CN1777843A - Electrophotographic photoreceptor, electrophotographic image forming method and electrophotographic device - Google Patents

Abstract

The present invention provides an electrophotographic photoreceptor which exhibits a high responsiveness even under a low-temperature, low-humidity environment, and can make compatible the downsizing of an electrophotographic device with a higher image forming speed. Oxotitanium phthalocayanine having a crystal type showing a diffraction peak at a Bragg angle 2theta (error: 2theta+-0.2 1/2 ) of 27.2 1/2 is included as a charge generating material (12) in the photosensitive layer (14) of the electrophotographic photoreceptor (1), and an enamine compound shown by the general formula (1), for example, the structural formula (1-1) is included as a charge transporting material (13). Accordingly, the electrophotographic photoreceptor (1) which exhibits a high responsiveness even under a low-temperature, low-humidity environment is attained.

Description

Electrophtography photosensor, electrophotographic image formation method and electro-photography apparatus

Technical field

The electrophotographic image formation method and the electro-photography apparatus that the present invention relates to Electrophtography photosensor and use this Electrophtography photosensor.More specifically, the present invention relates to have the electric charge photosensitive body of the photographic layer that contains special charge generation material and specific charge transport material and electrophotographic image formation method and the electro-photography apparatus that uses this Electrophtography photosensor.

Background technology

The image processing system (following abbreviate as sometimes " electro-photography apparatus ") that adopts electrophotographic image formation method to form image is used in duplicating machine, the Printers and Faxes machine more.Electro-photography apparatus forms image by following electronic camera technology.At first be installed in the charged equably regulation current potential that reaches in surface of the Electrophtography photosensor (following abbreviate as sometimes " photoreceptor ") in the device.Charged photosensitive surface is carried out exposure according to image information, form electrostatic latent image.With the developer that contains toner etc. the electrostatic latent image that forms is developed, form toner image as visual image.On the transfer printing body of the toner image that forms from the surface transfer of photoreceptor to paper etc., make its photographic fixing and form image.

Electrophtography photosensor comprises electric conductivity support that is formed by conductive material and the photographic layer that is arranged on the electric conductivity support.As the material of the photographic layer that constitutes photoreceptor, at present known have inorganic light conductive materials such as selenium, cadmium sulfide and zinc paste.Adopt the inorganic photoreceptor of these inorganic light conductive materials have can be in the dark charged to suitable current potential, in the dark electric charge dissipation less, many advantages such as the electric charge that can promptly dissipate by illumination, but relatively also have some shortcomings.For example adopt the difficulty of creating conditions of the selenium photoreceptor of selenium, the manufacturing cost height.And owing to, need carefully to use to a little less than heat and the physical shock.Use the cadmium sulfide photoreceptor of cadmium sulfide and use the zinc paste photoreceptor of zinc paste under the high environment of humidity, to can not get stable sensitivity, and when adding pigment as sensitizer, pigment is owing to the corona charging of photosensitive surface when charged produces charged deterioration, fade owing to exposure produces light, therefore can not provide characteristic steady in a long-term.

Because so inorganic photoreceptor has more shortcoming, the Organophotoreceptor that has therefore proposed to adopt the organic light-guide electric material is the photoreceptor of inorganic photoreceptor instead.The photoreceptor that the various organic photoconductive polymkeric substance that are representative are for example arranged with the Polyvinyl carbazole.Yet, adopt the photoreceptor of these polymkeric substance to compare with the inorganic photoreceptor of the inorganic light conductive material of described use, though better aspect the film forming of photographic layer and lightweight, its shortcoming is, its sensitivity, permanance and relatively poor to the aspects such as stability of environmental change.

Various research and development have been carried out in order to eliminate these shortcomings people, in these Organophotoreceptors, proposed with the organic photoconductive polymkeric substance born photoconductive function, i.e. the function divergence type photoreceptor shared by different material respectively of charge generation function and charge transport function.Function divergence type photoreceptor has laminated-type and single-layer type.The function divergence type photoreceptor of laminated-type is provided with the photographic layer of laminated-type, and it is by the charge generation layer that contains the charge generation material of bearing the charge generation function and contain the charge transport layer lamination of bearing the charge transport material and form.The function divergence type photoreceptor of single-layer type is provided with the photographic layer of single-layer type, and it is scattered in in one deck and form by charge generation material and charge transport material.

This function divergence type photoreceptor is wide to the material range of choice that constitutes photographic layer, by with combination of different materials so that electrofax characteristics such as charged characteristic, sensitivity, residual electric potential characteristic, repeat property and printability resistance reach optimum, high performance photoreceptor can be provided.In addition, owing to can form photographic layer by coating, thereby can provide throughput rate high and cheap photoreceptor.

In addition, in the function divergence type photoreceptor, the light that the charge generation material absorbing is radiated on the photoreceptor produces electric charge, and this electric charge is injected in the charge transport material, is transported to photosensitive surface, thus by the surface charge of the photoreceptor of light-struck part by cancellation.Owing to be radiated at light on the photoreceptor by the charge generation material absorbing,, can freely control the wavelength photoreceptor scope of photoreceptor therefore by suitably selecting the charge generation material.

In recent years,, need the image information of record and editor's input freely in order to obtain more images with high image quality, so the digitizing of image information development rapidly.Though up to now, the electro-photography apparatus that uses the image of digitized image information to form only limits to laser printer and LED (light emitting diode) printer and the partial colour laser copier etc. as the output device of word processor and computing machine etc., but using the analog image frame to form in the field of common duplicating machine of main flow, also to digital development in the past.

Digitized electro-photography apparatus is following carrying out to the exposure of photosensitive surface.For example, when direct use is formed by the digital image information image of computer manufacture, to be transformed to light signal as the digital electric signal of the image information of computing machine output, the rayed photosensitive surface by corresponding with this light signal exposes to photosensitive surface according to image information.In addition, when as duplicating machine, using the image information image that reads from original image to form, read the image information of original image with the form of light signal, after it is transformed to digital electric signal, be transformed to light signal once more, rayed photosensitive surface by corresponding with this light signal exposes to photosensitive surface according to image information.

In the digital electronic photographic means, as the light corresponding with the light signal of digital image information, this light that shines to photosensitive surface mainly adopts laser and LED light.The light of the near infrared light of wherein the most frequently used only wavelength 780nm and the isometric wavelength coverage of ruddiness of wavelength 660nm.Therefore, the photoreceptor that uses in digital photographic means at first need have sensitivity with respect to the light of these long wavelength's scopes.

As previously mentioned, by suitably selecting the charge generation material, can freely select the wavelength photoreceptor scope of photoreceptor.As light activated charge generation material, various materials are studied up to now described near infrared light and the isometric wavelength coverage of ruddiness.Wherein phthalocyanine compound is easy owing to synthesizing, and mostly to the photaesthesia of long wavelength's scope, is therefore studied widely and use.

For example, use the photoreceptor (opening clear 61-28557 communique) of the photoreceptor (with reference to special fair 5-55860 communique) of titanyl phthalocyanine, the photoreceptor (opening clear 59-155851 communique) that uses β type indium phthalocyanine, the photoreceptor (opening flat 2-233769 communique) that uses X type nonmetal phthalocyanine and use vanadyl phthalocyanine with reference to the spy with reference to the spy with reference to the spy.

In addition, there is titanyl phthalocyanine that report finds to have specific crystal formation that the light of long wavelength's scope is demonstrated extra high susceptibility recently, and proposed to use its photoreceptor.The photoreceptor that adopts the titanyl phthalocyanine with following crystal formation is for example arranged, promptly have, in X-ray diffraction spectrum, show the maximum diffraction peak for 27.3 ° in Bragg angle 2 θ (error: 2 θ ± 0.2 °), at 7.4 °, 9.7 ° and 24.2 ° of titanyl phthalocyanines (with reference to special fair 7-91486 communique) that show the crystal formation of diffraction peaks, have in 9.5 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 ° show the titanyl phthalocyanine (with reference to No. 2700859 communique of special permission) of the crystal formation of main diffraction peaks and have in 9.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 14.2 °, 23.9 ° and 27.1 ° of titanyl phthalocyanines (opening flat 3-128973 communique) that show the crystal formation of main diffraction peaks with reference to the spy.

In addition, known also has, the photoreceptor that employing has the titanyl phthalocyanine of following crystal formation has extra high susceptibility to the light of long wavelength's scope, and characteristic has good stability when reusing, its crystal formation that has is in X-ray diffraction spectrum, in 7.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.9 °, 24.1 ° and 27.2 ° show main diffraction peaks, wherein the overlapping diffraction peak bundle of the diffraction peak of 9.4 ° diffraction peak and 9.6 ° shows maximum intensity, and 27.2 ° diffraction peak demonstrates the 2nd high strength (opening the 2000-129155 communique with reference to the spy).

In addition, also proposed to use the photoreceptor of two or more phthalocyanine compounds.For example have, use contains titanyl phthalocyanine and nonmetal phthalocyanine and for CuK α characteristic X-ray (wavelength: in the X-ray diffraction spectrum 1.541 ), in 7.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 9.0 °, 14.1 °, 18.0 °, 23.7 ° and 27.3 ° photoreceptors (opening the 2000-313819 communique), use the photoreceptor (opening flat 4-372663 communique) of the phthalocyanine mixed crystal that titanyl phthalocyanine and potassium halide phthalocyanine or indium halide phthalocyanine make etc. with reference to the spy with reference to the spy with phthalocyanine composition of diffraction peak.

On the other hand, for electro-photography apparatus, also require miniaturization and image to form the high speed of speed.For electro-photography apparatus such as duplicating machine, Printers and Faxes machines, what generally use is the photoreceptor that photographic layer is set on the outer peripheral face of cylindric or cylindric electric conductivity support, for the miniaturization of electro-photography apparatus, must make the photoreceptor minor diameterization.Yet the photoreceptor that diameter is little is because the distance from the exposure position to the developing location is short, and when carrying out electronic camera technology when forming the high speed of speed for image under high speed, the time from exposing to developing shortens, and produces following problem.For example, if adopt the low photoreceptor of response, i.e. the slow photoreceptor of the rate of decay of the surface potential after the exposure then should be developed under the state of fully decaying not have by the surface potential of the part of exposure cancellation.Therefore, when standard is developed, adhering toner on the part that should become the image white background, produce be called scumming (Di れ) phenomenon, when upset was developed, image color reduced.Therefore, in order to take into account the high speed that electro-photography apparatus miniaturization and image form speed, require the high photoreceptor of response.

Open flat 3-128973 communique, spy the fair 7-91486 communique of described spy, special permission No. 2700859 communique, spy and open 2000-129155 communique, special fair 5-55860 communique, spy and open clear 59-155851 communique, spy and open that clear 61-28557 communique, spy are opened flat 2-233769 communique, the spy opens the phthalocyanine compound that uses in the photoreceptor of putting down in writing in 2000-313819 communique and the flat 4-372663 communique of Te Kai and has high charge generation ability and high electric charge injection efficiency, so the photoreceptor of putting down in writing in these communiques has response to a certain degree.Yet, inappropriate in these photoreceptors as the combination of the phthalocyanine compound of charge generation material and charge transport material, therefore can not get sufficient response.In particularly low and the environment (following this environment is called " low temperature and low humidity environment ") that humidity is low in temperature, can not obtain sufficient response, when these photoreceptors by minor diameterization, when being used for high-velocity electrons photograph technology, produce scumming (dirty れ) or image color and reduce.Thereby, when these photoreceptors use, must suppress the speed of electronic camera technology after minor diameterization, the image of electro-photography apparatus forms speed can not realize high speed.That is to say, when using these photoreceptors, can not take into account the high speed that electro-photography apparatus miniaturization and image form speed.

Summary of the invention

The present invention is intended to by making up specific charge generation material and specific charge transport material, even provide under the low temperature and low humidity environment and also can demonstrate high responsiveness, can take into account electro-photography apparatus miniaturization and image and form the Electrophtography photosensor of high speed of speed and electrophotographic image formation method and the electro-photography apparatus that uses this Electrophtography photosensor.

The present invention relates to Electrophtography photosensor, it is characterized in that, have the electric conductivity support that forms by conductive material and

Be located at the photographic layer on the described electric conductivity support, photographic layer contains titanyl phthalocyanine and the enamine compound shown in following general formula (1), described titanyl phthalocyanine has, in X-ray diffraction spectrum, in 27.2 ° of crystal formations that show diffraction peak of Bragg angle 2 θ (error: 2 θ ± 0.2 °).

(in the formula, Ar ¹And Ar ²Expression can have substituent aryl and maybe can have substituent heterocyclic radical separately.Ar ³Expression can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl, maybe can have substituent alkyl.Ar ⁴And Ar ⁵Represent hydrogen atom separately, can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl and maybe can have substituent alkyl.But, Ar ⁴And Ar ⁵Be not hydrogen atom simultaneously.Ar ⁴And Ar ⁵Also can be by atom or the atomic group formation ring structure that interosculates.A represents to have substituent alkyl, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom, and m represents 1～6 integer.When m was at least 2, a plurality of a can be identical or different, and the formation ring structure also can interosculate.R ¹Expression hydrogen atom, halogen atom maybe can have substituent alkyl.R ², R ³And R ⁴Represent hydrogen atom separately, can have substituent alkyl, can have substituent aryl, can have substituent heterocyclic radical and maybe can have substituent aralkyl.N represents 0～3 integer, when n is 2 or 3, and a plurality of R ²Can be identical or different, a plurality of R ³Can be identical or different, but n is 0 o'clock, Ar ³Expression can have substituent heterocyclic radical.)

According to the present invention, Electrophtography photosensor has electric conductivity support and photographic layer, in photographic layer, contain, have in X-ray diffraction spectrum, the titanyl phthalocyanine of specific crystal formation that shows diffraction peak in 27.2 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) is as the charge generation material, contains as described above the enamine compound shown in the general formula (1) as the charge transport material.Thus, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor of high responsiveness.Infer that Electrophtography photosensor of the present invention shows that under the low temperature and low humidity environment reason of high responsiveness is, as the contained titanyl phthalocyanine of charge generation material and suitable as the combination between the enamine compound shown in the contained general formula as described above (1) of charge transport material with described specific crystal formation.Promptly, because having the titanyl phthalocyanine of described specific crystal formation is the charge generation material with high charge generation ability and high electric charge injection efficiency, therefore when producing a large amount of electric charge by absorbing light, the electric charge that is produced not within it portion gather but be injected into expeditiously in the electron transport material.In addition because the enamine compound shown in the aforementioned formula (1) is the charge transport material with high charge delivery capability, therefore the titanyl phthalocyanine with described specific crystal formation injects the enamine compound shown in the aforementioned formula (1) expeditiously by the electric charge that light absorption produced, and is transported to the photographic layer surface swimmingly.Therefore, as previously mentioned, have the titanyl phthalocyanine and the enamine compound shown in the aforementioned formula (1) of described specific crystal formation and it is included in the photographic layer by combination, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor of high responsiveness.

Thus, even therefore Electrophtography photosensor of the present invention when being used for high-velocity electrons photograph technology after the miniaturization, can provide high quality images owing to also can show high responsiveness under the low temperature and low humidity environment under various environment such as low temperature and low humidity environment.That is, when miniaturization Electrophtography photosensor of the present invention uses, do not need to control the speed of electronic camera technology, can realize that the image of electro-photography apparatus forms the high speed of speed.Thereby, the Electrophtography photosensor of the application of the invention, can take into account the miniaturization of electro-photography apparatus and the high speed that image forms speed, it is fast to realize that miniaturization and image form speed, and the high-reliability electronic photographic means of high quality image can be provided under various environment such as low temperature and low humidity environment.

Feature of the present invention in addition is that also the enamine compound shown in the aforementioned formula (1) is the enamine compound shown in the following general formula (2).

(in the formula, b, c, d represent to have substituent alkyl separately, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom, and i, k and j represent 1～5 integer separately.When i was at least 2, a plurality of b can be identical or different, and the formation ring structure also can interosculate.When k was at least 2, a plurality of c can be identical or different, and the formation ring structure also can interosculate.When j was at least 2, a plurality of d can be identical or different, and the formation ring structure also can interosculate.Ar ⁴, Ar ⁵, a and m definition identical with aforementioned formula (1).)

According to the present invention, owing to contain the enamine compound shown in the aforementioned formula (1) in photographic layer, the enamine compound shown in the particularly described general formula (2) can obtain showing the more Electrophtography photosensor of high responsiveness.By using this Electrophtography photosensor, the image that can further improve Electrophtography photosensor forms speed.In addition, in the enamine compound shown in the aforementioned formula (1), enamine compound shown in the described general formula (2) synthetic than be easier to and yield higher, can make at an easy rate, therefore can show the Electrophtography photosensor described of the present invention of described high responsiveness with lower manufacturing cost manufacturing.

In addition, feature of the present invention also is: described titanyl phthalocyanine has following crystal formation, promptly in X-ray diffraction spectrum, show main diffraction peaks in 7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.9 °, 24.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.2 °, in described diffraction peak, 9.4 ° diffraction peak and the overlapping diffraction peak bundle of 9.6 ° diffraction peak show maximum intensity, and 27.2 ° diffraction peak demonstrates the 2nd high-intensity crystal formation.

According to the present invention, in photographic layer, contain the titanyl phthalocyanine of the specific crystal formation shown in the X-ray diffraction spectrum with Fig. 2 as described later.Titanyl phthalocyanine with described specific crystal formation demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain the optimum wavelength photoreceptor scope of Electrophtography photosensor have to(for) following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.In addition,, be difficult to change into other crystal formation owing to have the stable crystal form of the titanyl phthalocyanine of described specific crystal formation, even thereby can obtain reusing the time reduction of response also less, the Electrophtography photosensor that the stable in properties during repeated use is good.

In addition, feature of the present invention also is: described titanyl phthalocyanine has following crystal formation, promptly in X-ray diffraction spectrum, in 9.5 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 ° of crystal formations that show main diffraction peaks.

According to the present invention, in photographic layer, contain the titanyl phthalocyanine of the specific crystal formation shown in the X-ray diffraction spectrum with Fig. 3 as described later.Titanyl phthalocyanine with described specific crystal formation demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain the optimum wavelength photoreceptor scope of Electrophtography photosensor have to(for) following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.In addition,, be difficult to change into other crystal formation owing to have the stable crystal form of the titanyl phthalocyanine of described specific crystal formation, even thereby can obtain reusing the time reduction of response also less, the Electrophtography photosensor that the stable in properties during repeated use is good.

In addition, feature of the present invention also is: described titanyl phthalocyanine has following crystal formation, promptly in X-ray diffraction spectrum, in 9.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 14.2 °, 23.9 ° and 27.1 ° of crystal formations that show main diffraction peaks.

According to the present invention, in photographic layer, contain the titanyl phthalocyanine of the specific crystal formation shown in the X-ray diffraction spectrum with Fig. 4 as described later.Titanyl phthalocyanine with described specific crystal formation demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain the optimum wavelength photoreceptor scope of Electrophtography photosensor have to(for) following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.In addition,, be difficult to change into other crystal formation owing to have the stable crystal form of the titanyl phthalocyanine of described specific crystal formation, even thereby can obtain reusing the time reduction of response also less, the Electrophtography photosensor that the stable in properties during repeated use is good.

