perylene pigments of the present invention.

In one embodiment, a multilayered photosensitive imaging member comprises a supporting substrate, an arylamine hole transport layer, and a photoexciter layer therebetween comprising a sublimated perylene pigment prepared as described below. include.

Another embodiment of the present invention is a positively charged multilayer photosensitive image comprising a supporting substrate, an aryl anion hole transport layer, and a sublimated perylene photoexciter layer comprising a purified perylene pigment as described below as a top over coating. It relates to a shape or member. Furthermore, according to the invention, a sublimated perylene photoexciter comprising a supporting substrate, a thin adhesive layer, and optionally a perylene pigment of the invention dispersed in a polymeric resin binder;
and ryolamine hole transport molecules dispersed in a polymeric resin binder as a top layer. Furthermore,
In accordance with the present invention there is provided a dipolar photosensitive image member or member comprising a supporting substrate, a monolayer containing a sublimation purified perylene compound obtained by the method of the present invention, and a hole transport layer.

The improved photosensitive image forming members of this invention can be made by a number of methods, the process parameters and the order of coating the multilayers depending on the desired member. For example, these image-forming members can be made by depositing a photoexciter layer onto a supporting substrate with an adhesive layer, followed by depositing a hole transport layer by solution coating. Images or members suitable for positive charging can be created by reversing the order of deposition of the photoexciter layer and the tag transport layer.

Images or members containing perylene pigments of the present invention are useful in a variety of electrophotographic imaging systems, particularly those commonly known as electrostatography. In particular, the image-forming member of the present invention has a perylene pigment of about 400 nm to about 80 Or+.
It is useful in electrostatographic imaging methods that absorb light at wavelengths of m. In these methods, an electrostatic latent image is first formed on an image form or member, then developed, and the image is then transferred to a suitable substrate.

Furthermore, the imageforms or members of the present invention are constructed using gallium arsenide light emitting diodes (LEs) that typically function at a wavelength of 660 nm.
D) It can also be used in electronic copying methods using arrays.

In FIG. 1, bisbenzimidazo(2.1-a-1', 1'-b) anthra( 2,1.9-def:6.5.to-d'e'
f') diisoquinoline-6,11-dione and bisbenzimidazo (2+ i a-1.1'-b
) Anthra (2, 1. 9-def: 6.5.1
0-d'e'f' ) diisovinoline-10.
A photoconductive layer 3 comprising a mixture of cis and trus isomers of 21-diones, and an inert polyester, N,N'-diphenyl-N, dispersed in a fatty binder composition 8.
, N'-bis(3-methylphenyl)-Cl, 1'-bifenino, etc., and a charge carrier hole transport layer 5 containing 4,4'-diamine 7. Members are illustrated.

Figure 2 shows essentially the same image form or material B as shown in Figure 1, but with a hole transport layer placed between the supporting substrate and the photoconductive layer. There is. Further details: In FIG. 2, a support substrate 15, a hole transport layer 17 containing arylamine hole transport molecules 19 partitioned into an inert polycarbonate resin binder 20, and a resin binder set are shown. A photosensitive image forming member is shown comprising a photoconductive layer 21 comprising a train-sublimated perylene compound 23 of the present invention optionally dispersed in a material 25.

In FIG. 3, a substrate 31 and preferably a dia short charge carrier or hole transport molecule cis, trans 3
1 and an inert binder 36 in a solid solution of about 1:1 to about 1:20 ratio.
Two preferred ambipolar photosensitive imaging members are illustrated.

In FIG. 4, an example of an apparatus that can be used for train sublimation of perylene photoconductive pigments of the present invention is shown, such as an oven or furnace 41; three or more independently controlled heaters 42; a glass, stainless steel or aluminum sublimation tube 43 with a diameter of 75 mm and a length of 1000 m; an inert gas supply cylinder 44; a flow meter 45 (Gilmont*F1200): It includes a pressure gauge 46 (Edwards Billini); a cold trap 47; and a rotary vacuum pump 48.