In addition, the invention still further relates to Electrophtography photosensor, it is characterized in that, have the electric conductivity support that formed by conductive material and be arranged on photographic layer on the electric conductivity support, described photographic layer contains the two or more metal phthalocyanines that comprise titanyl phthalocyanine and the enamine compound shown in the aforementioned formula (1).

According to the present invention, Electrophtography photosensor has electric conductivity support and photographic layer, in photographic layer, contain the two or more metal phthalocyanines that comprise titanyl phthalocyanine, promptly comprise metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine, also contain as described above the enamine compound shown in the general formula (1) as the charge transport material as the charge generation material.Thus, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor of high responsiveness.

Can show also that under the low temperature and low humidity environment reason of high responsiveness is even infer Electrophtography photosensor of the present invention, as the contained two or more metal phthalocyanines that comprise titanyl phthalocyanine of charge generation material and suitable as the combination between the enamine compound shown in the contained general formula as described above (1) of charge transport material.Promptly, because comprising the metal phthalocyanine of titanyl phthalocyanine is the charge generation material with high charge generation ability and high electric charge injection efficiency, therefore when producing a large amount of electric charge by absorbing light, the electric charge that is produced not within it portion gather but be injected into expeditiously in the electron transport material.In addition because the enamine compound shown in the aforementioned formula (1) is the charge transport material with high charge delivery capability, therefore the two or more metal phthalocyanines that comprise titanyl phthalocyanine inject the enamine compound shown in the aforementioned formula (1) expeditiously by the electric charge that light absorption produced, and are transported to the photographic layer surface swimmingly.Therefore, as previously mentioned, comprise the two or more metal phthalocyanines and the enamine compound shown in the aforementioned formula (1) of titanyl phthalocyanine and it is included in the photographic layer by combination, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor of high responsiveness.

In addition, as previously mentioned, in the photographic layer in the Electrophtography photosensor of the present invention, contain titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition as the charge generation material.Therefore, by changing the ratio of titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition, can easily change the wavelength photoreceptor scope of Electrophtography photosensor, therefore the Electrophtography photosensor that can easily obtain having desirable wavelength photoreceptor scope.

In addition, feature of the present invention also is: described metal phthalocyanine is the mixed crystal of the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine.

According to the present invention, in photographic layer, the mixed crystal that contains titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition is as the charge generation material.By making the form of the two or more metal phthalocyanines formation mixed crystal that comprise titanyl phthalocyanine, can improve the stability of crystal formation, the reduction of response in the time of therefore can suppressing to reuse obtains the good Electrophtography photosensor of stable in properties when reusing.In addition, by making the two or more metal phthalocyanines that comprise titanyl phthalocyanine form the form of mixed crystal, can also improve dispersiveness, when forming photographic layer by coating, can improve the aging stability of coating liquid, improve the quality stability and the throughput rate of Electrophtography photosensor.

In addition, feature of the present invention also is: described mixed crystal is the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine.

According to the present invention, the mixed crystal that contains titanyl phthalocyanine and gallium chloride phthalocyanine in photographic layer is as the charge generation material.Because the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

In addition, feature of the present invention also is: described mixed crystal is the mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine.

According to the present invention, the mixed crystal that contains titanyl phthalocyanine and inidum chloride phthalocyanine in photographic layer is as the charge generation material.Because the mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

In addition, the invention still further relates to Electrophtography photosensor, it is characterized in that having electric conductivity support that is formed by conductive material and the photographic layer that is arranged on the electric conductivity support, described photographic layer contains the enamine compound shown in nonmetal phthalocyanine and the aforementioned formula (1).

According to the present invention, Electrophtography photosensor has electric conductivity support and photographic layer, contains nonmetal phthalocyanine as the charge generation material in photographic layer, contains as described above the enamine compound shown in the general formula (1) as the charge transport material.Thus, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor of high responsiveness.

Infer that Electrophtography photosensor of the present invention shows that under the low temperature and low humidity environment reason of high responsiveness is, as the contained nonmetal phthalocyanine of charge generation material and suitable as the combination between the enamine compound shown in the contained general formula as described above (1) of charge transport material.Promptly, because nonmetal phthalocyanine is the charge generation material with high charge generation ability and high electric charge injection efficiency, therefore when producing a large amount of electric charge by absorbing light, the electric charge that is produced not within it portion gather but be injected into expeditiously in the electron transport material.In addition because the enamine compound shown in the aforementioned formula (1) is the charge transport material with high charge delivery capability, therefore nonmetal phthalocyanine injects the enamine compound shown in the aforementioned formula (1) expeditiously by the electric charge that light absorption produced, and is transported to the photographic layer surface swimmingly.Therefore, as previously mentioned, by the enamine compound shown in combination non metal phthalocyanine and the aforementioned formula (1) and it is included in the photographic layer, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor of high responsiveness.

Thus, even therefore Electrophtography photosensor of the present invention when being used for high-velocity electrons photograph technology after the miniaturization, can provide high quality images owing to also can show high responsiveness under the low temperature and low humidity environment under various environment such as low temperature and low humidity environment.That is, when using, do not need to control the speed of electronic camera technology, can realize that the image of electro-photography apparatus forms the high speed of speed at miniaturization Electrophtography photosensor of the present invention.Thereby, the Electrophtography photosensor of the application of the invention, can take into account the miniaturization of electro-photography apparatus and the high speed that image forms speed, it is fast to realize that miniaturization and image form speed, and the high-reliability electronic photographic means of high quality image can be provided under various environment such as low temperature and low humidity environment.

Feature of the present invention in addition also is: described nonmetal phthalocyanine is an X type nonmetal phthalocyanine.

According to the present invention, in photographic layer, contain X type nonmetal phthalocyanine as the charge generation material.Because X type nonmetal phthalocyanine demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

Feature of the present invention in addition also is: also contain metal phthalocyanine in the described photographic layer.

According to the present invention, contain nonmetal phthalocyanine and metal phthalocyanine as the charge generation material at photographic layer.Therefore, by changing the ratio of nonmetal phthalocyanine and metal phthalocyanine, can easily change the wavelength photoreceptor scope of Electrophtography photosensor, therefore the Electrophtography photosensor that can easily obtain having desirable wavelength photoreceptor scope.

Feature of the present invention in addition also is: described nonmetal phthalocyanine and described metal phthalocyanine are the mixed crystal of nonmetal phthalocyanine and metal phthalocyanine.

According to the present invention, in photographic layer, the mixed crystal that contains nonmetal phthalocyanine and metal phthalocyanine is as the charge generation material.By making the form of nonmetal phthalocyanine and metal phthalocyanine formation mixed crystal, can improve the stability of crystal formation, the reduction of response in the time of therefore can suppressing to reuse obtains the good Electrophtography photosensor of stable in properties when reusing.In addition, form the form of mixed crystal, can also improve dispersiveness, when forming photographic layer, can improve the aging stability of coating liquid, improve the quality stability and the throughput rate of Electrophtography photosensor by coating by making nonmetal phthalocyanine and metal phthalocyanine.

Feature of the present invention in addition also is: described metal phthalocyanine is a titanyl phthalocyanine.

According to the present invention, in photographic layer, contain nonmetal phthalocyanine and titanyl phthalocyanine as the charge generation material.Because titanyl phthalocyanine demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

In addition, the invention still further relates to electrophotographic image formation method, comprise: make the operation of the surface charging of Electrophtography photosensor, to the expose operation that forms electrostatic latent image and of charged described surface with the operation of described latent electrostatic image developing,

It is characterized in that: use described Electrophtography photosensor of the present invention in the described Electrophtography photosensor.

According to the present invention, electrophotographic image passes through, and makes the surface charging of described Electrophtography photosensor of the present invention, to the surface of the charged Electrophtography photosensor formation electrostatic latent image that exposes, the electrostatic latent image that forms is developed and forms.Because described Electrophtography photosensor of the present invention also can show high responsiveness under described low temperature and low humidity environment, therefore even when beginning from being exposed in the Electrophtography photosensor surface to the development of electrostatic latent image finishes time shortening, by electrophotographic image formation method of the present invention, also can under various environment such as low temperature and low humidity environment, provide high quality images.

In addition, feature of the present invention also is: described begin from being exposed in the Electrophtography photosensor surface to time that the development of described electrostatic latent image finishes for being no more than 90 milliseconds (90msec).

According to the present invention, be no more than 90 milliseconds (90msec) owing to begin from being exposed in the Electrophtography photosensor surface to foreshorten to the time that the development of electrostatic latent image finishes, therefore can form image at a high speed.Begin from being exposed in the Electrophtography photosensor surface to time that the development of electrostatic latent image finishes more in short-term, under the low temperature and low humidity environment, though the response of Electrophtography photosensor reduces, image quality reduces, even but electrophotographic image formation method of the present invention is owing to used the Electrophtography photosensor of the present invention that also can show high responsiveness under described low temperature and low humidity environment, even therefore begin from being exposed in the Electrophtography photosensor surface to time that the development of electrostatic latent image finishes more in short-term, also can under various environment such as low temperature and low humidity environment, provide high quality images.

The invention still further relates to electro-photography apparatus in addition, it is characterized in that comprising:

Described Electrophtography photosensor of the present invention,

Make the surface charging of described Electrophtography photosensor Charging system,

The exposure device that is exposed in charged described surface and

The developing apparatus that the electrostatic latent image that forms by exposure is developed.

According to the present invention, electro-photography apparatus has described electro-photography apparatus of the present invention, Charging system, exposure device and developing apparatus.Even because described Electrophtography photosensor of the present invention also can show high responsiveness under described low temperature and low humidity environment, therefore, even when beginning from being exposed in the Electrophtography photosensor surface to shorten to the time that the development of electrostatic latent image finishes, for example with the electro-photography apparatus miniaturization, when under high speed, carrying out electronic camera technology, also can under various environment such as low temperature and low humidity environment, provide high quality images.Therefore, it is fast to realize that miniaturization and image form speed, and the high-reliability electronic photographic means of high quality image can be provided under various environment such as low temperature and low humidity environment.

The invention still further relates to electro-photography apparatus in addition, it is characterized in that comprising: the Electrophtography photosensor described of the present invention that supports and can rotate freely by apparatus main body,

With rotation round velocities Vp rotation drive described Electrophtography photosensor the photoreceptor drive unit,

Make the charged Charging system of the outer peripheral face of described Electrophtography photosensor,

The exposure device that is exposed in charged described surface,

The developing apparatus that the electrostatic latent image that forms by exposure is developed and

Control the running of described photoreceptor drive unit so that the exposure position along described Electrophtography photosensor outer peripheral face from described exposure device to the distance L of the developing location of described developing apparatus divided by the value d of described rotation round velocities Vp (=L/Vp) be no more than the control device of 90 milliseconds (90msec).

According to the present invention, electro-photography apparatus has described Electrophtography photosensor of the present invention, photoreceptor drive unit, Charging system, exposure device, developing apparatus and control device.The photoreceptor drive unit drives Electrophtography photosensor with the rotation of rotation round velocities Vp.Control the running of this photoreceptor drive unit by control device so that the exposure position along the Electrophtography photosensor outer peripheral face from described exposure device to the distance L of the developing location of described developing apparatus divided by the value d of rotation round velocities Vp (=L/Vp) be no more than 90 milliseconds (90msec).Described d value with begin to electrostatic latent image being developed time of finishing about equally from the Electrophtography photosensor outside surface being exposed by developing apparatus by exposure device.Therefore, begin to short to develop time of finishing of electrostatic latent image from the Electrophtography photosensor outside surface being exposed by developing apparatus by exposure device.Be that electro-photography apparatus of the present invention can carry out electronic camera technology at a high speed, can realize that image forms fireballing electro-photography apparatus.

When beginning to electrostatic latent image being developed time of finishing in short-term by developing apparatus from the Electrophtography photosensor outside surface being exposed by exposure device, for example use the short miniature electric photosensitive body of described distance L, increase described rotation round velocities Vp, carry out under the situation of electronic camera technology at a high speed, sometimes the response of Electrophtography photosensor reduces under the low temperature and low humidity environment, and image quality reduces.

Yet, even because electro-photography apparatus of the present invention has the Electrophtography photosensor described of the present invention that also can show high responsiveness under described low temperature and low humidity environment, even therefore under the situation of the time weak point that begins from the Electrophtography photosensor outside surface being exposed to finish, also can under various environment such as low temperature and low humidity environment, provide high quality images to electrostatic latent image being developed by developing apparatus by exposure device.Thereby, as previously mentioned, running by described Electrophtography photosensor of the present invention, control sensitization body drive are set is so that described d value is no more than 90msec, and it is fast and the high-reliability electronic photographic means of high quality image can be provided under various environment such as low temperature and low humidity environment to realize that image forms speed.

In addition, the invention is characterized in: described Electrophtography photosensor has cylindric or columned shape, and the diameter of described Electrophtography photosensor is 24mm～40mm.

According to the present invention, the miniature electric photosensitive body that have cylindric or columned shape owing in electro-photography apparatus, being provided with, diameter is 24mm～40mm, thereby can miniaturization electronics photographic means.Thereby, can realize small-sized and image to form speed fast, and can under various environment such as low temperature and low humidity environment, provide the high-reliability electronic photographic means of high quality image.

The accompanying drawing summary

By following detailed description and accompanying drawing, can further to define purpose of the present invention, characteristics and advantage.

Figure 1A is the skeleton view of formation of the Electrophtography photosensor 1 of reduced representation the 1st embodiment of the present invention.Figure 1B is the fragmentary cross-sectional view of the formation of reduced representation Electrophtography photosensor 1.

Fig. 2 is the figure that shows the X-ray diffraction spectrum of titanyl phthalocyanine of the present invention.

Fig. 3 is the figure that shows the X-ray diffraction spectrum of titanyl phthalocyanine of the present invention.

Fig. 4 is the figure that shows the X-ray diffraction spectrum of titanyl phthalocyanine of the present invention.

Fig. 5 is the constructed profile of formation of the Electrophtography photosensor 2 of reduced representation the 2nd embodiment of the present invention.

Fig. 6 is the fragmentary cross-sectional view of formation of the Electrophtography photosensor 3 of reduced representation the 3rd embodiment of the present invention.

Fig. 7 is the side arrangement plan of formation of the electro-photography apparatus 100 of reduced representation the 4th embodiment of the present invention.

Fig. 8 is the product that shows Production Example 1-3 ¹The figure of H-NMR spectrum.

Fig. 9 is the figure that enlarges the 6ppm～9ppm that shows spectrum shown in Figure 8.

Figure 10 shows product by conventional determining Production Example 1-3 ¹³The figure of C-NMR spectrum.

Figure 11 is the figure that enlarges the 110ppm～160ppm that shows spectrum shown in Figure 10.

Figure 12 shows the product of measuring Production Example 1-3 by DEPT135 ¹³The figure of C-NMR spectrum.

Figure 13 is the figure that enlarges the 110ppm～160ppm that shows spectrum shown in Figure 12.

Figure 14 is the product that shows Production Example 2 ¹The figure of H-NMR spectrum.

Figure 15 is the figure that enlarges the 6ppm～9ppm that shows spectrum shown in Figure 14.

Figure 16 shows product by conventional determining Production Example 2 ¹³The figure of C-NMR spectrum.

Figure 17 is the figure that enlarges the 110ppm～160ppm that shows spectrum shown in Figure 16.

Figure 18 shows the product of measuring Production Example 2 by DEPT135 ¹³The figure of C-NMR spectrum.

Figure 19 is the figure that enlarges the 110ppm～160ppm that shows spectrum shown in Figure 180.

Preferred forms of the present invention

Below with reference to accompanying drawing, describe preferred implementation of the present invention in detail.

Figure 1A is the skeleton view of formation of the Electrophtography photosensor 1 of reduced representation the 1st embodiment of the present invention.Figure 1B is the fragmentary cross-sectional view of the formation of reduced representation Electrophtography photosensor 1.Electrophtography photosensor 1 (following be called for short sometimes " photoreceptor ") comprises cylindric electric conductivity support 11 that is formed by conductive material and the photographic layer 14 that is located on electric conductivity support 11 outer peripheral faces.Photographic layer 14 be by on the outer peripheral face of electric conductivity support 11 in turn lamination contain by absorbing light produce the charge generation material 12 of electric charge charge generation layer 15, contain the laminated-type photographic layer that the charge transport layer 16 of the resin of binding property 17 of the charge transport material 13 that can accept and carry the electric charge that is produced by charge generation material 12 and bonding charge transport material 13 forms.Be that photoreceptor 1 is the laminated-type photoreceptor.

Photoreceptor 14 contains: have in X-ray diffraction spectrum, show the titanyl phthalocyanine of the crystal formation of diffraction peak, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine as charge generation material 12 in 27.2 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), also contain enamine compound shown in following general formula (1) as charge transport material 13.

In aforementioned formula (1), Ar ¹And Ar ²Expression can have substituent aryl and maybe can have substituent heterocyclic radical separately.Ar ³Expression can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl, maybe can have substituent alkyl.Ar ⁴And Ar ⁵Represent hydrogen atom separately, can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl and maybe can have substituent alkyl.But Ar ⁴And Ar ⁵Be not hydrogen atom simultaneously.Ar ⁴And Ar ⁵Also can be by atom or the atomic group formation ring structure that interosculates.

In this external aforementioned formula (1), a represents to have substituent alkyl, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom, and m represents 1～6 integer.When m was at least 2, a plurality of a can be identical or different, and the formation ring structure also can interosculate.

In this external aforementioned formula (1), R ¹Expression hydrogen atom, halogen atom maybe can have substituent alkyl.R ², R ³And R ⁴Represent hydrogen atom separately, can have substituent alkyl, can have substituent aryl, can have substituent heterocyclic radical and maybe can have substituent aralkyl.N represents 0～3 integer, when n is 2 or 3, and a plurality of R ²Can be identical or different, a plurality of R ³Can be identical or different.

Wherein, in aforementioned formula (1), when n is 0, Ar ³Expression can have substituent heterocyclic radical.

Thus, owing to contain in the photoreceptor 14: have in X-ray diffraction spectrum, show that in 27.2 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) titanyl phthalocyanine of the crystal formation of diffraction peak, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine are as charge generation material 12, also contain the enamine compound shown in the aforementioned formula (1) as charge transport material 13, even therefore can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor 1 of high responsiveness.

The Electrophtography photosensor 1 of inferring present embodiment shows that under the low temperature and low humidity environment reason of high responsiveness is, as the contained titanyl phthalocyanine with described specific crystal formation of charge generation material 12, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine and suitable as the combination between the enamine compound shown in the contained general formula as described above (1) of charge transport material 13.Promptly, because having the titanyl phthalocyanine of described specific crystal formation, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine is the charge generation material with high charge generation ability and high electric charge injection efficiency, therefore when producing a large amount of electric charge by absorbing light, the electric charge that is produced not within it portion gather but be injected into expeditiously in the electron transport material 13.In addition because the enamine compound shown in the aforementioned formula (1) is the charge transport material with high charge delivery capability, therefore have the titanyl phthalocyanine of described specific crystal formation, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine and inject the enamine compound shown in the aforementioned formula (1) expeditiously, be transported to photographic layer surface 14 swimmingly by the electric charge that light absorption produced.Therefore, as previously mentioned, have the titanyl phthalocyanine of described specific crystal formation, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or the enamine compound shown in nonmetal phthalocyanine and the aforementioned formula (1) and it is included in the photographic layer 14 by combination, even can obtain under the low temperature and low humidity environment, also showing the Electrophtography photosensor 1 of high responsiveness.