FIG. 5 shows a plot of 1/E Il2 (reciprocal) value versus nanometer (nm) wavelength for a photosensitive image or member prepared according to Example 3. In detail, curve 1 contains train sublimation purified perylene 3.4.9.10-tetracarboxylic acid bisbenzimidazole of formula 2 in the negatively charged two-layer photosensitive member shown in FIG. 1, and the photoexcitation layer is 1 micron thick. Figure 3 shows the photosensitivity of the image forming member of Example 3 containing 80% by weight of the above perylene dispersed in a polyvinyl carbazole resin.

The substrate layer used in the image forming element of the present invention may be opaque or substantially transparent and may include any suitable material having predetermined mechanical properties. That is, the substrate is a layer of an insulating material including an inorganic or organic polymeric material such as mylar, which is a commercially available polymer; a layer of an organic or inorganic material with a semiconducting surface layer such as indium tin oxide or aluminum; , chromium, nickel,
Conductive materials may include titanium, zirconium, brass, and the like. The substrate can be flexible or rigid, e.g.
It can have many different shapes such as plates, cylindrical drums, scrolls, endless flexible belts, etc. Preferably, the substrate is in the form of a seamless flexible belt. In some cases, especially when the substrate is a flexible organic polymeric material, the backside of the substrate may be coated with an anti-curl layer, such as a polycarbonate material commercially available as Makrolon. is desirable.

The thickness of the substrate layer depends on many factors including economics, i.e.
The base layer may contain, for example, 2,
It may have a substantial thickness or a minimum thickness of 500ξ ξcm or more. In one preferred implementation B4F=:
The thickness of this layer ranges from about 75 to about 250 microns.

Furthermore, regarding the image-forming element of the present invention, the photoexciter layer preferably contains the purified perylene dispersed in a resin binder. In general, the thickness of the perylene photoexciter layer depends on a number of factors, including the thickness of other layers and the proportion of the photoexciter material contained in the layer. Thus, this layer may have a thickness of about 0.05 to about 10 microns when the photoexciter perylene compound is present in an amount of about 5 to about 100% by weight.

Preferably, this layer contains 8 photoexciter perylene compounds.
When present in an amount of 0% by weight, it has a thickness of about 0.25 to about 2 microns. In one highly preferred embodiment, the vacuum deposited photoexcitation layer has a thickness of about 0.05 to about 1.5
It has a thickness of 1.5 cm. The maximum thickness of this layer depends primarily on factors such as its photosensitivity, electrical properties and mechanical properties.

Specific examples of polymeric binder resin materials that can be used for photoexciter pigments include polymers such as those disclosed in U.S. Pat. No. 3,121,006, the entire contents of which are incorporated herein by reference. ), polyester,
Polyvinyl butyral, Formvar
, registered trademark), polycarbonate resins, polyvinylcarbazole, epoxy resins, phenoxy resins, and especially commercially available poly(hydroxyether) resins.

The arylamine used in the hole transport layer having a thickness of about 5 to about 50 microns per meter and a thickness of about 10 to about 40 microns dispersed in a highly insulating transparent organic resin binder has the following formula: [Wherein, X is an alkyl group or a halogen, especially (ortho)CHs, (rose)CH3, (ortho)Ci',
(Meta) Cj! There is a molecule which has a substituent selected from the group consisting of and (l). Examples of specific arylamines include:
N,N'-diphenyl-N,N'-bis(alkylphenyl)[1. 1'-biphenyl]-4,4'-diamine, where alkyl is methyl, ethyl, probyl, such as 2-methyl, 3-methyl and 4-methyl;
Selected from the group consisting of butyl, hexyl, etc. In the chloro substitution, the amine is N,N'-diphenyl-N,N'-bis(halophenyl)-(1.1'-biphenyl)-4,4'-diaξ, where halo is 2
1 Rolo, 3-'F Rolo Mataha 4-Chloro. Examples of highly insulating transparent resin binders or inert resin binders for the transport layer include materials such as those described in U.S. Pat. No. 3,121,006, the disclosure of which is incorporated herein by reference. Quote in the book. Particular examples of organic resin materials include polycarbonates, acrylate polymers, vinyl polymers, cellulose polymers, polyesters, polysiloxanes, polyamides, polyurethanes and epoxies, and block, random or alternating copolymers thereof. Preferred electrically inert binders have a molecular weight of about 20,000 to about 100,000. OQO (molecular weight approximately 50.00
0 to about 100,000 is particularly preferred). Generally, the resin binder is about 10% to about 75% by weight, preferably about 35% to about 50% by weight.
contains an active substance corresponding to the above-mentioned formula.

As adhesive layer or silane layer present on the supporting substrate,
E.I. A variety of known materials can be used including polyesters such as those commercially available as 49,000 Polyester from DuPont.

This layer has a thickness of about 0.05-1 micron.

Further, the image form or member of the present invention forms an electrostatic latent image on the image form, develops this image with a toner composition, and then transfers the image to a suitable substrate. It is useful in imaging methods that generally involve permanently fixing a material to a substrate. If the device is to be used in a printing mode, the imaging or method involves the same steps except that the exposure step may be performed by a laser device or an image bar.

Example 1 817 g (2.
08 mol> of perylene-3.4,9.10-tetracarboxylic dianhydride, 1. 169 g (10.4 mol) of 0-phenylenediamine and 9.36 l of l
- chloronaphthalene was mixed. The resulting mixture was heated with stirring at 240-25 (l) for 3 hours and then cooled to room temperature. A solid product was then obtained by filtering the mixture through a filter cloth and then diluted with N,N-dimethylforma Washed three times with ξ. The solid was then slurried with alcoholic sodium hydroxide solution. After filtration,
The solid was washed with N,N-dimethylformamide, methanol, and then dried in an oven at 95°C overnight.
, 100 g (7) of PelJren-3.4,9.10-tetracarboxylic acid bisbenzimidazole (2) was obtained.

Various breast foods Bakhchi PP479 prepared by this procedure
, PP52Q, and PP571 are shown in Table 1. The results of extraction analysis of yellow sulfur and acid dianhydride are shown in Table 1, and the results of multi-element analysis are shown in Table 2. In general, perylene pigments are highly contaminated and their staining values vary from batch to batch.

Example 2 Tog unpurified perylene-3.4,9.10 tetracarboxylic acid bisbenzi ξ dazole pigment (batch number PP4
79) was placed inside a 75m x 1.000m Pyrex tube at its I end, and the tube was then placed in a three-zone furnace (see Figure 4). Each heater in the furnace was adjusted to create a temperature gradient along the length of the tube. Attach the end of the tube containing the perylene pigment to about 5
It was heated to 50° C. and the resulting perylene vapor was blown away with a low pressure inert nitrogen carrier gas. Impurities and decomposition products more volatile than perylene were kept at 25-300°C. It was transferred to the cold end of the tube where it was contracted for 43 minutes. Purified perylene was deposited in the center of the tube, which was maintained at a temperature of 380-460°C. At the end of the treatment, unsublimated residue remained where the starting material had been placed. Approximately 7g (approximately 70
% yield) of pure perylene pigment was carefully collected from the central region of the tube. Sulfur, iron, extractable dianhydride, trace metals and weight of sublimated perylene in the second train? As shown in Tables 1 and 2, the J&loss analysis was all below the detectable value. High purity (electrophotographic grade) perylene-3 obtained by this method. 4. 9.10-Tetracarboxylic acid bisbenzimidazole pigments exhibited improved electrostatographic performance (see Example 3).