Thus, even therefore the Electrophtography photosensor of present embodiment 1 when being used for high-velocity electrons photograph technology after the miniaturization, can provide high quality images owing to also can show high responsiveness under the low temperature and low humidity environment under various environment such as low temperature and low humidity environment.That is, when miniaturization photoreceptor 1 uses, do not need to suppress the speed of electronic camera technology, can realize that therefore the image of electro-photography apparatus forms the high speed of speed.Thereby, by using photoreceptor 1, can take into account the miniaturization of electro-photography apparatus and the high speed that image forms speed, it is fast to realize that miniaturization and image form speed, and the high-reliability electronic photographic means of high quality image can be provided under various environment such as low temperature and low humidity environment.

In addition, in metal phthalocyanine such as titanyl phthalocyanine that uses in the present embodiment and the nonmetal phthalocyanine, the hydrogen atom of the phenyl ring that the phthalocyanine base is contained can be replaced by substituting groups such as halogen radicals such as chlorine or fluorine, nitro, cyano group or sulfonic groups.Perhaps the central metal of metal phthalocyanine also can have part.

In the charge generation layer 15 there be the object lesson of the contained titanyl phthalocyanine with described specific crystal formation as charge generation material 12: for example can enumerate, and in X-ray diffraction spectrum,

(A-1) have as shown in Figure 2, show main diffraction peaks in 7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.9 °, 24.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.2 °, in described diffraction peak, 9.4 ° diffraction peak and the overlapping diffraction peak bundle of 9.6 ° diffraction peak show maximum intensity, and 27.2 ° diffraction peak demonstrates the titanyl phthalocyanine of the 2nd high-intensity crystal formation

(A-2) have as shown in Figure 3, in 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.3 ° of titanyl phthalocyanines that show the crystal formation of main diffraction peaks,

(A-3) have as shown in Figure 4, show in 9.0 °, 14.2 °, 23.9 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.1 ° main diffraction peaks crystal formation titanyl phthalocyanine and

(A-4) have in Bragg angle 2 θ (error: 2 θ ± 0.2 °) and show the maximum diffraction peak for 27.3 °, in 7.4 °, 9.7 ° and 24.2 ° of titanyl phthalocyanines that show the crystal formation of diffraction peaks,

Deng.In addition, in this manual, Bragg angle 2 θ are meant incident X-rays and diffraction X ray angulation, promptly so-called angle of diffraction.These titanyl phthalocyanines can use a kind separately, also can mix at least 2 kinds of uses.

Titanyl phthalocyanine with described specific crystal formation not only has described high charge generation ability and high electric charge injection efficiency, and the light of near infrared light and the isometric wavelength coverage of ruddiness is demonstrated higher susceptibility.In having the titanyl phthalocyanine of described specific crystal formation, titanyl phthalocyanine with crystal formation of Fig. 2, Fig. 3 or X-ray diffraction spectrum shown in Figure 4 demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore by these titanyl phthalocyanines are used as charge generation material 12, can obtain having for following digital and electronic photographic means the Electrophtography photosensor 1 of optimum wavelength photoreceptor scope, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.In addition, because the stable crystal form of these titanyl phthalocyanines, be difficult to change into other crystal formation, even thereby can obtain reusing the time reduction of response also less, the Electrophtography photosensor that the stable in properties during repeated use is good.

Titanyl phthalocyanine with described specific crystal formation also can mix use with other charge generation material.As mixing other charge generation material that uses, can enumerate titanyl phthalocyanine, other phthalocyanine compound and Network ロ ロ ダ イ ア Application Block Le one bisdiazo compounds such as (Chloro Diane Blue), ジ Block ロ モ ア Application サ Application ス ロ Application polycyclic quinones such as (dibromoanthanthron) compound, perylene compounds, quinoline a word used for translation ketone based compound and the Azulene salt compounds etc. that have with described specific crystal formation different crystal forms with titanyl phthalocyanine with described specific crystal formation.

At least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine when use are during as charge generation material 12, preferred crystalline titanyl phthalocyanine.As crystalline titanyl phthalocyanine, especially preferably have those of specific crystal formation, specifically can enumerate, for example Y type titanyl phthalocyanine and I type titanyl phthalocyanine.In having the titanyl phthalocyanine of specific crystal formation,, can enumerate the titanyl phthalocyanine of above-mentioned (A-1)～(A-4) as particularly preferred.

As with the object lesson of titanyl phthalocyanine, can enumerate for example indium phthalocyanines as the metal phthalocyanine of charge generation material 12, the gallium phthalocyanines, the vanadyl phthalocyanines, the copper phthalocyanine class, the aluminium phthalocyanines, the germanium phthalocyanines, the lithium phthalocyanines, the sodium phthalocyanines, the potassium phthalocyanines, the zirconium phthalocyanines, the hafnium phthalocyanines, the magnesium phthalocyanines, the tin phthalocyanines, the zinc phthalocyanines, the cobalt phthalocyanines, the nickel phthalocyanine class, the barium phthalocyanines, the beryllium phthalocyanines, the cadmium phthalocyanines, the cobalt phthalocyanines, the iron-phthalocyanine class, the silicon phthalocyanine class, plumbous phthalocyanines, the silver phthalocyanines, the gold phthalocyanines, the platinum phthalocyanines, ruthenium phthalocyanines and palladium phthalocyanines etc.

Be selected from a kind or at least 2 kinds metal phthalocyanine and titanyl phthalocyanine and usefulness in these metal phthalocyanines.In described metal phthalocyanine, preferably use vanadyl phthalocyanine, aluminum chloride phthalocyanine, gallium chloride phthalocyanine, inidum chloride phthalocyanine, anium dichloride phthalocyanine, hydroxy Al phthalocyanine, hydroxy gallium phthalocyanine, hydroxyl indium phthalocyanine and dihydroxy germanium phthalocyanine etc.

Thus, when charge generation material 12 use at least two kinds of metal phthalocyanines comprising titanyl phthalocyanine, when being the metal phthalocyanine beyond titanyl phthalocyanine and the described titanyl phthalocyanine, by changing the ratio of titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition, can easily change the wavelength photoreceptor scope of photoreceptor 1, therefore the photoreceptor 1 that can easily obtain having desirable wavelength photoreceptor scope.

Metal phthalocyanine beyond titanyl phthalocyanine and the described titanyl phthalocyanine can use with various forms, for example, can use

(I) it is same to open in the flat 9-73182 communique potpourri of disclosed nonmetal phthalocyanine and titanyl phthalocyanine as the spy, with the potpourri that obtains of physical mixed simply of the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine,

(II) open the mixed crystal of the flat 2-84661 communique phthalocyanine compound different as the spy with disclosed center material in the flat 2-170166 communique of Te Kai, i.e. the mixed crystal of the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine, or

(III) it is same to open in the flat 10-90926 communique mixed aggregate of disclosed X type nonmetal phthalocyanine and titanyl phthalocyanine as the spy, the mixed aggregate of the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine etc.

In addition, in this manual, mixed crystal is meant the material that at least two kinds of compounds mix with molecular level, and the mixed crystal of the metal phthalocyanine beyond described titanyl phthalocyanine and the titanyl phthalocyanine comprises following any:

(II-a) spy opens that disclosed phthalocyanine mixed crystal, the spy who is formed by titanyl phthalocyanine and gallium halide phthalocyanine or indium halide phthalocyanine opens the disclosed mixed crystal such as phthalocyanine mixed crystal that formed by titanyl phthalocyanine and hydroxy metal phthalocyanine in the flat 4-351673 communique in the flat 4-372663 communique,

(II-b) open 2002-244321 communique, spy and open 2003-107763 communique, spy and open 2000-313819 communique, spy and open flat 2-272067 communique, spy and open the composition that flat 1-142658 communique and the disclosed phthalocyanine composition of the flat 1-142659 communique of Te Kai similarly contain the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine with the special 2002-23396 communique, spy opened.

As previously mentioned, the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine can use with various forms, but preferably uses with the form of mixed crystal.By use titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition with the form of mixed crystal, can improve the stability of crystal formation, the reduction of response in the time of therefore can suppressing to reuse can access the good photoreceptor 1 of stable in properties when reusing.In addition, can also improve dispersiveness, therefore when coating forms photographic layer 14, can improve the aging stability of coating liquid, improve the quality stability and the throughput rate of photoreceptor 1.

As the object lesson of the mixed crystal of the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine, can enumerate for example titanyl phthalocyanine and the mixed crystal of gallium halide phthalocyanine and the mixed crystal of titanyl phthalocyanine and indium halide phthalocyanine etc.

Among the mixed crystal of titanyl phthalocyanine and gallium halide phthalocyanine, can enumerate as preferred mixed crystal, in X-ray diffraction spectrum,

(B-1) in 27.2 ° of demonstrations of Bragg angle 2 θ (error: 2 θ ± 0.2 °) the strongest diffraction peak mixed crystal,

(B-2) in 8.9 °, 27.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) show strong diffraction peaks mixed crystal,

(B-3) in 9.3 °, 10.6 °, 13.3 °, 15.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 26.3 ° show strong diffraction peaks mixed crystal,

(B-4) in 7.4 °, 11.1 °, 17.9 °, 20.1 °, 26.6 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 29.2 ° show strong diffraction peaks mixed crystal,

(B-5) in 7.5 °, 16.7 °, 22.1 °, 24.7 °, 25.6 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.6 ° show strong diffraction peaks mixed crystal,

(B-5) in 7.6 °, 16.7 °, 22.5 °, 24.2 °, 25.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.6 ° of mixed crystal that show strong diffraction peaks.

Among the mixed crystal of titanyl phthalocyanine and indium halide phthalocyanine, can enumerate as preferred mixed crystal, in X-ray diffraction spectrum,

(C-1) in 7.6 °, 16.4 °, 22.4 °, 25.5 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.6 ° show strong diffraction peaks mixed crystal,

(C-2) in 7.6 °, 10.6 °, 15.2 °, 26.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.7 ° show strong diffraction peaks mixed crystal,

(C-3) in 7.5 °, 11.1 °, 18.1 °, 20.3 °, 26.7 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 29.2 ° show strong diffraction peaks mixed crystal,

(C-4) in 9.4 °, 15.2 °, 26.4 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.4 ° show strong diffraction peaks mixed crystal,

(C-5) in 7.4 °, 16.6 °, 25.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.2 ° show strong diffraction peaks mixed crystal,

(C-6) in 7.3 °, 16.7 °, 25.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.8 ° of mixed crystal that show strong diffraction peaks etc.

In these mixed crystal, preferably use the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine or the mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine.Because the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine and the mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine demonstrate extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore by using these mixed crystal as charge generation material 12, can obtain having the photoreceptor 1 of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

When using nonmetal phthalocyanine as charge generation material 12, preferred crystalline nonmetal phthalocyanine.As crystalline nonmetal phthalocyanine, preferably have the nonmetal phthalocyanine of specific crystal formation, as object lesson, can enumerate for example nonmetal phthalocyanine of X type, α type, β type, γ type, τ type, π type, τ ' type, η type or η ' type.These nonmetal phthalocyanines can use a kind separately, also can mix at least 2 kinds of uses.

Among the described nonmetal phthalocyanine, preferred X type nonmetal phthalocyanine.Because X type nonmetal phthalocyanine demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore by using X type nonmetal phthalocyanine as charge generation material 12, can obtain having the photoreceptor 1 of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

In X type nonmetal phthalocyanine, preferred X type nonmetal phthalocyanine can be enumerated, in X-ray diffraction spectrum, in 7.4 °, 9.0 °, 16.5 °, 17.2 °, 22.1 °, 23.8 °, 27.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.4 ° of X type nonmetal phthalocyanines that show main diffraction peaks.

Nonmetal phthalocyanine preferably is used as charge generation material 12 together with metal phthalocyanine.Thus, when charge generation material 12 uses nonmetal phthalocyanine and metal phthalocyanine,, can easily change the wavelength photoreceptor scope of photoreceptor 1 by changing the ratio of nonmetal phthalocyanine and metal phthalocyanine.So photoreceptor 1 that can easily obtain having desirable wavelength photoreceptor scope.

As the metal phthalocyanine that uses with nonmetal phthalocyanine, can enumerate titanyl phthalocyanine and described titanyl phthalocyanine metal phthalocyanine in addition etc.Wherein preferably use titanyl phthalocyanine.Because titanyl phthalocyanine demonstrates extra high susceptibility to the light of near infrared light and the isometric wavelength coverage of ruddiness, therefore by in charge generation material 12, using nonmetal phthalocyanine and titanyl phthalocyanine, can obtain having the photoreceptor 1 of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

When using nonmetal phthalocyanine and metal phthalocyanine simultaneously, nonmetal phthalocyanine and metal phthalocyanine can with aforesaid at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine similarly, can with nonmetal phthalocyanine and metal phthalocyanine simply various forms such as the mixed crystal of the potpourri, nonmetal phthalocyanine and the metal phthalocyanine that obtain of physical mixed or the mixed aggregate of nonmetal phthalocyanine and metal phthalocyanine use.

In addition, the mixed crystal of described nonmetal phthalocyanine and metal phthalocyanine also comprises: the spy opens 2002-244321 communique and the disclosed crystallinity phthalocyanine composition that contains nonmetal phthalocyanine and titanyl phthalocyanine of Te Kai 2003-107763 communique, the spy opens 2002-23396 communique and the disclosed phthalocyanine composition that contains nonmetal phthalocyanine and titanyl phthalocyanine of Te Kai 2000-313819 communique, the disclosed X type phthalocyanine composition that contains X type nonmetal phthalocyanine and titanyl phthalocyanine of Te Kaiping 2-272067 communique, and special flat 1-142658 communique and the disclosed α type titanyl phthalocyanine composition that contains nonmetal phthalocyanine and α type titanyl phthalocyanine of the flat 1-142659 communique of Te Kai opened.

As previously mentioned, nonmetal and metal phthalocyanine can use with various forms, but preferably uses with the form of mixed crystal.Use nonmetal and metal phthalocyanine by form with mixed crystal, when using metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine with described form with mixed crystal similarly, the reduction of response in the time of can suppressing to reuse can access the good photoreceptor 1 of stable in properties when reusing.In addition, when coating forms photographic layer 14, can improve the aging stability of coating liquid, improve the quality stability and the throughput rate of photoreceptor 1.

Among the mixed crystal of nonmetal and metal phthalocyanine, preferably use the mixed crystal of nonmetal phthalocyanine and titanyl phthalocyanine.Among the mixed crystal of nonmetal phthalocyanine and titanyl phthalocyanine,, can enumerate as the mixed crystal of preferred nonmetal phthalocyanine and titanyl phthalocyanine:

(D-1) mixed crystal of nonmetal phthalocyanine and titanyl phthalocyanine, in X-ray diffraction spectrum, in 7.0 °, 9.0 °, 14.1 °, 18.0 °, 23.7 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.3 ° of mixed crystal that show diffraction peaks,

(D-2) mixed crystal of X type nonmetal phthalocyanine and titanyl phthalocyanine is in X-ray diffraction spectrum, in 7.5 °, 9.1 °, 16.7 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 17.3 ° of mixed crystal that show strong diffraction peaks etc.

Described metal phthalocyanine and nonmetal phthalocyanine can pass through present known preparation method's preparations such as method of Mo Saier (Moser) and Thomas's (Thmoas) record in " phthalocyanine compound (Phthalocyanine.Compounds) ".For example, titanyl phthalocyanine can dissolve phthalonitrile and titanium tetrachloride by heating, perhaps makes it add thermal response in appropriate solvent, and synthetic titanium chloride phthalocyanine is hydrolyzed then and makes.Perhaps prepare by making isoindoline and four alkoxytitaniums in appropriate solvent, add thermal response.

Metal phthalocyanine and nonmetal phthalocyanine with specific crystal formation can stir in appropriate solvent by the metal phthalocyanine or the nonmetal phthalocyanine that will as above make, and perhaps prepare by grinding to handle.

Titanyl phthalocyanine with crystal formation of X-ray diffraction spectrum shown in Figure 2 can be opened the disclosed preparation method's preparation of 2000-129155 communique by for example spy.The titanyl phthalocyanine that has the crystal formation of X-ray diffraction spectrum shown in Figure 3 in addition can be by for example speciallyying permit No. 2700859 disclosed preparation method's preparation of communique.Titanyl phthalocyanine with crystal formation of X-ray diffraction spectrum shown in Figure 4 can be opened the disclosed preparation method's preparation of flat 3-128973 communique by for example spy.Aforesaid in addition have in X-ray diffraction spectrum, in 27.3 ° of the strongest diffraction peaks of demonstration of Bragg angle 2 θ (error: 2 θ ± 0.2 °), can be at 7.4 °, 9.7 ° and the 24.2 ° titanyl phthalocyanines that show the crystal formation of diffraction peaks by preparation method's preparation of for example special fair 7-91486 communique record.In nonmetal phthalocyanine, aforesaid have in X-ray diffraction spectrum, the X type nonmetal phthalocyanines that show main diffraction peaks in 7.4 °, 9.0 °, 16.5 °, 17.2 °, 22.1 °, 23.8 °, 27.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.4 ° can be by for example, and the spy opens the disclosed preparation method's preparation of flat 2-233769 communique.

The mixed crystal of the metal phthalocyanine beyond described titanyl phthalocyanine and the titanyl phthalocyanine can for example pass through, mix titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition in the proper ratio and make its amorphization, perhaps respectively with the metal phthalocyanine amorphization beyond titanyl phthalocyanine and the titanyl phthalocyanine, after mixing in the proper ratio, by in appropriate solvent, stirring, perhaps prepare by grinding (milling) processing.As the method for amorphization, can adopt mechanical crushing method or sour gelatinization (acid pasting) method etc.Mechanical crushing method is to adopt bowl mill, automatic mortar or paint regulator etc., is crushed to the method that can not demonstrate clear and definite X-ray diffraction peak.Acid gelatinization method is that it is dissolved in the strong acid such as sulfuric acid, the solution that obtains is injected the method that lean solvent such as water makes its particlized.For example, the mixed crystal of titanyl phthalocyanine and gallium halide phthalocyanine or indium halide phthalocyanine can be opened preparation method shown in the flat 4-372663 communique etc. by the spy and is prepared.

The mixed crystal of described nonmetal phthalocyanine and metal phthalocyanine can by with titanyl phthalocyanine and titanyl phthalocyanine beyond the same method of the mixed crystal of metal phthalocyanine be prepared.For example, in the mixed crystal of described titanyl phthalocyanine and nonmetal phthalocyanine, (D-1) mixed crystal can be opened disclosed preparation method of 2000-313819 communique etc. by the spy and be prepared, and mixed crystal (D-2) can be opened disclosed preparation method of flat 2-272067 communique etc. by the spy and be prepared.

The mixed aggregate of the metal phthalocyanine beyond aforesaid in addition titanyl phthalocyanine and the titanyl phthalocyanine can for example be passed through, metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine is dissolved in the sulfuric acid etc., the solid matter of separating out is carried out purifying, and promptly common wet method is prepared.In addition, the mixed aggregate of nonmetal phthalocyanine and metal phthalocyanine also can similarly be made.For example, the mixed aggregate of X type nonmetal phthalocyanine and titanyl phthalocyanine can be opened disclosed preparation method of flat 10-90926 communique etc. by the spy and is prepared.

Described at least two kinds of metal phthalocyanines and the nonmetal phthalocyanine that comprises titanyl phthalocyanine also can mix use with other charge generation material.As mixing other charge generation material that uses, can enumerate Network ロ ロ ダ イ ア Application Block Le one bisdiazo compounds such as (Chloro Diane Blue), ジ Block ロ モ ア Application サ Application ス ロ Application polycyclic quinones such as (dibromoanthanthron) compound, perylene compounds, quinoline a word used for translation ketone compounds and Azulene salt compounds etc. with at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine.

Formation method as charge generation layer 15, can adopt the method that on the outer peripheral face of electric conductivity support 11, forms by vacuum evaporation charge generation material 12, perhaps with resin of binding property solvent or dispersion in appropriate solvent, obtain resin of binding property solution, hybrid charge produces material 12 and makes its dispersion in this solution, preparation charge generation layer coating fluid is coated on this coating fluid on the outer peripheral face of electric conductivity support 11 and the method for film forming.Wherein, preferably adopt the latter's method.Below this method is described.

Object lesson as the resin of binding property that is used for charge generation layer 15, can enumerate for example melamine resin, epoxy resin, silicones, urethane resin, acryl resin, polycarbonate resin, polyarylate resin, phenoxy resin and polyvinyl butyral resin and comprise at least 2 kinds of copolymer resins that constitute the repetitive of these resins, for example can enumerate insulative resin such as vinyl chloride vinyl acetate copolymer resin and acrylonitritrile-styrene resin resin etc.Adhesive resin is not limited to these, and normally used resin all can be used as adhesive resin.These resins can use a kind separately, also can mix at least 2 kinds of uses.

As the solvent of charge generation layer with coating fluid, can enumerate for example halogenated hydrocarbons such as methylene chloride, the ketone of acetone, MEK and cyclohexanone etc., ester such as ethyl acetate and butyl acetate class, ethers such as tetrahydrofuran and dioxane, arenes such as benzene, toluene and dimethylbenzene, and N, aprotic polar solvents such as dinethylformamide etc.These solvents can use a kind separately, also can mix at least 2 kinds of uses.

The blending ratio of charge generation material 12 and resin of binding property, preferably the ratio of charge generation material 12 is in the scope of 10 weight %～99 weight %.When the ratio of charge generation material 12 during less than 10 weight %, sensitivity reduces.When the ratio of charge generation material 12 during greater than 99 weight %, not only the film strength of charge generation layer 15 reduces, and, the dispersiveness of charge generation material 12 descends, produce thick particle, the part part surface electric charge in addition that should be eliminated by exposure reduces, and formation image deflects, particularly toner adhere to the image photographic fog that is called blackspot that forms small stain on the white background to be increased.Therefore, be set in the scope of 10 weight %～99 weight %.

As charge generation material 12 is blended in the method that makes its dispersion in the binder resin solution, can adopt usual ways such as using coating vibrator, bowl mill, sand mill, refiner, vibration grinding machine, colloid mill and ultrasonic dispersing machine.As the coating process of charge generation layer, can adopt usual ways such as dip coated method, spray-on process, sessile drop method (bead method) or nozzle process with coating fluid.

The thickness of charge generation layer 15 is preferably 0.05 μ m～5.0 μ m, more preferably 0.1 μ m～1.0 μ m.When the thickness of charge generation layer 15 during less than 0.05 μ m, efficiency of light absorption descends, and sensitivity reduces.When the thickness of charge generation layer 15 during greater than 5 μ m, the electric charge in charge generation layer inside moves becomes the rate-determing step of eliminating photosensitive body surface surface charge process, and sensitivity reduces.Therefore, be set at 0.05 μ m～5.0 μ m.

As previously mentioned, contain the enamine compound shown in the aforementioned formula (1) in the charge transport layer 16 that forms on the outer peripheral face of charge generation layer 15 as charge transport material 13.

In aforementioned formula (1), as Ar ¹, Ar ², Ar ³, Ar ⁴, Ar ⁵, a, R ², R ³Or R ⁴The object lesson of shown aryl can be enumerated phenyl, naphthyl, pyrenyl and anthryl etc.The substituting group that can have as these aryl, for example can enumerate, alkyl such as methyl, ethyl, propyl group and trifluoromethyl, thiazolinyls such as 2-propenyl and styryl, alkoxys such as methoxyl, ethoxy and propoxyl group, amino such as methylamino and dimethylamino, halogen radicals such as fluorine, chlorine and bromine, aryl such as phenyl and naphthyl, arylthio such as aryloxy group such as phenoxy group and sulfo-phenoxy group etc.As object lesson, for example can enumerate tolyl, methoxyphenyl, xenyl, terphenyl, Phenoxyphenyl with these substituent aryl.Right-(thiophenyl) phenyl and right-styryl phenyl etc.

In aforementioned formula (1), as Ar ¹, Ar ², Ar ³, Ar ⁴, Ar ⁵, R ², R ³Or R ⁴The object lesson of shown heterocyclic radical can be enumerated for example furyl, thienyl, thiazolyl, benzofuranyl, benzothienyl and benzoxazolyl etc.As the substituting group that these heterocyclic radicals can have, can enumerate and described Ar ¹The substituting group that the substituting group that shown aryl can have is same as the object lesson with substituent heterocyclic radical, can be enumerated for example N-methyl indol base and N-ethyl carbazole base etc.

In aforementioned formula (1), as Ar ³, Ar ⁴, Ar ⁵, R ², R ³And R ⁴The object lesson of shown aralkyl, for example benzyl and 1-menaphthyl etc.As the substituting group that these aralkyl can have, can enumerate and described Ar ¹The substituting group that the substituting group that shown aryl can have is same as the object lesson with substituent aralkyl, can be enumerated for example to methoxy-benzyl.

In aforementioned formula (1), as Ar ³, Ar ⁴, Ar ⁵, a, R ¹, R ², R ³Or R ⁴Shown alkyl, the alkyl of preferred carbon number 1～6, as object lesson, can enumerate for example chain-like alkyls such as methyl, ethyl, n-pro-pyl, isopropyl and the tert-butyl group, and naphthenic base such as cyclohexyl and cyclopentyl etc.As the substituting group that these alkyl can have, can enumerate and described Ar ¹The substituting group that the substituting group that shown aryl can have is same, as object lesson, can enumerate alkyl that for example alkoxyalkyl such as haloalkyl such as trifluoromethyl and methyl fluoride, 1-methoxy ethyl and 2-thienyl methyl etc. replaced by heterocyclic radical etc. with substituent alkyl.

In aforementioned formula (1), as the alkoxy shown in a, the alkoxy of preferred carbon number 1～4 as object lesson, can be enumerated for example methoxyl, ethoxy, positive propoxy and isobutoxy etc.As the substituting group that these alkoxys can have, can enumerate and described Ar ¹The substituting group that the substituting group that shown aryl can have is same.

In aforementioned formula (1),,, can enumerate for example dimethylamino, lignocaine, diisopropylaminoethyl etc. as object lesson as the amino that the alkyl of the dialkyl amido shown in a, preferred carbon number 1～4 replaces.As the substituting group that these dialkyl amidos can have, can enumerate and described Ar ¹The substituting group that the substituting group that shown aryl can have is same.

In aforementioned formula (1), as a and R ¹The object lesson of shown halogen atom can be enumerated for example fluorine atom and chlorine atom etc.

In aforementioned formula (1), as with Ar ⁴, Ar ⁵In conjunction with the object lesson of atom, can enumerate for example oxygen atom, sulphur atom and nitrogen-atoms etc.Nitrogen-atoms for example can be with the form and the Ar of divalent bases such as imino group or N-alkyl imino ⁴And Ar ⁵In conjunction with.As with Ar ⁴And Ar ⁵In conjunction with the object lesson of atomic group, can enumerate for example alkylidenes such as methylene, ethylidene and methyl methylene, alkenylenes such as ethenylidene, allylidene, oxygen methylene (chemical formula-O-CH ₂-) etc. contain heteroatomic alkylidene, and the sulphur ethenylidene (chemical formula-S-CH=CH-) etc. contains divalent bases such as heteroatomic alkenylene etc.

In the enamine compound shown in the aforementioned formula (1), the enamine compound shown in the preferred following general formula of use (2) is as charge transport material 13 especially.

In described general formula (2), b, c and d represent to have substituent alkyl separately, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom, and i, k and j represent 1～5 integer separately.When i was at least 2, a plurality of b can be identical or different, and the formation ring structure also can interosculate.When k was at least 2, a plurality of c can be identical or different, and the formation ring structure also can interosculate.When j was at least 2, a plurality of d can be identical or different, and the formation ring structure also can interosculate.

Object lesson as b, c and d, except that hydrogen atom, can enumerate the alkyl of methyl, ethyl, n-pro-pyl, isopropyl, trifluoromethyl, methyl fluoride and 1-methoxy ethyl etc., the alkoxy of methoxyl, ethoxy, positive propoxy and isopropoxy etc., the dialkyl amido of dimethylamino, lignocaine and diisopropylaminoethyl etc., the aryl of phenyl, tolyl, methoxyphenyl and naphthyl etc., and halogen atom such as fluorine atom, chlorine atom.

In addition, in aforementioned formula (2), Ar ⁴, Ar ⁵, a and m definition with the definition in the aforementioned general formula (1).

In the enamine compound shown in the aforementioned formula (1), enamine compound shown in the described general formula (2) has extra high charge delivery capability, therefore by in charge transport material 13, using the enamine compound shown in the described general formula (2), can obtain showing the more Electrophtography photosensor 1 of high responsiveness.By using this Electrophtography photosensor 1, can make the image of electro-photography apparatus form the further high speed of speed.In addition, in the enamine compound shown in the aforementioned formula (1), therefore enamine compound shown in the described general formula (2) is synthetic can prepare at an easy rate than being easier to and the yield height, can make the Electrophtography photosensor 1 of described demonstration high responsiveness with lower manufacturing cost.

In the enamine compound shown in the aforementioned formula (1),, can enumerate Ar as from characteristic, cost and the particularly preferred compound of throughput rate equal angles ¹And Ar ²Be all the compound of phenyl.Wherein, preferred especially Ar ¹And Ar ²Be all phenyl, Ar ³Be phenyl, tolyl, right-methoxyphenyl, xenyl, naphthyl or thienyl, Ar ⁴And Ar ⁵In any is phenyl, p-methylphenyl, right-methoxyphenyl, naphthyl, thienyl or thiazolyl at least, R ¹, R ², R ³And R ⁴Be all hydrogen atom, n is 1 compound.

As the object lesson of the enamine compound shown in the aforementioned formula (1), can enumerate down the exemplary compounds shown in the tabulation 1～table 32, but be not limited thereto.In addition, in table 1～table 32 with each exemplary compounds of basis representation corresponding to each group of aforementioned formula (1).For example, the exemplary compounds No.1 shown in the table 1 is the enamine compound shown in following structural formula (1-1).Wherein, in table 1～table 32, when representing by Ar ⁴And Ar ⁵Interosculate when forming ring structure, Ar ⁴Hurdle and Ar ⁵The hurdle merges, and represents Ar in the lump ⁴And Ar ⁵In conjunction with carbon-to-carbon double bond, and Ar ⁴And Ar ⁵The ring structure that forms with the carbon atom of this carbon-to-carbon double bond.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

[table 13]

[table 14]

[table 15]

[table 16]

[table 17]

[table 18]

[table 19]

[table 20]

[table 21]

[table 22]

[table 23]

[table 24]

[table 25]

[table 26]

[table 27]

[table 28]

[table 29]

[table 30]

[table 31]

[table 32]

Compound shown in the aforementioned formula (1) for example can followingly be prepared.

At first, the amines of stretching shown in aldehyde compound shown in the following general formula (3) or ketone compounds and the following general formula (4) carries out dehydration condensation, prepares the enamine compound intermediate shown in the following general formula (5) thus.

(in the formula, Ar ¹, Ar ²And R ¹Definition identical with the definition in the aforementioned formula (1).)

(in the formula, Ar ³, a and m definition identical with the definition in the aforementioned formula (1).)

(in the formula, Ar ¹, Ar ², Ar ³, R ¹, a and m definition identical with the definition in the aforementioned formula (1).)

This dehydration condensation for example, can followingly carry out.The aldehyde compound shown in the described general formula (3) or ketone compounds and with it roughly the secondary amine compound shown in the described general formula (4) of equimolar amounts be dissolved in aromatic series series solvent, alcohols or the ethers equal solvent, make solution.As the object lesson of solvent for use, for example can enumerate toluene, dimethylbenzene, chlorobenzene, butanols and diethylene glycol dimethyl ether etc.Add catalyzer in the solution of making, for example the acid catalyst of p-toluenesulfonic acid, camphorsulfonic acid or p-toluenesulfonic acid pyridiniujm etc. reacts under the heating.The addition of catalyzer is aldehyde compound or the ketone compounds shown in the described relatively general formula (3), preferred 1/10～1/1000 molar equivalent, more preferably 1/25～1/500 molar equivalent, most preferably 1/50～1/200 molar equivalent.In the reaction, because water byproduct hinders reaction, so, make the water and the solvent azeotropic of generation, drain into outside the system.Thus, can prepare the enamine compound intermediate shown in the described general formula (5) with high yield.

Then; to the enamine compound intermediate shown in the described general formula (5); come Ford (Friedel-Crafts) reaction to carry out acidylate by Weir Si Maier (Vilsmeier) reaction carrying out formylation or by Knut Fridell-Ke, prepare the enamine-carbonyl intermediates shown in the following general formula (6).At this moment, when carrying out formylation, can prepare R in the enamine-carbonyl intermediates shown in the following general formula (6) by Weir Si Maier reaction ⁵Enamine-aldehyde intermediate for hydrogen atom; When coming the Ford reaction to carry out acidylate by Knut Fridell-Ke, can make R in the enamine-carbonyl intermediates shown in the following general formula (6) ⁵Enamine ketone intermediate for the group beyond the hydrogen atom.

(in the formula, in aforementioned formula (1), when n is 0, R ⁵Expression R ⁴, but n is 1,2 or 3 o'clock, R ⁵Expression R ²Ar ¹, Ar ², Ar ³, R ¹, R ², R ⁴, a, m and n definition and aforementioned formula (1) in identical.)

Weir Si Maier reaction for example can followingly be carried out.At first, to N, dinethylformamide (being called for short DMF) or 1, add phosphoryl chloride phosphorus oxychloride and N in the 2-ethylene dichloride equal solvent, dinethylformamide, phosphoryl chloride phosphorus oxychloride and N-methyl-N-phenyl formamide or phosphoryl chloride phosphorus oxychloride and N, the N-diphenylformamide is made Weir Si Maier reagent.In Weir Si Maier reagent 1.0 equivalents～1.3 equivalents of making, add the enamine intermediate shown in the 1.0 equivalent aforementioned formula (5), in 60～110 ℃ of heating down, stirred 2～8 hours.Then, be hydrolyzed with alkaline aqueous solutions such as 1～8N sodium hydrate aqueous solution or potassium hydroxide aqueous solutions.Thus, can prepare R in the enamine-carbonyl intermediates shown in the described general formula (6) with high yield ⁵Enamine-aldehyde intermediate for hydrogen atom.

In addition, Knut Fridell-Ke comes the Ford reaction, for example can followingly carry out.To 1, add reagent that 1.0 equivalents～1.3 equivalents are made by aluminum chloride and oxychloride and the enamine intermediate shown in the 1.0 equivalent aforementioned formula (5) in the 2-ethylene dichloride equal solvent, stirred 2～8 hours in-40～80 ℃.At this moment, according to circumstances heat.Then, be hydrolyzed with alkaline aqueous solutions such as 1～8N sodium hydrate aqueous solution or potassium hydroxide aqueous solutions.Can prepare R in the enamine-carbonyl intermediates shown in the described general formula (6) with high yield thus ⁵Enamine-ketone intermediate for the group beyond the hydrogen atom.

At last, with the enamine-carbonyl intermediates shown in the aforementioned formula (6) and following general formula (7-1) or Wittig (Wittig) reagent (7-2), under alkali condition, carry out Wittig-Huo Na (Wittig-Horner) reaction, can prepare the enamine compound shown in the aforementioned formula (1) thus.At this moment, if adopt the Witting reagent shown in the following general formula (7-1), can obtain n wherein and be the enamine compound shown in 0 the aforementioned formula (1), if when adopting the Witting reagent shown in the described general formula (7-2), can obtain n wherein and be the enamine compound shown in 1,2 or 3 the aforementioned formula (1).

(in the formula, R ⁶Expression can have substituent alkyl maybe can have substituent aryl.Ar ⁴And Ar ⁵Definition identical with the definition of aforementioned formula (1).)

(in the formula, R ⁶Expression can have substituent alkyl maybe can have substituent aryl; N represents 1～3 integer; Ar ⁴, Ar ⁵, R ², R ³And R ⁴Definition identical with the definition in the aforementioned formula (1).)

This Wittig-Huo Na reaction for example can followingly carry out.To toluene, dimethylbenzene, diethyl ether, tetrahydrofuran (being called for short THF), glycol dimethyl ether, N, in dinethylformamide or the dimethyl sulfoxide (DMSO) equal solvent, add the enamine-carbonyl intermediates shown in the 1.0 equivalent aforementioned formula (6), the described general formula of 1.0～1.20 equivalents (7-1) or (7-2) shown in Witting reagent and metal alkoxides such as 1.0～1.5 equivalent potassium tert-butoxides, caustic alcohol or sodium methoxide, in room temperature or 30～60 ℃ of following heated and stirred 2～8 hours.Can prepare the enamine compound shown in the aforementioned formula (1) with high yield thus.

Enamine compound shown in the aforementioned formula (1) can be selected a kind or at least 2 kinds of uses of mixing from the compound that described table 1～table 32 is enumerated.

Enamine compound shown in the aforementioned formula (1) also can mix the back with other charge transport material to be used.As mixing other charge transport materials that use with the enamine compound shown in the aforementioned formula (1), can enumerate heterogeneous ring compounds such as carbazole, indoles, imidazoles, oxazole, pyrazoles, oxadiazole, pyrazoline, thiadiazoles, aniline based compound, hydrazone based compound, aromatic amine compound, polystyrene compound, triphenylamine based compound, triphenyl methane based compound and stilbene based compound, and on main chain or side chain, have from the sub-property materials of power supply such as polymkeric substance of the group of these compound derivings.When the enamine compound shown in the aforementioned general formula (1) and other charge transport materials mix when using, preferably will contain the enamine compound shown in the aforementioned formula (1) as the potpourri of principal ingredient as charge transport material 13.