Example 3 A photosensitive image-shaped bottom member was prepared on a 75 micron thick aluminized Mylar substrate and then applied to the substrate using a multiple clearance film applicator.
-Methyl-3-aminopropyltrimethoxysilane (available from PCR Research Chemicals, Florida)
A layer of 1:20 volume ratio in ethanol was applied at a wet thickness of 12.5 microns. The layer was then dried at room temperature for 5 minutes, followed by curing in a forced air oven at 110° C. for 10 minutes to obtain a silane layer with a dry thickness of 0.05 microns.

Next, the silane layer was coated with 49.
000 polyester in methylene chloride and 1,1.2-}lichloroethane (4:1 volume ratio). 5% by weight was applied to a wet thickness of 12.5 microns using a multiple clearance film applicator. This layer was dried for 1 minute at room temperature and 10 minutes at 100° C. in a forced air oven. The resulting layer is 0.05
It had a dry thickness of microns.

The photoexcitation layer was prepared in the following manner: In a 2 oz. amber bottle, 0.0 ml of purified perylene compound obtained by the method of Example 2 was added. 4
0 g, 70 g of 1/8 inch (3.175 m) stainless steel balls, and 9.5 g of methylene chloride were added. The mixture was ball milled for 2-120 hours, 0.1 g of polyvinylcarbazole was added to the resulting slurry, and ξ-ringing continued for an additional 17 hours. The resulting mixture was coated onto the polyester adhesive layer with a multiple clearance film applicator to a wet thickness of 25 microns. The resulting photoexcitation layer was air-dried for 5 minutes and then dried in a forced air oven at 135° C. for 6 minutes. The dry thickness of the photoexcitation layer was 1.0 micron.

Next, the transfer layer was made of 65% by weight macrolone polycarbonate resin and 35% by weight N,N'-diphenyl N,N
'-bis(3-methylphenyl)-cl,i'-biphenyl)-4.4'-diayone was prepared by mixing. This solution was then mixed to 9% by weight in methylene chloride. All of these ingredients were placed in an amber bottle and dissolved. The resulting mixture was coated with a multi-clearance film applicator (200 micron wet gap thickness) and coated with the above Perile® film applicator (200 micron wet gap thickness). A layer with a dry thickness of 20 microns was obtained on top of the photoexcitation layer. The resulting image-shaped parts were dried at room temperature for 20 minutes and then in a forced air oven at 135° C. for 6 minutes.

The photosensitivity of this member is determined by electrostatically charging its surface with a corona discharge source until the surface potential obtains an initial dark value v0 of -800 volts, as measured by a capacitively coupled probe connected to an electrometer. It was measured by Next, the front surface of the charged member is exposed to a filtered xenon lamp XB.
Exposure to light from an O75 watt source, 400-800 nm
Light with a range of wavelengths was allowed to reach the surface of the member. Next, the % discharge of the surface potential was measured with exposure EI 7■ which reduced the surface potential to half of its initial value and with various exposure energies. The photosensitivity was measured for the exposure in ergs/d required to discharge the member from its initial surface potential to half its value. The higher the photosensitivity, the lower the exposure energy required to discharge the layer to 50% of its surface potential. The photosensitivity spectrum response results are shown in Figure 5, where:
The reciprocal of E+7t is plotted against wavelength (nm). In white light, 4.00 to 800 nm exposure,
E+zz value is 3.9-4.2 erg/1, 1.0
The % discharge at an exposure level of Erg/1 was 82-84. Dark decay was 13-20 volts/second and charge acceptance was 840 volts. In comparison, a photosensitive element containing crude perylene PP479, prepared as described in Example 1, had poor electrostatographic electrical properties, high dark decay of 48 volts/second, and high dark decay of 430 volts/sec. It showed a low charge acceptance of volts (Table 3). Example 4 In a three-necked flask, 5.85 g of perylene-3.4.
9. 10-Tetracarboxylic dianhydride, 23.8 mA of aniline, and 7 tel of glacial acetic acid were mixed. The resulting mixture was heated with stirring at 210° C. for 8 hours, then cooled to room temperature. A solid product was then obtained by filtering the mixture through a sintered glass funnel and then washed with 1 liter of ethanol.