Charge transport layer 16 is to form in charge transport material 13 bonded property resin 17 bonding modes.Charge transport layer 16 for example can followingly form, dissolving or disperse resin of binding property 17 in the same solvent of the solvent that uses in coating fluid with described charge generation layer, obtain resin of binding property solution, dissolved charge transportation of substances 13 preparation charge transport layer coating fluids in this solution, by with described charge generation layer the same method of coating process with coating fluid, this coating fluid of coating forms charge transport layer 16 on the outer peripheral face of charge generation layer 15.

Adhesive resin 17 in the charge transport layer 16 can use with described charge generation layer 15 in the same resin of resin of binding property that uses.The wherein preferred and good resin of charge transport material 13 compatibilities.For example can use, the vinyl polymerization resin of plexiglass, polystyrene resin, Corvic etc. or comprise at least 2 kinds of copolymer resins that constitute their repetitives, resins such as polycarbonate resin, vibrin, polyestercarbonate resin, polysulfone resin, phenoxy resin, epoxy resin, silicones, polyarylate resin, polyamide, polyether resin, urethane resin, polyacrylamide resin, phenolics.In addition, also can use these resins partial cross-linked and the preparation thermoset resin.These resins both can use separately, also can mix at least 2 kinds of uses.In above-mentioned resin, the specific insulation of polystyrene resin, polycarbonate resin, polyarylate resin or polyphenylene oxide is not less than 10 ¹³Ω cm, electrical insulating property is good, and film forming and potential property etc. are also good, so preferred especially.

Angle from the printability resistance of photographic layer 14, the ratio A/B of the weight A of the charge transport material 13 in the charge transport layer 16 and the weight B of resin of binding property 17 is preferably in weight ratio and is no more than 2/3, if described ratio A/B surpasses 2/3, the ratio of resin of binding property 17 reduces, compare when then higher with the ratio of resin of binding property 17, the printability resistance of photographic layer 14 reduces.

In addition, when adopting infusion process to form the occasion of charge transport layer 16, described ratio A/B preferably is not less than 1/3.If described ratio A/B is lower than 1/3, the ratio of resin of binding property 17 raises, and then because coating fluid viscosity strengthens, causes that coating speed descends, and causes throughput rate significantly to reduce.In addition,, then produce whiting (blushing) phenomenon, in the charge transport layer 16 that forms, produce white casse if, increase the solvent in the coating fluid in large quantities for the viscosity that suppresses coating fluid strengthens.

The thickness of charge transport layer 16 is preferably 5 μ m～50 μ m, more preferably 10 μ m～40 μ m.When the thickness of charge transport layer 16 during less than 5 μ m, the charged hold facility of photosensitive surface descends.When the thickness of charge transport layer 16 during greater than 50 μ m, the resolution of photoreceptor descends.Therefore, the thickness of charge transport layer 16 is set in 5 μ m～50 μ m.

As previously mentioned, photographic layer 14 is by the charge generation layer 15 that as above forms and charge transport layer 16 laminations and the laminated-type photographic layer that forms.Bear by different layers respectively with the charge transport function by making the charge generation function, can select optimal charge generation function and charge transport function as the material that constitutes each layer, the good especially Electrophtography photosensor 1 of character stability in can obtaining reusing respectively.

Conductive material as constituting electric conductivity support 11 can use for example metals such as aluminium, copper, zinc, nickel or titanium, and the metal material of alloys such as aluminium alloy or stainless steel.In addition, electric conductivity support 11 is not limited to these metal materials, also can use on surfaces such as macromolecular materials such as polyethylene terephthalate, phenolics, nylon or polystyrene, cardboard or glass and carry out conductive processing, as laminated metal foil or evaporation metal material and the material that obtains, or the material that is coated with suitable resin of binding property of conductive material such as titanium dioxide, tin oxide, indium oxide, carbon black etc.The shape of electric conductivity support 11 is cylindric in the present embodiment, but is not limited to this, can also be cylindric, sheet or endless belt etc.

As mentioned above, in the present embodiment, photographic layer 14 on the outer peripheral face of electric conductivity support 11 according to the order of charge generation layer 15, charge transport layer 16 with its in turn lamination form, but be not limited thereto, also can be on the outer peripheral face of electric conductivity support 11 according to the order of charge transport layer 16, charge generation layer 15 in turn lamination form.

Fig. 5 is the constructed profile of the Electrophtography photosensor 2 of reduced representation the 2nd embodiment of the present invention.The Electrophtography photosensor 2 of present embodiment is similar to the Electrophtography photosensor 1 of the 1st embodiment, and its counterpart omits the part of its explanation with identical symbolic representation.

It should be noted that between electric conductivity support 11 and photographic layer 14 for Electrophtography photosensor 2 and to be provided with undercoat 18.

Thus, can prevent from from electric conductivity support 11 can to improve the electric charge barrier to photographic layer 14 iunjected charges.Therefore, can prevent the reduction of photographic layer 14 charging property, the surface charge on the part beyond the part that suppresses should be eliminated by exposure reduces, and can prevent to produce on the image that forms defectives such as photographic fog.Can suppress photographic layer 14 in addition and peel off, the connectivity of electric conductivity support 11 and photographic layer 14 is provided from electric conductivity support 11.

Undercoat 18 uses mostly with the layer of resin as principal ingredient.Because the photographic layer 14 that is located on the outer peripheral face of undercoat 18 uses described solvent to form, the resin that therefore constitutes undercoat 18 uses preferably that normally used organic solvent is the resin of indissoluble when forming photographic layer 14.As this resin, can enumerate water soluble resins such as polyvinyl alcohol (PVA), casein and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxy nylon, and acryl resin, polyurethane, melamine resin, phenolics and epoxy resin etc. form the gel-type resin of three-dimensional net structure etc.

Also can add for example fine powder pigment of metal oxides such as titanium dioxide, monox, aluminium oxide, zirconia, tin oxide or indium oxide in the undercoat 18.By adding these metal oxides, can prevent that electric charge from accumulating on the undercoat 18, can reduce owing to reuse the rising of the photoreceptor residual electric potential that causes.In addition, can also prevent from the image that forms, to produce the interference fringe that is called ripple.

Undercoat 18 can followingly form, for example dissolving or disperse described resin in appropriate solvent, and the preparation coating liquid for undercoat layer is coated on this coating fluid on the outer peripheral face of electric conductivity support 11 and forms.When the fine powder pigment that in undercoat 18, adds described metal oxide etc., undercoat 18 can followingly form, dissolving or dispersions in appropriate solvent such as fine powder pigment with described resin and metal oxide, the preparation coating liquid for undercoat layer is coated on this coating fluid on the outer peripheral face of electric conductivity support 11 and forms undercoat 18.

The solvent of coating liquid for undercoat layer can use the same solvent of solvent that uses with coating fluid with aforesaid charge generation layer.

Method as the fine powder pigment that makes described resin and metal oxide dissolves or disperses in solvent can adopt usual ways such as bowl mill, sand mill, refiner, vibrating mill, colloid mill or ultrasonic dispersing machine.With coating process, can adopt usual ways such as dip coated method, spray-on process, sessile drop method or nozzle process as undercoat with coating fluid.

The thickness of undercoat 18 is preferably 0.1 μ m～20 μ m, more preferably 1 μ m～5 μ m.When the thickness of undercoat 18 during less than 0.1 μ m, can not play the effect of undercoat 18 in fact, it can't cover the defective of electric conductivity support 11, can not obtain uniform surface, can not prevent from electric conductivity support 11 that to photographic layer 14 iunjected charges the charging property of photographic layer 14 descends.When the thickness of undercoat 18 during greater than 20 μ m, when forming undercoat 18, be difficult to be formed uniformly undercoat 18 by the dip coated method, simultaneously, the physical strength of the undercoat 18 of formation reduces, and sensitivity descends, and is therefore not preferred.

Fig. 6 is the fragmentary cross-sectional view of formation of the Electrophtography photosensor 3 of reduced representation the 3rd embodiment of the present invention.The Electrophtography photosensor 3 of present embodiment and the Electrophtography photosensor 1 of the 1st embodiment are similar, and its counterpart omits the part of its explanation with identical symbolic representation.

Electrophtography photosensor 3 it should be noted that it has by the single formed single-layer type photographic layer 140 of layer that contains charge generation material 12 and charge transport material 13.Described charge generation material 12 comprises titanyl phthalocyanine with described specific crystal formation, comprise at least two kinds of metal phthalocyanines or the nonmetal phthalocyanine of titanyl phthalocyanine, and described charge transport material 13 comprises the enamine compound shown in the aforementioned formula (1).Be that Electrophtography photosensor 3 is individual layer photoreceptors.

Electrophtography photosensor 3 for present embodiment, with the Electrophtography photosensor 1 of described the 1st embodiment similarly, contain to have in X-ray diffraction spectrum and show that the titanyl phthalocyanine of the specific crystal formation of diffraction peak, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine or nonmetal phthalocyanine are as charge generation material 12 in 27.2 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °).Thereby, with the 1st embodiment similarly, by using Electrophtography photosensor 3, can take into account the miniaturization of electro-photography apparatus and the high speed that image forms speed, it is fast to realize that miniaturization and image form speed, and the high-reliability electronic photographic means of high quality image can be provided under various environment such as low temperature and low humidity environment.

Photographic layer 140 is to be formed by resin of binding property 17 bonding modes with charge generation material 12 and charge transport material 13.Photographic layer 140 for example can followingly form, to contain titanyl phthalocyanine with described specific crystal formation, at least two kinds of metal phthalocyanines that comprise titanyl phthalocyanine, the perhaps charge generation material 12 of nonmetal phthalocyanine, the charge transport material 13 that contains the enamine compound shown in the aforementioned formula (1), and resin of binding property 17 with described charge generation layer with the same appropriate solvent of the employed solvent of coating fluid in dissolving or disperse, preparation photographic layer coating fluid, adopt and the coating process same method of described charge generation layer, this coating fluid is coated on the outer peripheral face of electric conductivity support 11 and forms photographic layer 140 with coating fluid.

The ratio A/B of the weight A of the charge transport material 13 in the charge transport layer 16 of ratio the A '/B ' of the weight A ' of the charge transport material 13 in the photographic layer 140 and the weight B ' of adhesive resin 17 and the photoreceptor 1 of the 1st embodiment and the weight B of adhesive resin 17 is same, preferably is no more than 2/3.In addition, when forming photographic layer 140 by the dip coated method, described ratio A/B preferably is not less than 1/3.

The thickness of photographic layer 140 is preferably 5 μ m～50 μ m, more preferably 5 μ m～40 μ m, more preferably 10 μ m～40 μ m.When the thickness of photographic layer 140 during less than 5 μ m, the charged hold facility on photographic layer surface descends.When the thickness of photographic layer 140 during greater than 50 μ m, throughput rate reduces.Therefore, be set at 5 μ m～50 μ m.

On the outer peripheral face of the photographic layer 14,140 that is provided with on the Electrophtography photosensor 1,2,3 of above-mentioned the 1st～the 3rd embodiment, the surface of protective seam with protection photographic layer 14,140 can be set also.Protective seam can use the layer that for example is made of thermoplastic resin, light-cured resin or thermoset resin etc.Protective seam also can contain inorganic material, organometallics and electronics acceptance materials such as UV resistant agent, antioxidant, metal oxide.

In addition, in photographic layer 14,140 and sealer, can add plastifier such as dibasic acid ester, fatty acid ester, phosphate or chlorinated paraffin such as phthalic ester in case of necessity.Thus, can improve processability.It is flexible to pay photographic layer 14,140 and sealer in addition, improves mechanical property.

In addition, in photographic layer 14,140 and sealer, can add levelling agents such as silicones.Can improve surface smoothing thus.

As the electro-photography apparatus of the 4th embodiment of the present invention, below illustration have an electro-photography apparatus 100 of the Electrophtography photosensor 1 (photoreceptor 1) of described the 1st embodiment.Fig. 7 is the side arrangement plan of the formation of reduced representation electro-photography apparatus 100.

But electro-photography apparatus 100 has the Electrophtography photosensor 1 that is supported by apparatus main body (not illustrating among the figure) with free rotation mode, direction along arrow 41 drives the photoreceptor drive unit 37 of photoreceptor 1 around rotation 44 rotations, the control device 38 of the running of control sensitization body drive 37.Photoreceptor drive unit 37 for example has motor etc. as power source, and the transmission of power that will come from motor by gear (not illustrating among the figure) drives photoreceptor 1 with the rotation of rotation round velocities Vp to the support of the core body that constitutes photoreceptor 1.

Around the photoreceptor 1, side is provided with charged device 32, exposure device 30, developer 33, transfer printing device 34 and clearer 36 in turn downstream along the sense of rotation of the photoreceptor 1 shown in the arrow 41 from upstream side.Clearer 36 also is provided with except that electrical equipment (not illustrating among the figure).

Charged device 32 is the outer peripheral face 43 charged Charging systems that reach the regulation current potential that make photoreceptor 1.Charged device 32 can be the Charging system of contact such as charged mode of cylinder for example.

Exposure device 30 for example has semiconductor laser as light source, by outer peripheral face 43, the outer peripheral face 43 of charged photoreceptor 1 is carried out the exposure corresponding with image information by the photoreceptor 1 of light such as laser 31 irradiation between charged device 31 and developer 32 of light emitted.

Developer 33 is the developing apparatuss that the electrostatic latent image that is formed by exposure on the outer peripheral face 43 of photoreceptor 1 developed by developer, it has in the face of what photoreceptor 1 was provided with and toner is fed to developing roller 33a on photoreceptor 1 outer peripheral face, with can make developing roller 33a around the mode of the turning axle rotation parallel with the turning axle 44 of photoreceptor 1 support this developing roller 33a and within it the portion space accommodate the housing 33b of the developer that contains toner.

Transfer printing device 34 is to be fed between photoreceptor 1 and the transfer printing device 34 as the transfer device on the transfer paper 51 of recording medium being transferred to by the direction of conveyer (not illustrating among the figure) along arrow 42 by the toner image as visual image that forms on the outer peripheral face 43 that is developed in photoreceptor 1.Transfer printing device 34 can be following contactless transfer device, and it has for example Charging system, by giving the electric charge of transfer paper 51 with the toner reversed polarity, toner image is transferred on the transfer paper 51.

Clearer 36 is to remain in the cleaning device that the toner on the outer peripheral face 43 of photoreceptor 1 is removed and reclaimed behind the transfer operation with transfer printing device 34, it has cleaning spade 36a that the toner that remains on the outer peripheral face 43 of photoreceptor 1 is peeled off from described outer peripheral face 43 and the recovery housing 36b that takes in the toner of being peeled off by cleaning spade 36a.

In addition, on the carriage direction of the transfer paper 51 after passing through between photoreceptor 1 and the transfer printing device 34, be provided with the fixing device fuser 35 of the image fixing that makes transfer printing.Fuser 35 has the heated roller 35a that contains heating arrangement (not illustrating among the figure) and is heated cylinder 35a with passing through of being oppositely arranged of heated roller 35a pushes the pressing roller 35b that forms contact site.

The diameter of photoreceptor 1 is preferably 24mm～40mm.Thus, can be with electro-photography apparatus 100 miniaturizations.

Electrophotographic image formation method as one of embodiments of the present invention comprises: the operation that makes the Electrophtography photosensor surface charging, charged Electrophtography photosensor surface exposed form the operation of electrostatic latent image, the operation that the electrostatic latent image that forms is developed, described Electrophtography photosensor is characterised in that, uses Electrophtography photosensor of the present invention.This electrophotographic image formation method is implemented by the electro-photography apparatus 100 of present embodiment.

Below, 100 runnings describe to electro-photography apparatus.At first, by the direction rotation driving photoreceptor 1 of photoreceptor drive unit 37 along arrow 41, by being arranged on the more charged device 32 of upstream side of sense of rotation that imaging point than the light 31 of exposure device 30 is positioned at photoreceptor 1, make outer peripheral face 43 uniform chargeds of photoreceptor 1 reach the positive potential or the negative potential of regulation.

Then, from outer peripheral face 43 irradiates lights 31 of 30 pairs of photoreceptors 1 of exposure device.Scan repeatedly at length direction from the light 31 of light emitted as the photoreceptor 1 of main scanning direction.By photoreceptor 1 rotation being driven, and scan light 31 repeatedly, the outer peripheral face 43 of photoreceptor 1 is carried out the exposure of correspondence image information from light source.By exposure, the surface charge of light 31 illuminated portions is by cancellation, and the surface potential of light 31 illuminated portions and do not produce difference between the surface potential of the part of irradiates light 31 forms electrostatic latent image thus on the outer peripheral face 43 of photoreceptor 1.

Then, by from be arranged on sense of rotation that imaging point than the light 31 of light emitted is positioned at photoreceptor 1 more the developing roller 33a of the developer 33 in downstream toner is fed on the outer peripheral face 43 of the photoreceptor 1 that has formed electrostatic latent image, latent electrostatic image developing forms toner image on the outer peripheral face 43 of photoreceptor 1.

In addition and exposure same period of photoreceptor 1 ground, transfer paper 51 is fed between photoreceptor 1 and the developer 34 by the direction of conveyer along arrow 42.When being fed to transfer paper 51 between photoreceptor 1 and the developer 34, transfer printing device 34 gives the electric charge of transfer paper 51 with the toner reversed polarity.Thus, the toner image that forms on the outer peripheral face 43 of photoreceptor 1 is transferred on the transfer paper 51.

Transfer printing the transfer paper 51 of toner image be transported to fuser 35 by conveyer, be heated pressurization when heated roller 35a by fuser 35 and the contact site between the pressing roller 35b.Thus, the photographic fixing on transfer paper 51 of the toner image on the transfer paper 51 forms firm image.The transfer paper 51 that so forms image is sent to the outside of electro-photography apparatus 100 by conveyer.

On the other hand, remain in the be cleaned cleaning spade 36a of device 36 of toner on the outer peripheral face 43 of photoreceptor 1 behind the transfer operation through transfer printing device 34 and peel off, be recycled to and reclaim with in the housing 36b from the outer peripheral face 43 of photoreceptor 1.The electric charge of outer peripheral face 43 of so having removed the photoreceptor 1 of toner is removed electrical equipment and is removed, and the electrostatic latent image on the outer peripheral face 43 of photoreceptor 1 disappears.Then, photoreceptor 1 is further rotated driving, and charged from photoreceptor 1 repeats a series of operation once more.The image that forms continuously as implied above.

At this moment, by the running of control device 38 control sensitization body drives 37 so that the exposure position 45 of exposure device 30 along Electrophtography photosensor 1 outer peripheral face 43 from the imaging point that is equivalent to light 31 to the distance L of developing location 46 divided by the value d of described rotation round velocities Vp (=L/Vp) be no more than 90 milliseconds (90msec).Like this, when using described diameter, can control the rotation round velocities Vp and make its increase as the short small-sized photoreceptor 1 of the described distance L of 24mm～40mm.

Described d value begins time of finishing to developing by 33 pairs of electrostatic latent images of developing apparatus about equally with exposing from the outside surface 43 by 30 pairs of photoreceptors 1 of exposure device.Therefore, foreshorten to and be no more than 90msec from expose time of beginning to finish of the outside surface 43 by 30 pairs of photoreceptors 1 of exposure device to developing by 33 pairs of electrostatic latent images of developing apparatus.Be that present embodiment can be carried out electronic camera technology at a high speed, thereby can realize that image forms fireballing electro-photography apparatus 100.

Begin time of finishing to developing by 33 pairs of electrostatic latent images of developing apparatus when exposing from the outside surface 43 by 30 pairs of photoreceptors 1 of exposure device in short-term, the response of Electrophtography photosensor reduces sometimes under the low temperature and low humidity environment, and image quality reduces.

Yet, even because the electro-photography apparatus 100 of present embodiment is provided with the photoreceptor with photographic layer 14 1 that also can show high responsiveness under described low temperature and low humidity environment, described photographic layer 14 comprises titanyl phthalocyanine with aforementioned specific crystal formation, contain at least two kinds of metal phthalocyanines of titanyl phthalocyanine or the enamine compound shown in nonmetal phthalocyanine and the aforementioned formula (1).Even therefore under the situation that the time that begins to finish to developing by 33 pairs of electrostatic latent images of developing apparatus when exposing from the outside surface 43 by 30 pairs of photoreceptors 1 of exposure device lacks, also can under various environment such as low temperature and low humidity environment, provide high quality images.Thereby it is fast and the high-reliability electronic photographic means 100 of high quality image can be provided under various environment such as low temperature and low humidity environment to realize that image forms speed.

As mentioned above, the electro-photography apparatus 100 of present embodiment has the Electrophtography photosensor 1 of the 1st embodiment, but is not limited thereto, and also can have the Electrophtography photosensor 2 of the 2nd embodiment or the Electrophtography photosensor 3 of the 3rd embodiment.

Charged in addition device 32 is the Charging system of contact, but is not limited thereto, and also can be contactless Charging systems such as corona charging mode.

Transfer printing device 34 has Charging system in addition, it is to make toner image be transferred to contactless transfer device on the transfer paper 51 by the electric charge of paying transfer paper 51 and toner reversed polarity, but be not limited thereto, also can be to have cylinder, by using cylinder to make transfer paper 51 and photoreceptor crimping, toner image is transferred to contact transfer device on the transfer paper 51.

In addition, around photoreceptor 1, be respectively equipped with charged device 32, exposure device 30 and developer 33 each 1, but be not limited thereto, between developer 33 and transfer printing device 34, the 2nd Charging system, the 2nd exposure device and the 2nd developing apparatus can also be set further.Thus, form the toner image of first kind of color by charged device 32, exposure device 30 and developer 33, by being located at the 2nd Charging system, the 2nd exposure device and the 2nd developing apparatus between developer 33 and the transfer printing device 34, form and first kind of toner image that color is not homochromy, can realize on transfer paper, to form the electro-photography apparatus of multicolor image.

Embodiment

Below, explain the present invention with embodiment, but the present invention is not limited.

The preparation of (Production Example 1) exemplary compounds No.1

The preparation of (Production Example 1-1) enamine intermediate

In 100ml toluene, add N-(p-methylphenyl)-alpha-naphthylamine and diphenyl acetaldehyde shown in 20.6g (1.05 equivalent) following structural formula (9) and 0.23g (0.01 equivalent) the DL-10-camphorsulfonic acid shown in 23.3g (1.0 equivalent) following structural formula (8), heating, byproduct water and methylbenzene azeotropic are discharged to outside the system, reacted 6 hours.Behind the reaction terminating, reaction solution is concentrated into about 1/10, slowly drops in the 100ml hexane of vigorous stirring, generate crystal.Leach the crystal that is generated, wash, obtain 36.2g pale yellow powder shape compound with cold ethanol.

Analyze the gained compound with liquid chromatography-mass spectrometry (being called for short LC-MS), consequently, observe the peak at 412.5 places, it is equivalent at (the calculated value of molecular weight: 411.20) go up the molion [M+H] that adds proton of the enamine intermediate shown in the following structural formula (10) ⁺Thereby,, can judge that the compound that obtains is the enamine compound intermediate (yield: 88%) shown in the following structural formula (10).In addition, can judge that the purity of the enamine compound intermediate that obtains is 99.5% from the analysis result of LC-MS.

As mentioned above, as N-(the p-methylphenyl)-alpha-naphthylamine shown in the described structural formula (8) of secondary amine compound and as the diphenyl acetaldehyde shown in the described structural formula (9) of aldehyde compound by carrying out dehydration condensation, can obtain the enamine intermediate shown in the said structure formula (10).

The preparation of (Production Example 1-2) Production Example 1-2 enamine-aldehyde intermediate

To the anhydrous N of 100ml, in the dinethylformamide (DMF), slowly add 9.2g (1.2 equivalent) phosphoryl chloride phosphorus oxychloride down, stir about 30 minutes, preparation Weir Si Maier reagent ice-cooled.Enamine intermediate shown in the said structure formula (10) that in this solution, in ice-cooled slow down adding 20.6g (1.0 equivalent) Production Example 1-1, obtains.Then, slowly heating makes temperature of reaction rise to 80 ℃, remains on 80 ℃ of heated and stirred 3 hours.After reaction finishes, this reaction solution is put cold, slowly added in the 4N sodium hydrate aqueous solution of 800ml cooling, generate precipitation.Leach the precipitation of generation, fully after the washing, carry out recrystallization, obtain 20.4g yellow powder shape compound with the mixed solvent of ethanol and ethyl acetate.

The compound that obtains is analyzed with LC-MS, observed the peak at 440.5 places, it is equivalent to the enamine shown in the following structural formula (11)-aldehyde intermediate (calculated value of molecular weight: 439.19) go up the molion [M+H] that adds proton ⁺, thus, can judge that the compound that obtains is the enamine compound shown in the following structural formula (11)-aldehyde intermediate (yield: 93%).In addition, according to the analysis result of LC-MS as can be known, the purity of gained enamine-aldehyde intermediate is 99.7%.

As mentioned above,, carry out formylation, can obtain the enamine shown in the said structure formula (11)-aldehyde intermediate by Weir Si Maier reaction to the enamine intermediate shown in the said structure formula (10).

The preparation of (Production Example 1-3) exemplary compounds No.1

Enamine-aldehyde intermediate shown in the said structure formula (11) that 8.8g (1.0 equivalent) Production Example 1-2 is obtained and the cinnamyl diethyl phosphate shown in 6.1g (1.2 equivalent) following structural formula (12) are dissolved in the 80ml dry DMF, after in this solution, slowly adding 2.8g (1.25 equivalent) potassium tert-butoxide under the room temperature, be heated to 50 ℃, remained on 50 ℃ of following heated and stirred 5 hours.Reaction mixture put cold after, inject excessive methyl alcohol.Collect precipitate, be dissolved in and make toluene solution in the toluene.This toluene solution is moved into separating funnel, wash, take out organic layer.The organic layer dried over mgso of taking out.After the drying, the organic layer of having removed solids is concentrated, adopt silica gel column chromatography to separate, obtain the 10.1g yellow crystal.

Analyze resulting crystal with LC-MS, observe the peak at 540.5 places, it is equivalent at the enamine compound of the exemplary compounds No.1 shown in the table 1 (calculated value of molecular weight: 539.26) go up the molion [M+H] that adds proton ⁺

In addition, at deuterochloroform (chemical formula: CDCl ₃) the middle nuclear magnetic resonance (abbreviation: NMR) spectrum, the spectrum of the enamine compound structure of supported exemplary compounds No.1 of measuring crystal.Fig. 8 is the product of Production Example 1-3 ¹H-NMR spectrum, Fig. 9 are the enlarged drawings of the 6ppm～9ppm of spectrum shown in Figure 8.Figure 10 is the standard test of the product of Production Example 1-3 ¹³C-NMR spectrum, Figure 11 are the enlarged drawings of the 110ppm～160ppm of spectrum shown in Figure 10.Figure 12 is that the DEPT135 of the product of Production Example 1-3 measures ¹³C-NMR spectrum, Figure 13 are the enlarged drawings of the 110ppm～160ppm of spectrum shown in Figure 12.Also have, in Fig. 8～Figure 13, transverse axis is represented chemical shift δ (ppm).In addition, in Fig. 8 and Fig. 9, the numerical value of putting down in writing between signal and transverse axis is the relative integral value that the integrated value of the signal shown in the label 500 of Fig. 8 is made as each signal of 3 o'clock.

From the measurement result of the analysis result of LC-MS and NMR spectrum as can be known, resulting crystal is exactly the enamine compound (yield: 94%) of exemplary compounds No.1.In addition, can judge that the purity of the enamine compound of the exemplary compounds No.1 that obtains is 99.8% according to the analysis result of LC-MS.

As mentioned above, carry out Wittig-Huo Na reaction the enamine-aldehyde intermediate shown in the said structure formula (11) with as the cinnamyl diethyl phosphate shown in the said structure formula (12) of Witting reagent, can obtain the enamine compound of the exemplary compounds No.1 shown in the table 1.

The preparation of (Production Example 2) exemplary compounds No.61

Except replace N-(the p-methylphenyl)-alpha-naphthylamine shown in 23.3g (1.0 equivalent) the said structure formula (8) with 4.9g (1.0 equivalent) N-(p-methoxyphenyl)-alpha-naphthylamine, with Production Example 1 similarly, pass through dehydration condensation, preparation enamine intermediate (yield: 94%) and by Weir Si Maier prepared in reaction enamine-aldehyde intermediate (yield: 85%), by Wittig-Huo Na reaction, obtain 7.9g yellow powder shape compound again.In addition, the reagent that uses in each reaction and the equivalent relation of raw material are identical with the equivalent relation of reagent that uses in the Production Example 1 and raw material.

Analyze the compound that obtains through LC-MS, observe the peak at 556.7 places, it is equivalent at the enamine compound of the exemplary compounds No.61 shown in the table 9 (calculated value of molecular weight: 555.26) go up the molion [M+H] that adds proton ⁺

In addition, at deuterochloroform (chemical formula: CDCl ₃) the middle NMR spectrum of measuring the compound that obtains, the spectrum of the enamine compound structure of supported exemplary compounds No.1.Figure 14 is the product of Production Example 2 ¹H-NMR spectrum, Figure 15 are the enlarged drawings of the 6ppm～9ppm of spectrum shown in Figure 14.Figure 16 is the standard test of the product of Production Example 2 ¹³C-NMR spectrum, Figure 17 are the enlarged drawings of the 110ppm～160ppm of spectrum shown in Figure 16.Figure 18 is that the DEPT135 of the product of Production Example 2 measures ¹³C-NMR spectrum, Figure 19 are the enlarged drawings of the 110ppm～160ppm of spectrum shown in Figure 180.Also have, in Figure 14～Figure 19, transverse axis is represented chemical shift δ (ppm).In Figure 14 and Figure 15, the value of putting down in writing between signal and transverse axis is the relative integral value that the signal integration value shown in Figure 14 label 501 is made as each signal of 3 o'clock.

Judge that according to the analysis result of LC-MS and the measurement result of NMR spectrum obtaining compound is exactly the enamine compound (yield: 92%) of exemplary compounds No.61.In addition, according to the analysis result of LC-MS as can be known, the purity of the enamine compound of exemplary compounds No.61 is 99.0%.

As mentioned above, by the 3 steps reaction of dehydration condensation, Weir Si Maier reaction and Wittig-Huo Na reaction, obtain the enamine compound of the exemplary compounds No.61 shown in the table 9,3 step total recoverys are 73.5%.

The preparation of (Production Example 3) exemplary compounds No.46

Enamine-aldehyde intermediate shown in the said structure formula (11) that 2.0g (1.0 equivalent) Production Example 1-2 is obtained and the Witting reagent shown in 1.53g (1.2 equivalent) following structural formula (13) are dissolved in the 15ml dry DMF, after in this solution, slowly adding 0.71g (1.25 equivalent) potassium tert-butoxide under the room temperature, be heated to 50 ℃, remained on 50 ℃ of heated and stirred 5 hours.Reaction mixture put cold after, pour in the excessive methyl alcohol.Collect precipitate, be dissolved in and make toluene solution in the toluene.This toluene solution is moved into separating funnel, after the washing, take out organic layer, the organic layer of taking-up uses magnesium sulphate in dry.After the drying, the organic layer of having removed solids is concentrated, adopt silica gel column chromatography to separate, obtain the 2.37g yellow crystals.

Analyze the compound that obtains through LC-MS, observe the peak at 566.4 places, it is equivalent at the enamine compound of the exemplary compounds No.46 shown in the table 7 (calculated value of molecular weight: 565.28) go up the molion [M+H] that adds proton ⁺, hence one can see that, and the crystallization that obtains is the enamine compound (yield: 92%) of exemplary compounds No.46.In addition, according to the analysis of LC-MS as can be known, the purity of the enamine compound of the exemplary compounds No.46 that obtains is 99.8%.

As mentioned above, Witting reagent shown in the enamine shown in the said structure formula (11)-aldehyde intermediate and the said structure formula (13) carries out Wittig-Huo Na reaction, can obtain the enamine compound of exemplary compounds No.46 as shown in table 7.

The preparation of the compound shown in (relatively Production Example 1) following structural formula (14)

Alms bowl is dissolved among the anhydrous THF of 15ml in the middle of enamine shown in the said structure formula (11) that 2.0g (1.0 equivalent) Production Example 1-2 is obtained-aldehyde, in 0 ℃ of THF solution (volumetric molar concentration: 1.0mol/L) of slowly adding the Grignard reagent allyl bromination magnesium that 5.23ml (1.15 equivalent) makes by allyl bromide, bromoallylene and magnesium metal in this solution.After 0.5 hour, with the situation of carrying out of thin-layered chromatography inspection reaction, the result shows in 0 ℃ of stirring, the reaction product that is not fixed, and obtain a plurality of different products.After carrying out aftertreatment, extraction, concentrate with the method for routine, recycle silicon glue column chromatography is carried out the separation and the purifying of reaction mixture.

Yet, can not get the target compound shown in the following structural formula (14).

[embodiment]

The mensuration of the X-ray diffraction spectrum of the titanyl phthalocyanine that uses in following embodiment and comparative example is with Cu-K α characteristic X-ray (wavelength: 1.54050 ) as x-ray source, carry out with θ/2 θ scanning methods.

(embodiment 1)

Material shown in the table 33 was disperseed 10 hours the preparation coating liquid for undercoat layer with coating vibrator.When adjusting thickness, with the coating liquid for undercoat layer dip coated that obtains on the outer peripheral face of the cylindric electric conductivity support 11 of the aluminum of diameter 30mm, long 335mm, the undercoat 18 of formation thickness 1 μ m.In addition, behind the painting bottom coating coating fluid, do not heat-treat.

Table 33

Coating liquid for undercoat layer
		Material	Consumption
(Ishihara Sangyo Kaisha, Ltd. makes titanium dioxide: TTO-55A)	6 weight portions
		Copolymer nylon (eastern レ Co., Ltd.: ア ミ ラ Application CM8000)	4 weight portions
Methyl alcohol
		130 weight portions
Normal butyl alcohol			60 weight portions

Then, the material shown in the table 34 was disperseed 2 hours preparation charge generation layer coating fluid with coating vibrator.In addition, in charge generation material 12, use the titanyl phthalocyanine of crystal formation with described X-ray diffraction spectrum shown in Figure 2.According to Fig. 2, the titanyl phthalocyanine of present embodiment use has following crystal formation as can be known, promptly in X-ray diffraction spectrum, show main diffraction peaks in 7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.9 °, 24.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.2 °, in described diffraction peak, 9.4 ° diffraction peak and the overlapping diffraction peak bundle of 9.6 ° diffraction peak show maximum intensity, and 27.2 ° diffraction peak demonstrates the 2nd high strength.

After charge generation layer that dip coated on the outer peripheral face of the undercoat 18 that forms before obtains is with coating fluid, 120 ℃ dry 10 minutes down, form the charge generation layer 15 of thickness 0.2 μ m.

Table 34

The charge generation layer coating fluid
		Material	Consumption
Titanyl phthalocyanine (Fig. 2)	2 weight portions
		(Sekisui Chemical Co., Ltd makes polyvinyl butyral resin: ェ ス レ Star Network BL-1)	2 weight portions
Cyclohexanone
		100 weight portions

Then, the material shown in the stirring and dissolving table 35, preparation charge transport layer coating fluid.In addition, in charge transport material 13, use the enamine compound of the exemplary compounds No.61 shown in the aforementioned table 9.After charge transport layer that dip coated on the outer peripheral face of the charge generation layer 15 that forms before obtains is with coating fluid, 110 ℃ dry 60 minutes down, form the charge transport layer 16 of thickness 25 μ m.

Table 35

The charge transport layer coating fluid
		Material	Consumption
Exemplary compounds No.61	5 weight portions
		(Mitsubishi Gas Chemical Co., Ltd makes polycarbonate resin: Z300)	10 weight portions
(Shin-Etsu Chemial Co., Ltd makes silicone oil: KF50)	0.002 weight portion
		Tetrahydrofuran	60 weight portions

As above make the Electrophtography photosensor of the structure as shown in Figure 5 that satisfies important document of the present invention.

(embodiment 2)

Except in the charge generation material 12 of embodiment 1, replace having with titanyl phthalocyanine beyond the titanyl phthalocyanine of crystal formation of aforementioned X-ray diffraction spectrum shown in Figure 2 with crystal formation of X-ray diffraction spectrum shown in the earlier figures 3, similarly to Example 1, make the Electrophtography photosensor that satisfies important document of the present invention.

According to Fig. 3 as can be known, the used titanyl phthalocyanine of present embodiment has following crystal formation, promptly in X-ray diffraction spectrum, in 9.5 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 ° of crystal formations that show main diffraction peaks.

(embodiment 3)

Except in the charge generation material 12 of embodiment 1, replace having with titanyl phthalocyanine beyond the titanyl phthalocyanine of crystal formation of aforementioned X-ray diffraction spectrum shown in Figure 2 with crystal formation of X-ray diffraction spectrum shown in the earlier figures 4, similarly to Example 1, make the Electrophtography photosensor that satisfies important document of the present invention.

According to Fig. 4 as can be known, the used titanyl phthalocyanine of present embodiment has following crystal formation, promptly in X-ray diffraction spectrum, in 9.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 14.2 °, 23.9 ° and 27.1 ° of crystal formations that show main diffraction peaks.

(embodiment 4)

Except in the charge transport material 13 of embodiment 1, beyond the replacement of the exemplary compounds No.1 shown in the aforementioned table 1 exemplary compounds No.61, similarly to Example 1, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 5)

Except in the charge generation material 12 of embodiment 1, the titanyl phthalocyanine that has the crystal formation of aforementioned X-ray diffraction spectrum shown in Figure 2 with titanyl phthalocyanine replacement with crystal formation of X-ray diffraction spectrum shown in the earlier figures 3, in charge transport material 13, beyond the replacement of the exemplary compounds No.1 shown in the aforementioned table 1 exemplary compounds No.61, similarly to Example 1, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 6)

Except in the charge generation material 12 of embodiment 1, the titanyl phthalocyanine that has the crystal formation of aforementioned X-ray diffraction spectrum shown in Figure 2 with titanyl phthalocyanine replacement with crystal formation of X-ray diffraction spectrum shown in the earlier figures 4, in charge transport material 13, beyond the replacement of the exemplary compounds No.1 shown in the aforementioned table 1 exemplary compounds No.61, similarly to Example 1, make the Electrophtography photosensor that satisfies important document of the present invention.