The solids were then slurried with 500 Ill1 of 1% sodium hydroxide solution. After filtration, the solid was washed with 600 ml of water and then dried in an oven at 80° C. overnight to yield 70 g of crude product of formula (2). Example 5 2 grams of the perylene pigment of Example 4 was placed in a Pyrex tube (1 inch outside diameter (2.54 value), 2.5 mm long).
8 inches (71.1 mark)] (approximately 5 inches (76.2 co+) from one end). Next, a thick-walled tube [0.5 inch (1.27 CI1
) Thickness] was placed in a furnace containing a copper tube. 550℃～25
A temperature gradient in °C was obtained along the length of the tube and monitored by a thermocouple probe. The Pyrex tube was positioned so that the perylene to be sublimated was within the heater band. Subsequently, the perylene was heated to approximately 550° C. and the resulting vapor was blown to the cold end with a low pressure (2 mbar) nitrogen carrier gas. Perylene vapor has a temperature of 4
It condensed to form a distinct red precipitate between 60 and 380°C, whereas the more volatile impurities separated well from the purified perylene and precipitated below 360°C. A small amount of unsublimated residue remained where the raw material of the combined mirror was placed. 1.4 g of purified perylene (yield 70%) was obtained.

Example 6 Two photosensitive images or members A and B were made by repeating the procedure of Example 3, but using N.I. as the photoexcitable pigment.
N'-diphenylperylene-3,4.9.10-tetracarboxylic acid diimide was used. The refined unrefined perylene pigment of Example 4 was used in the first image form or member A, and the sublimation purified perylene pigment of Example 5 was used in the second member B. Thereafter, the photosensitivity of each obtained member was measured by repeating the procedure of Example 3. The results are shown in Table 4. Imaging member of sublimation purified pigment of Example 5? This represents a substantial improvement over the composite pigment of Example 4.

For example, excellent charging properties, ie, high charge acceptance, low dark decay, and high photosensitivity indicated by low El/■ values have been demonstrated in purified perylenes.

Example 7 Photosensitive images or members were prepared by repeating the procedure of Example 3, but each with a thickness of 0.85 mm as the photoexcitation layer.
, 1. Purified perylene of 0 and 1.5 microns was used.

The photosensitivity of each obtained member was measured according to the procedure of Example 3. The results are as follows: perylene thickness El/2 (erg/cni) 0. 5ξcm 5.01.0 micron
3.91.5 microns 3.41.5
The ξ micron member is slightly more photosensitive than the 1.0 micron member. N,N'-diphenylperylene-3.4.9
．． 10-Tetracarboxylic acid diimide compared to image form or member B of Example 6 containing a photoexcitation layer? Then, the 1.0ξ Cron member is about twice as sensitive at the El/■ value.

Example 8 Photosensitive images or members were prepared by repeating the procedure of Example 3, but using pigment to polyvinylcarbazole weight ratios of 15, 30, 60, 80 and 90% by weight pigment content, respectively. Each exciter layer containing

The photosensitivity of each member obtained was measured according to the procedure of Example 3, and the following results were obtained.

It is also slightly photosensitive, and it is believed that this slightly higher photosensitivity is caused by higher light absorption.

Example 9 A photosensitive image or member was prepared by repeating the procedure of Example 3, but using polyvinyl butyral (PVB), polyvinyl formal (
PVF), polyvinyl acetate (PVA), polyvinylcarbazole (PVK), polycarbonate Z (P
C (Z)), DEEPON 49,000 polyester (49K), polystyrene (PS), epoxy resin (EPON manufactured by Ciel and manufactured by Dow), polyvinylpyrrolidone (PVP), hydroxybrobyl cellulose (HPC)
) and phenoxy resin were used, respectively. The photosensitivity of each member obtained was measured according to Example 3, and the following results were obtained.