(comparative example 1)

Except in the charge transport material 13 of embodiment 1, beyond the enamine compound replacement exemplary compounds No.61 shown in the following structural formula (15), similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 2)

Except in the charge generation material 12 of embodiment 1, the titanyl phthalocyanine that has the crystal formation of aforementioned X-ray diffraction spectrum shown in Figure 2 with titanyl phthalocyanine replacement with crystal formation of X-ray diffraction spectrum shown in the earlier figures 3, in charge transport material 13, beyond the replacement of the enamine compound shown in the described structural formula (15) exemplary compounds No.61, similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 3)

Except in the charge generation material 12 of embodiment 1, the titanyl phthalocyanine that has the crystal formation of aforementioned X-ray diffraction spectrum shown in Figure 2 with titanyl phthalocyanine replacement with crystal formation of X-ray diffraction spectrum shown in the earlier figures 4, in charge transport material 13, beyond the replacement of the enamine compound shown in the described structural formula (15) exemplary compounds No.61, similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 4)

Except in the charge generation material 12 of embodiment 1, with having in X-ray diffraction spectrum, in 7.5 °, 12.3 °, 16.3 °, 25.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.7 ° of titanyl phthalocyanines that show the crystal formation of main diffraction peaks, be beyond the titanyl phthalocyanine of the so-called α type titanyl phthalocyanine crystal formation that replaces having aforementioned X-ray diffraction spectrum shown in Figure 2, similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 5)

Except in the charge generation material 12 of embodiment 1, use aforesaid α type titanyl phthalocyanine replacement to have the titanyl phthalocyanine of the crystal formation of X-ray diffraction spectrum shown in Figure 2, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 6)

Except in the charge generation material 12 of embodiment 1, use the trisazo pigment shown in the following structural formula (16) to replace having beyond the titanyl phthalocyanine of crystal formation of X-ray diffraction spectrum shown in Figure 2, similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 7)

Except in the charge generation material 12 of embodiment 1, use the trisazo pigment replacement shown in the aforementioned structural formula (16) to have the titanyl phthalocyanine of the crystal formation of X-ray diffraction spectrum shown in Figure 2, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 1, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(estimating 1)

Each Electrophtography photosensor of above embodiment 1～6 and comparative example 1～7 making is installed on (Sharp Corporation's manufacturing: AR-M450) in the digital copier respectively, the developer of this duplicating machine is removed, and replaces at the development section branch and is provided with (the Gentec company manufacturing: CATE751) of surface potential meter.In duplicating machine, part to photosensitive surface is exposed, the data that the other parts input does not expose, at the development position, measure the surface potential of the photoreceptor of unexposed portion, (V), measure the surface potential of the photoreceptor of exposed portion as dark space current potential Vo, (V), this result is as the initial stage measurement result as area pellucida current potential VL.In addition, at the digital copier that is used for estimating, the laser that uses 780nm is as exposure light source.

Then, from digital copier, take out the surface potential meter, replace the installation developer, duplicate the test image of 30,000 predetermined patterns.Then, take out developer once more, described surface potential meter be set at the development position, with the initial stage similarly, measure dark space current potential Vo and area pellucida current potential VL, with it as the evaluation result after reusing.

(estimating 2)

(Sharp Corporation makes: DM4501) reequip with commercially available laser printer, so that it can carry out light quantity and rotation round speed that standard is developed and can be changed exposure light source, each Electrophtography photosensor that embodiment 1～6 and comparative example 1～7 are made is installed on respectively in this device.In addition, at the laser printer that is used for estimating, the laser that uses 780nm is as exposure light source.

By changing the rotation round speed of photoreceptor, begin to be set to 50 milliseconds (50msec), 90 milliseconds (msec) and 130 milliseconds (msec) to the time that the development of electrostatic latent image finishes from photosensitive surface is exposed, this each setting-up time summer forms image on recording chart.The image that visualization obtains, the quality of evaluation map picture.Wherein, when finding to produce scumming on image, the light quantity that increases exposure light source is concatenated to form image, up to no longer producing scumming, till perhaps the degree of scumming can not get improving, the image that finally obtains is used for estimating.In addition, above evaluation is to be that 25 ℃, relative humidity are under the ambient temperature and moisture environment of 55% (55%RH) in temperature, and temperature is that 5 ℃, relative humidity are to carry out under the low temperature and low humidity environment of 20% (20%RH).

More than the result of evaluation 1 and evaluation 2 is shown in table 36.

Table 36

Photoreceptor	The charge generation material	The charge transport material	Surface potential				Image quality
													Initial stage		After using repeatedly		25℃，55％RH			5℃，20％RH
			Vo(-V)	VL(- V)	Vo(-V)	VL(- V)	50msec	90msec	130msec	50msec	90msec	130msec
													Embodiment 1	Titanyl phthalocyanine (Fig. 2)	Exemplary compounds No.61	620	80	600	90	Well	Well	Well	Well	Well	Well
Embodiment 2	Titanyl phthalocyanine (Fig. 3)	Exemplary compounds No.61	630	70	610	90	Well	Well	Well	Well	Well	Well
													Embodiment 3	Titanyl phthalocyanine (Fig. 4)	Exemplary compounds No.61	610	90	600	100	Well	Well	Well	Well	Well	Well
Embodiment 4	Titanyl phthalocyanine (Fig. 2)	Exemplary compounds No.1	600	70	590	90	Well	Well	Well	Well	Well	Well
													Embodiment 5	Titanyl phthalocyanine (Fig. 3)	Exemplary compounds No.1	610	70	600	80	Well	Well	Well	Well	Well	Well
Embodiment 6	Titanyl phthalocyanine (Fig. 4)	Exemplary compounds No.1	610	80	600	100	Well	Well	Well	Well	Well	Well
													Comparative example 1	Titanyl phthalocyanine (Fig. 2)	Enamine compound (15)	580	90	580	100	Well	Well	Well	Produce scumming	Produce scumming	Well
Comparative example 2	Titanyl phthalocyanine (Fig. 3)	Enamine compound (15)	590	100	560	100	Well	Well	Well	Produce scumming	Produce scumming	Well
													Comparative example 3	Titanyl phthalocyanine (Fig. 4)	Enamine compound (15)	590	90	570	110	Well	Well	Well	Produce scumming	Produce scumming	Well
Comparative example 4	α type titanyl phthalocyanine	Exemplary compounds No.61	620	180	610	310	Produce scumming	Produce scumming	Well	Produce scumming	Produce scumming	Produce scumming
													Comparative example 5	α type titanyl phthalocyanine	Exemplary compounds No.1	610	200	600	320	Produce scumming	Produce scumming	Well	Produce scumming	Produce scumming	Produce scumming
Comparative example 6	Trisazo pigment (16)	Exemplary compounds No.61	620	230	600	320	Well	Well	Well	Produce scumming	Well	Well
													Comparative example 7	Trisazo pigment (16)	Exemplary compounds No.1	630	240	610	350	Well	Well	Well	Produce scumming	Well	Well

According to embodiment 1～6 and comparative example 1～3 more as can be known, in the charge generation material, use has in X-ray diffraction spectrum, show the embodiment 1～6 of titanyl phthalocyanine of specific crystal formation of diffraction peak and the photoreceptor of comparative example 1～3 in 27.2 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), with in the charge generation material, use has the photoreceptor of the comparative example 4～7 of α type titanyl phthalocyanine beyond the described specific crystal formation or the trisazo pigment shown in the described structural formula (16) and compares, the absolute value of area pellucida current potential VL is little, and response is good.The absolute value of the potential difference (PD) between the area pellucida current potential VL after the area pellucida current potential VL at the initial stage of the photoreceptor of embodiment 1～6 and comparative example 1～3 and the repeated use is little in addition, and the reduction of repeated use back response that hence one can see that is little.

In addition, according to table 36 as can be known, in the photoreceptor of embodiment 1～6 and comparative example 1～3, the device of photoreceptor that the embodiment 1～6 that uses the enamine compound shown in the aforementioned formula (1) in the charge transport material has been installed is under the low temperature and low humidity environment, even beginning from photosensitive surface is exposed to the time that the development of electrostatic latent image finishes is when carrying out electronic camera technology under the high speed of 50msec or 90msec, also can obtain high quality images.

On the other hand, though the photoreceptor of comparative example 1～3 that uses the enamine compound shown in the described structural formula (15) be not included in the aforementioned formula (1) with the photoreceptor of embodiment 1～6 and similarly, response is good, and the reduction of reusing the back response is little, but the device of photoreceptor that comparative example 1～3 has been installed produces scumming on image when highly carrying out electronic camera technology under the low temperature and low humidity environment.

As mentioned above, have in X-ray diffraction spectrum by in photographic layer, making up to contain, show the titanyl phthalocyanine of crystal formation of diffraction peak and the enamine compound shown in the aforementioned formula (1) in 27.2 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), under the low temperature and low humidity environment, also can show high responsiveness even can obtain, when after being miniaturized, being used for high-velocity electrons photograph technology, also can under various environment such as low temperature and low humidity environment, provide the Electrophtography photosensor of high quality images.

(embodiment 7)

Material shown in the table 37 was disperseed 10 hours the preparation coating liquid for undercoat layer with coating vibrator.When adjusting thickness, with the coating liquid for undercoat layer dip coated that obtains on the outer peripheral face of the cylindric electric conductivity support 11 of the aluminum of diameter 30mm, long 335mm, the undercoat 18 of formation thickness 0.2 μ m.In addition, behind the painting bottom coating coating fluid, do not heat-treat.

Then, the material shown in the table 37 was disperseed 2 hours preparation charge generation layer coating fluid with coating vibrator.After charge generation layer that dip coated on the outer peripheral face of the undercoat 18 that forms before obtains is with coating fluid, 120 ℃ dry 10 minutes down, form the charge generation layer 15 of thickness 0.2 μ m.

Table 37

The charge generation layer coating fluid
		Material	Consumption
The mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine	2 weight portions
		(Sekisui Chemical Co., Ltd makes polyvinyl butyral resin: ェ ス レ Star Network BL-1)	2 weight portions
Cyclohexanone
		100 weight portions

In addition, open the embodiment 3 of flat 4-372663 communique record according to the spy as the mixed crystal of titanyl phthalocyanine shown in the table 37 of charge generation material 12 and gallium chloride phthalocyanine, the gallium chloride phthalocyanine that in 9 weight portion titanyl phthalocyanines, mixes 1 weight portion, with its be crushed to can not demonstrate clear and definite X-ray diffraction peak after, in methylene chloride, grind and handle and make with the beaded glass of diameter 1mm.The mixed crystal of titanyl phthalocyanine that obtains and gallium chloride phthalocyanine shows strong diffraction peaks in 9.3 °, 10.6 °, 13.3 °, 15.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 26.3 ° in X-ray diffraction spectrum.

Then, the material shown in the stirring and dissolving table 35, preparation charge transport layer coating fluid.In addition, in charge transport material 13, use the enamine compound of the exemplary compounds No.61 shown in the aforementioned table 9.After charge transport layer that dip coated on the outer peripheral face of the charge generation layer 15 that forms before obtains is with coating fluid, 110 ℃ dry 60 minutes down, form the charge transport layer 16 of thickness 25 μ m.

As above make the Electrophtography photosensor of the structure as shown in Figure 5 that satisfies important document of the present invention.

(embodiment 8)

Except in the charge generation material 12 of embodiment 7, use the mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine to replace beyond the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

In addition, the mixed crystal of titanyl phthalocyanine that uses in the present embodiment and inidum chloride phthalocyanine is opened the embodiment 19 of flat 4-372663 communique record according to the spy, the inidum chloride phthalocyanine that in the titanyl phthalocyanine of 9 weight portions, mixes 1 weight portion, with its be crushed to can not demonstrate clear and definite X-ray diffraction peak after, in methylene chloride, grind and handle and make with the beaded glass of diameter 1mm.The mixed crystal of titanyl phthalocyanine that obtains and inidum chloride phthalocyanine shows strong diffraction peaks in 7.6 °, 16.4 °, 22.4 °, 25.5 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.6 ° in X-ray diffraction spectrum.

(embodiment 9)

Except in the charge generation material 12 of embodiment 7, use the mixed crystal of titanyl phthalocyanine and nonmetal phthalocyanine to replace beyond the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

In addition, the titanyl phthalocyanine that uses in the present embodiment and the mixed crystal of nonmetal phthalocyanine are opened the synthesis example 5 of 2000-313819 communique record according to the spy, the nonmetal phthalocyanine that in the titanyl phthalocyanine of 7 weight portions, mixes 3 weight portions, after adopting sour gelatinization method amorphization, in water, make with the naphthalene heated and stirred.The titanyl phthalocyanine that obtains and the mixed crystal of nonmetal phthalocyanine show diffraction peaks in 7.0 °, 9.0 °, 14.1 °, 18.0 °, 23.7 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.3 ° in X-ray diffraction spectrum.

(embodiment 10)

Except in the charge generation material 12 of embodiment 7, with 1 weight portion titanyl phthalocyanine and (the Dainippon Ink. ﹠ Chemicals Inc's manufacturing: FastogenBlue 8120BS) beyond the mixed crystal of replacement titanyl phthalocyanine and gallium chloride phthalocyanine of 1 weight portion X type nonmetal phthalocyanine, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

In addition, the titanyl phthalocyanine that uses in the present embodiment is opened the Production Example 1 of 2000-129155 communique record according to the spy, to in MEK, grind processing by the Y type titanyl phthalocyanine coarse crystallization that hydrolysis titanium chloride phthalocyanine obtains with the beaded glass of diameter 2mm, after methanol wash, carry out drying and make.The titanyl phthalocyanine that obtains is in X-ray diffraction spectrum, show main diffraction peaks in 7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.9 °, 24.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.2 °, the overlapping diffraction peak bundle of the diffraction peak of 9.4 ° diffraction peak and 9.6 ° shows maximum intensity in the described diffraction peak, and 27.2 ° diffraction peak demonstrates the 2nd high strength.

(embodiment 11)

Except in the charge generation material 12 of embodiment 7, (Dainippon Ink. ﹠ Chemicals Inc makes: Fastogen Blue 8120BS) beyond the mixed crystal of replacement titanyl phthalocyanine and gallium chloride phthalocyanine with X type nonmetal phthalocyanine, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 12)

Except in the charge transport material 13 of embodiment 7, beyond the replacement of the exemplary compounds No.1 shown in the aforementioned table 1 exemplary compounds No.61, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 13)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with the mixed crystal of titanyl phthalocyanine that uses among the embodiment 8 and inidum chloride phthalocyanine, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 14)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with the mixed crystal of titanyl phthalocyanine that uses among the embodiment 9 and nonmetal phthalocyanine, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 15)

Except in the charge generation material 12 of embodiment 7, with 1 weight portion titanyl phthalocyanine that uses among the embodiment 10 and (the Dainippon Ink. ﹠ Chemicals Inc's manufacturing: the mixed crystal of replacement titanyl phthalocyanine and gallium chloride phthalocyanine Fastogen Blue 8120BS) of 1 weight portion X type nonmetal phthalocyanine, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

(embodiment 16)

Except in the charge generation material 12 of embodiment 7, (Dainippon Ink. ﹠ Chemicals Inc makes: the mixed crystal that Fastogen Blue 8120BS) replaces titanyl phthalocyanine and gallium chloride phthalocyanine with X type nonmetal phthalocyanine, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 7, make the Electrophtography photosensor that satisfies important document of the present invention.

(comparative example 8)

Except in the charge transport material 13 of embodiment 7, beyond the enamine compound replacement exemplary compounds No.61 shown in the aforementioned structural formula (15), similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 9)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with the mixed crystal of titanyl phthalocyanine that uses among the embodiment 8 and inidum chloride phthalocyanine, in charge transport material 13, beyond the replacement of the enamine compound shown in the aforementioned structural formula (15) exemplary compounds No.61, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 10)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with the mixed crystal of titanyl phthalocyanine that uses among the embodiment 9 and nonmetal phthalocyanine, in charge transport material 13, beyond the replacement of the enamine compound shown in the aforementioned structural formula (15) exemplary compounds No.61, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 11)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with 1 weight portion titanyl phthalocyanine that uses among the embodiment 10 and 1 weight portion X type nonmetal phthalocyanine (Dainippon Ink. ﹠ Chemicals Inc makes ..Fastogen Blue 8120BS), in charge transport material 13, beyond the replacement of the enamine compound shown in the aforementioned structural formula (15) exemplary compounds No.61, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 12)

Except in the charge generation material 12 of embodiment 7, (Dainippon Ink. ﹠ Chemicals Inc makes: the mixed crystal that Fastogen Blue 8120BS) replaces titanyl phthalocyanine and gallium chloride phthalocyanine with X type nonmetal phthalocyanine, in charge transport material 13, beyond the replacement of the enamine compound shown in the aforementioned structural formula (15) exemplary compounds No.61, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 13)

Except in the charge generation material 12 of embodiment 7, with having in X-ray diffraction spectrum, in 7.5 °, 12.3 °, 16.3 °, 25.3 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 28.7 ° of titanyl phthalocyanines that show the crystal formation of main diffraction peaks, be that so-called α type titanyl phthalocyanine replaces beyond the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 14)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with the α type titanyl phthalocyanine that uses in the comparative example 13, in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 15)

Except in the charge generation material 12 of embodiment 7, beyond the mixed crystal with trisazo pigment replacement titanyl phthalocyanine shown in the aforementioned formula (16) and gallium chloride phthalocyanine, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

(comparative example 16)

Except in the charge generation material 12 of embodiment 7, the mixed crystal that replaces titanyl phthalocyanine and gallium chloride phthalocyanine with the trisazo pigment shown in the aforementioned formula (16), in charge transport material 13, o.1 replace beyond the exemplary compounds No.61 with the illustration compound N, similarly to Example 7, produce the Electrophtography photosensor of discontented unabridged version invention important document.

＜estimate 3 〉

For each Electrophtography photosensor of embodiment 7～16 and comparative example 8～16 making, similarly estimate with above-mentioned evaluation 1.

＜estimate 4 〉

For each Electrophtography photosensor of embodiment 7～16 and comparative example 8～16 making, similarly estimate with above-mentioned evaluation 2.

More than the result of evaluation 3 and evaluation 4 is shown in table 38.

Table 38

Photoreceptor	The charge generation material	The charge transport material	Surface potential				Image quality
													Initial stage		After using repeatedly		25℃，55％RH			5℃，20％RH
			Vo(-V)	VL(-V)	Vo(-V)	VL(-V)	50msec	90msec	130msec	50msec	90msec	130msec
													Embodiment 7	The mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine	Exemplary compounds No.61	610	70	610	90	Well	Well	Well	Well	Well	Well
Embodiment 8	The mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine	Exemplary compounds No.61	620	60	600	80	Well	Well	Well	Well	Well	Well
													Embodiment 9	The mixed crystal of titanyl phthalocyanine and nonmetal phthalocyanine	Exemplary compounds No.61	600	150	590	160	Well	Well	Well	Well	Well	Well
Embodiment 10	Titanyl phthalocyanine, X type nonmetal phthalocyanine	Exemplary compounds No.61	610	120	600	130	Well	Well	Well	Well	Well	Well
													Embodiment 11	X type nonmetal phthalocyanine	Exemplary compounds No.61	600	210	590	230	Well	Well	Well	Well	Well	Well
Embodiment 12	The mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine	Exemplary compounds No.1	610	80	600	90	Well	Well	Well	Well	Well	Well
													Embodiment 13	The mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine	Exemplary compounds No.1	610	80	590	100	Well	Well	Well	Well	Well	Well
Embodiment 14	The mixed crystal of titanyl phthalocyanine and nonmetal phthalocyanine	Exemplary compounds No.1	620	160	600	180	Well	Well	Well	Well	Well	Well
													Embodiment 15	Titanyl phthalocyanine, X type nonmetal phthalocyanine	Exemplary compounds No.1	610	130	610	140	Well	Well	Well	Well	Well	Well
Embodiment 16	X type nonmetal phthalocyanine	Exemplary compounds No.1	610	220	600	240	Well	Well	Well	Well	Well	Well
													Comparative example 8	The mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine	Enamine compound (15)	600	110	580	130	Well	Well	Well	Produce scumming	Produce scumming	Well
Comparative example 9	The mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine	Enamine compound (15)	610	100	580	110	Well	Well	Well	Produce scumming	Produce scumming	Well
													Comparative example 10	The mixed crystal of titanyl phthalocyanine and nonmetal phthalocyanine	Enamine compound (15)	600	170	580	190	Well	Well	Well	Produce scumming	Produce scumming	Well
Comparative example 11	Titanyl phthalocyanine, X type nonmetal phthalocyanine	Enamine compound (15)	610	150	600	170	Well	Well	Well	Produce scumming	Produce scumming	Well
													Comparative example 12	X type nonmetal phthalocyanine	Enamine compound (15)	600	250	570	270	Well	Well	Well	Produce scumming	Produce scumming	Well
Comparative example 13	α type titanyl phthalocyanine	Exemplary compounds No.61	620	180	610	310	Produce scumming	Produce scumming	Well	Produce scumming	Produce scumming	Produce scumming
													Comparative example 14	α type titanyl phthalocyanine	Exemplary compounds No.1	610	200	600	320	Produce scumming	Produce scumming	Well	Produce scumming	Produce scumming	Produce scumming
Comparative example 15	Trisazo pigment (16)	Exemplary compounds No.61	620	230	600	320	Well	Well	Well	Produce scumming	Well	Well
													Comparative example 16	Trisazo pigment (16)	Exemplary compounds No.1	630	240	610	350	Well	Well	Well	Produce scumming	Well	Well

According to table 38 as can be known, installed in the charge generation material and to have used at least two kinds of metal phthalocyanines or the nonmetal phthalocyanine that comprises titanyl phthalocyanine, the device of photoreceptor of embodiment 7～16 that uses the enamine compound shown in the aforementioned formula (1) in the charge transport material is under the low temperature and low humidity environment, beginning from photosensitive surface is exposed to the time set that the development of electrostatic latent image finishes is to be no more than when carrying out electronic camera technology under the high speed of 90msec, also can obtain high quality images.In addition, can also see that the difference of the area pellucida current potential VL after the area pellucida current potential VL at the initial stage of the photoreceptor of embodiment 7～16 and the repeated use is little, the reduction of response is little during repeated use.

On the other hand, the device of photoreceptor that the comparative example 8～12 that uses the enamine compound shown in the described structural formula (15) that is not included in the aforementioned formula (1) has been installed in the charge transport material is under the low temperature and low humidity environment, if will begin from photosensitive surface is exposed to form image for being no more than 90msec, then on image, produce scumming to the time set that the development of electrostatic latent image finishes.

In addition, device for the photoreceptor that the comparative example 13,14 that only uses α type titanyl phthalocyanine in the charge generation material has been installed, when the time set that begins from photosensitive surface is exposed to finish to the development of electrostatic latent image when being no more than 90msec formation image, under any environment of ambient temperature and moisture environment and low temperature and low humidity environment, on image, all produce scumming.Particularly under the low temperature and low humidity environment, when being 130msec, the time set that the development of electrostatic latent image finishes on image, also produces scumming even will begin from photosensitive surface is exposed.About surface potential, the difference of the area pellucida current potential VL after the area pellucida current potential VL at the initial stage of the photoreceptor of comparative example 13,14 and the repeated use is big, and the reduction of reusing the back response is big.

In addition, device for the photoreceptor that the comparative example 15,16 that uses the trisazo pigment shown in the aforementioned structural formula (16) in the charge generation material has been installed, it is under the low temperature and low humidity environment, when begin on image, to produce scumming when the time set that the development of electrostatic latent image finishes is 50msec from photosensitive surface is exposed.About surface potential, the photoreceptor of the photoreceptor of comparative example 15,16 and comparative example 13,14 is same, and the difference of the area pellucida current potential VL after the area pellucida current potential VL at initial stage and the repeated use is big, and the reduction of reusing the back response is big.

As mentioned above, by in photographic layer, containing at least two kinds of metal phthalocyanines comprising titanyl phthalocyanine or the combination of the enamine compound shown in nonmetal phthalocyanine and the aforementioned formula (1), under the low temperature and low humidity environment, also can show high responsiveness even can obtain, when after being miniaturized, being used for high-velocity electrons photograph technology, also can under various environment such as low temperature and low humidity environment, provide the Electrophtography photosensor of high quality images.

In the scope that does not depart from design of the present invention or principal character, can other variety of way implement the present invention.Therefore, described embodiment only is to give an example simply, and scope of the present invention is not subjected to the qualification of instructions this paper shown in claim.

Also have, the modification or the change that belong in the claim scope also all comprise within the scope of the invention.

[industrial applicibility]

As mentioned above, according to the present invention, because photosensitive layer contains the titanyl phthalocyanine of the crystal formation with high charge generation ability and high charge injection efficient, and the charge transport material with high charge delivery capability, also showing high responsiveness under the low temperature and low humidity environment, can under the various environment such as low temperature and low humidity environment, provide miniaturization high quality image, that can take into account electro-photography apparatus and image to form the Electrophtography photosensor of the high speed of speed even therefore can obtain.

According to the present invention, since in photosensitive layer, have extra high charge delivery capability, synthetic than be easier to and yield higher, can the cheap enamine compound with ad hoc structure of making, therefore can have with lower manufacturing cost manufacturing the more Electrophtography photosensor of high responsiveness.

According to the present invention, extra high susceptibility is shown and is difficult to take place to the titanyl phthalocyanine with specific crystal formation of the transfer of other crystal formation owing in photosensitive layer, contain light display near infrared light and the isometric wave-length coverage of ruddiness, therefore can obtain having the wavelength photoreceptor of the most suitable digital and electronic photographic means and the good Electrophtography photosensor of stable in properties when reusing.

According to the present invention, owing in photosensitive layer, contain the two or more metal phthalocyanines that comprise titanyl phthalocyanine and the enamine compound with high charge delivery capability of ad hoc structure, even thereby can provide under the low temperature and low humidity environment, also show high responsiveness, in miniaturization be used for the process of high-velocity electrons photosensitive body, can under the various environment such as low temperature and low humidity environment, provide miniaturization high quality image, that can take into account electro-photography apparatus and image to form the Electrophtography photosensor of the high speed of speed. In addition by changing the ratio of titanyl phthalocyanine and titanyl phthalocyanine metal phthalocyanine in addition, the Electrophtography photosensor that can easily obtain having desirable wavelength photoreceptor scope.

According to the present invention, because the mixed crystal of the metal phthalocyanine beyond photosensitive layer contains titanyl phthalocyanine and titanyl phthalocyanine, therefore the reduction of response in the time of can suppressing to reuse, obtain the good Electrophtography photosensor of stable in properties when reusing, simultaneously when forming photosensitive layer by coating, can improve the aging stability of coating liquid, improve quality stability and the productivity ratio of Electrophtography photosensor.

According to the present invention, owing in photosensitive layer, contain the mixed crystal of titanyl phthalocyanine and specific metal phthalocyanine, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

According to the present invention, because the enamine compound that in photosensitive layer, contains nonmetal phthalocyanine and have the high charge delivery capability of ad hoc structure, even thereby can provide under the low temperature and low humidity environment, also show high responsiveness, in miniaturization be used for the process of high-velocity electrons photosensitive body, can under the various environment such as low temperature and low humidity environment, provide miniaturization high quality image, that can take into account electro-photography apparatus and image to form the Electrophtography photosensor of the high speed of speed.

According to the present invention, owing in photosensitive layer, contain the X-type nonmetal phthalocyanine, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

According to the present invention, owing in photosensitive layer, contain nonmetal phthalocyanine and metal phthalocyanine, therefore by changing the ratio of nonmetal phthalocyanine and metal phthalocyanine, the Electrophtography photosensor that can easily obtain having desirable wavelength photoreceptor scope.

According to the present invention, owing in photosensitive layer, contain the mixed crystal of nonmetal phthalocyanine and metal phthalocyanine. Therefore the reduction of response in the time of can suppressing to reuse, obtain the good Electrophtography photosensor of stable in properties when reusing, when forming photosensitive layer by coating, can improve the aging stability of coating liquid simultaneously, improve quality stability and the productivity ratio of Electrophtography photosensor.

According to the present invention, owing in photosensitive layer, contain nonmetal phthalocyanine and titanyl phthalocyanine, therefore can obtain having the Electrophtography photosensor of the wavelength photoreceptor scope that is fit to following digital and electronic photographic means, described digital and electronic photographic means adopts the light of long wavelength's scope of semiconductor laser or light emitting diode emission to expose.

According to the present invention, even owing to use the Electrophtography photosensor that under the low temperature and low humidity environment, also can show high responsiveness, therefore, even therefore begin from being exposed in the Electrophtography photosensor surface to time that the development of electrostatic latent image finishes in short-term, also can under the various environment such as low temperature and low humidity environment, provide high-quality image.

According to the present invention, even owing to be provided with the Electrophtography photosensor that under the low temperature and low humidity environment, also can show high responsiveness, thereby can realize small-sized and image to form speed fast, and can under the various environment such as low temperature and low humidity environment, provide the high-reliability electronic photographic means of high quality image.

According to the present invention, by the diameter range of the cylindric or columned Electrophtography photosensor selecting to be fit to, can the miniaturization electro-photography apparatus.

Claims (20)

1. Electrophtography photosensor, it is characterized in that, have electric conductivity support that forms by conductive material and the photographic layer that is arranged on the described electric conductivity support, described photographic layer contains titanyl phthalocyanine and the enamine compound shown in following general formula (1), described titanyl phthalocyanine has, in X-ray diffraction spectrum, in 27.2 ° of crystal formations that show diffraction peak of Bragg angle 2 θ (error: 2 θ ± 0.2 °)

In the formula, Ar ¹And Ar ²Expression can have substituent aryl and maybe can have substituent heterocyclic radical separately; Ar ³Expression can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl, maybe can have substituent alkyl; Ar ⁴And Ar ⁵Represent hydrogen atom separately, can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl and maybe can have substituent alkyl, but Ar ⁴And Ar ⁵Be not hydrogen atom simultaneously, Ar ⁴And Ar ⁵Also can be by atom or the atomic group formation ring structure that interosculates; A represents to have substituent alkyl, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom; M represents 1～6 integer, and when m was at least 2, a plurality of a can be identical or different, and the formation ring structure also can interosculate; R ¹Expression hydrogen atom, halogen atom maybe can have substituent alkyl; R ², R ³And R ⁴Represent hydrogen atom separately, can have substituent alkyl, can have substituent aryl, can have substituent heterocyclic radical and maybe can have substituent aralkyl; N represents 0～3 integer, when n is 2 or 3, and a plurality of R ²Can be identical or different, a plurality of R ³Can be identical or different, but n is 0 o'clock, Ar ³Expression can have substituent heterocyclic radical.

2. the Electrophtography photosensor of claim 1 record, it is characterized in that: the enamine compound shown in the aforementioned formula (1) is the enamine compound shown in the following general formula (2),

In the formula, b, c, d represent to have substituent alkyl separately, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom, i, k and j represent 1～5 integer separately, when i is at least 2, a plurality of b can be identical or different, the formation ring structure also can interosculate, when k is at least 2, a plurality of c can be identical or different, the formation ring structure also can interosculate, when j was at least 2, a plurality of d can be identical or different, and the formation ring structure also can interosculate; Ar ⁴, Ar ⁵, a and m definition identical with aforementioned formula (1).

Claim 1 or 2 the record Electrophtography photosensors, it is characterized in that: described titanyl phthalocyanine has following crystal formation, promptly in X-ray diffraction spectrum, show main diffraction peaks in 7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.9 °, 24.1 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °) and 27.2 °, in described diffraction peak, 9.4 ° diffraction peak and the overlapping diffraction peak bundle of 9.6 ° diffraction peak show maximum intensity, and 27.2 ° diffraction peak demonstrates the 2nd high-intensity crystal formation.

Claim 1 or 2 the record Electrophtography photosensors, it is characterized in that: described titanyl phthalocyanine has following crystal formation, promptly in X-ray diffraction spectrum, in 9.5 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 ° of crystal formations that show main diffraction peaks.

Claim 1 or 2 the record Electrophtography photosensors, it is characterized in that: described titanyl phthalocyanine has following crystal formation, promptly in X-ray diffraction spectrum, in 9.0 ° of Bragg angle 2 θ (error: 2 θ ± 0.2 °), 14.2 °, 23.9 ° and 27.1 ° of crystal formations that show main diffraction peaks.

6. Electrophtography photosensor, it is characterized in that, have the electric conductivity support that formed by conductive material and be arranged on photographic layer on the described electric conductivity support, described photographic layer contains at least two kinds of metal phthalocyanines comprising titanyl phthalocyanine and the enamine compound shown in the following general formula (1)

In the formula, Ar ¹And Ar ²Expression can have substituent aryl and maybe can have substituent heterocyclic radical separately; Ar ³Expression can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl maybe can have substituent alkyl; Ar ⁴And Ar ⁵Represent hydrogen atom separately, can have substituent aryl, can have substituent heterocyclic radical, can have substituent aralkyl and maybe can have substituent alkyl, but Ar ⁴And Ar ⁵Be not hydrogen atom simultaneously, Ar ⁴And Ar ⁵Also can be by atom or the atomic group formation ring structure that interosculates; A represents to have substituent alkyl, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom; M represents 1～6 integer, and when m was at least 2, a plurality of a can be identical or different, and the formation ring structure also can interosculate; R ¹Expression hydrogen atom, halogen atom maybe can have substituent alkyl; R ², R ³And R ⁴Represent hydrogen atom separately, can have substituent alkyl, can have substituent aryl, can have substituent heterocyclic radical and maybe can have substituent aralkyl; N represents 0～3 integer, when n is 2 or 3, and a plurality of R ²Can be identical or different, a plurality of R ³Can be identical or different, but n is 0 o'clock, Ar ³Expression can have substituent heterocyclic radical.

7. the Electrophtography photosensor of claim 6 record, it is characterized in that: described metal phthalocyanine is the mixed crystal of the metal phthalocyanine beyond titanyl phthalocyanine and the titanyl phthalocyanine.

8. the Electrophtography photosensor of claim 7 record, it is characterized in that: described mixed crystal is the mixed crystal of titanyl phthalocyanine and gallium chloride phthalocyanine.

9. the Electrophtography photosensor of claim 7 record, it is characterized in that: described mixed crystal is the mixed crystal of titanyl phthalocyanine and inidum chloride phthalocyanine.

10. Electrophtography photosensor is characterized in that, has electric conductivity support that is formed by conductive material and the photographic layer that is arranged on the described electric conductivity support, and described photographic layer contains the enamine compound shown in nonmetal phthalocyanine and the aforementioned formula (1).

11. the Electrophtography photosensor of claim 10 record, it is characterized in that: described nonmetal phthalocyanine is an X type nonmetal phthalocyanine.

12. the Electrophtography photosensor of claim 10 or 11 records is characterized in that: also contain metal phthalocyanine in the described photographic layer.

13. the Electrophtography photosensor of claim 12 record, it is characterized in that: described nonmetal phthalocyanine and described metal phthalocyanine are the mixed crystal of nonmetal phthalocyanine and metal phthalocyanine.

14. the Electrophtography photosensor of claim 12 or 13 records, it is characterized in that: described metal phthalocyanine is a titanyl phthalocyanine.

15. the Electrophtography photosensor of each record in the claim 6～14 is characterized in that: the enamine compound shown in the aforementioned formula (1) is the enamine compound shown in the following general formula (2).

In the formula, b, c, d represent to have substituent alkyl separately, can have substituent alkoxy, can have substituent dialkyl amido, can have substituent aryl, halogen atom or hydrogen atom; I, k and j represent 1～5 integer separately, when i is at least 2, a plurality of b can be identical or different, the formation ring structure that also can interosculate, when k was at least 2, a plurality of c can be identical or different, the formation ring structure also can interosculate, when j was at least 2, a plurality of d can be identical or different, and the formation ring structure also can interosculate; Ar ⁴, Ar ⁵, a and m definition identical with aforementioned formula (1).

16. electrophotographic image formation method comprises:

Make the operation of the surface charging of Electrophtography photosensor,

Exposed in charged described surface, form electrostatic latent image operation and

With the operation of described latent electrostatic image developing,

It is characterized in that,

Use the Electrophtography photosensor of each record in the claim 1～15 in the described Electrophtography photosensor.

17. the electrophotographic image method of formationing of claim 16 record is characterized in that: the time to the development end of described electrostatic latent image of beginning from being exposed in described Electrophtography photosensor surface is for being no more than 90 milliseconds (90msec).

18. electro-photography apparatus is characterized in that, comprising:

The Electrophtography photosensor of each record in the claim 1～15,

Make the Charging system of the surface charging of described Electrophtography photosensor,

The exposure device that is exposed in charged described surface and

The developing apparatus that the electrostatic latent image that forms by exposure is developed.

19. electro-photography apparatus is characterized in that, comprising:

The Electrophtography photosensor of each record in the claim 1～15 that supports by apparatus main body with rotating freely,

With the photoreceptor drive unit of the described Electrophtography photosensor of rotation round velocities Vp rotation driving,

Make the Charging system of the surface charging of described Electrophtography photosensor,

The exposure device that is exposed in charged described surface,

The developing apparatus that the electrostatic latent image that forms by exposure is developed and

Control the running of described photoreceptor drive unit so that the exposure position along described Electrophtography photosensor outer peripheral face from described exposure device to the distance L of the developing location of described developing apparatus divided by the value d of described rotation round velocities Vp (=L/Vp) be no more than the control device of 90 milliseconds (90msec).

20. the electro-photography apparatus of claim 19 record, it is characterized in that: described Electrophtography photosensor has cylindric or columned shape, and the diameter of described Electrophtography photosensor is 24mm～40mm.

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