All binder resins showed similar performance in the 90% by weight component compared to the 80% by weight component, but polyvinylpyrrolidone and hydroxypropyl cellulose decreased photosensitivity. Example 10 A photosensitive imaging member was prepared by repeating the procedure of Example 3, but using a titanium-treated Mylar substrate in place of the aluminum-treated Mylar substrate.

The photosensitivity of the obtained member was measured according to the procedure of Example 3, and the following results were obtained.

Titanium Treated Mylar 1 2-14 3.8 Example 11 Photosensitive image forming members were prepared by repeating the procedure of Example 3, but charge carrier hole transport layer thicknesses used were 17 microns and 27 microns, respectively. It was a long time ago. The photosensitivity of each member obtained was measured according to the procedure of Example 3, and the following results were obtained.

1 7 4 1~44 3.9
27 8～11 3.227
The micron members exhibit significantly lower dark decay and slightly higher photosensitivity than the 17 micron feature members.

[Brief explanation of drawings]

FIG. 1 is a partial sectional view of a negatively charged photosensitive image-forming member of the present invention. FIG. 2 is a partial cross-sectional view of the positively charged photosensitive imaging member of the present invention. FIG. 3 is a partial cross-sectional view of a bipolar photosensitive image or member of the present invention. FIG. 4 is a partial cross-sectional view of the apparatus used in the method of the invention. FIG. 5 is a line graph showing the spectral response of certain perylene pigments of the present invention. 1, 36, 25, 34, 42, 44, 15, 31... supporting base, 3, 17,... photoexcitation layer,
5, 19...Hole transport layer...Binder composition, 7
, l9, 35 arylamine hole transport molecule, 4, 23,
... Purified perylene pigment, 8, 20, 36 Inert binder, 41 ... Oven, ... Heater 43 ... Sublimation tube, ... Inert gas supply cylinder, 45 Flow meter, 46 ... Pressure gauge, 47... cold cup, 48.
...Vacuum bomb. FIG. 1 FIG. 2 400 500 600 700 800 i& (nrn) FIG. 3 FIG. 5

Claims (2)

[Claims] (1) (1) Bisbenzimidazo (2, 1-a-1',
1'-b) Anthra (2, 1, 9-def: 6, 5, 1
0-d'e'f') diisoquinoline-6,11-dione and bisbenzimidazo (2,1-a-1', 1'-b)
Anthra (2, 1, 9-def: 6, 5, 10-d'e
'f') a mixture of diisoquinoline-10,21-diones, and (2) N,N'-diphenylperylene-3,4
, 9,10-tetracarboxylic acid diimides are provided, and these components are heated to thereby remove impurities and decomposition products that are more volatile than these components to a temperature below 350°C. 1. A fractional sublimation method for the preparation of perylenes, characterized by separation at temperature and obtaining purified components at a temperature of about 350 to about 550°C. (2) Prepare unpurified perylene; then subject this perylene to temperature T_1;
condensate at _2; then more volatile impurities at temperature T
Condensate at _3; here, the temperature T_1 is about 350 to about 6
50°C, temperature T_2 is about 350 to about 550°C, and temperature T_3 is about 20 to about 350°C, provided that
Temperature T_2 is lower than temperature T_1, and temperature T_3 is lower than temperature T_1.
perylenes, characterized in that impurities and decomposition products that are less than _2 and thereby more volatile than perylene are separated at a temperature below 350°C, and a purified perylene component is obtained at a temperature of about 350 to about 550°C. Fractional sublimation method for the preparation of. (3) An imaging member comprising a supporting substrate, a photoexcitation layer comprising perylene obtained by the method of claim (2), and an arylamine hole transport layer.