JPH04181260A - Electrophotographic sensitive body, electrophotographic apparatus, and facsimile using same - Google Patents

Abstract

PURPOSE:To obtain high sensitivity in the long wavelength region of laser diode beams and to stabilize potential characteristics and image characteristics by using oxytitanium-phthalocyanine specified in crystal form as an electric charge generating material and a specified dihydrophenanthrene or phenanthrene compound as a charge transfer material for the electrophotographic sensitive body. CONSTITUTION:The electrophotographic sensitive body contains the crystalline oxytitanium-phthalocyanine having strong peaks in the Bragg angle 2theta+ or -0.2 deg. of 9.0 deg., 14.2 deg., 23.9 deg., and 27.1 deg. in the X-ray diffraction using CuKalpha, and the dihydrophenanthrene compound represented by formula I or the phenanthrene compound represented by formula II, and in formulae I and II, each of R1 - R8 is optionally substituted alkyl, aralkyl, or aryl, thus permitting the obtained electrophotographic sensitive body to be high in sensitivity in the long wavelength region of the laser diode beams and to obtain stabilized image characteristics and superior potential stability in the electrophotographic process.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to an electrophotographic photoreceptor, an electrophotographic apparatus equipped with the electrophotographic photoreceptor, and a facsimile. The present invention relates to an electrophotographic photoreceptor having a photosensitive layer containing the same, an electrophotographic device equipped with the electrophotographic photoreceptor, and a facsimile.

"Prior Art" Conventionally, inorganic photoreceptors having a photosensitive layer mainly composed of an inorganic photoconductive substance such as selenium, cadmium sulfide, or zinc oxide have been widely used as electrophotographic photoreceptors. These are not necessarily satisfactory in terms of thermal stability, 1ilF1 humidity, durability, etc. In particular, selenium and cadmium sulfide have limitations in production and handling due to their toxicity.

On the other hand, organic photoreceptors having a photosensitive layer containing an organic photoconductive compound as a main component have many advantages such as compensating for the above-mentioned drawbacks of inorganic photoreceptors, and have been attracting attention in recent years.

Such organic photoreceptors include photoconductive polymers typified by poly-N-vinylcarbazole and 2.
Electrophotographic photoreceptors having a photosensitive layer mainly composed of a charge transfer complex formed with a Lewis acid such as 4.7-trinitro-9-fluorenone have already been put into practical use. However, this electrophotographic photoreceptor cannot necessarily be improved in sensitivity and durability.

On the other hand, functionally separated electrophotographic photoreceptors, in which charge generation and charge transport functions are performed by separate substances, have brought about significant improvements in sensitivity and durability, which were considered to be shortcomings of conventional organic photoreceptors.

Such a functionally separated electrophotographic photoreceptor uses a charge-generating substance,
Each of the charge transport substances has a wide selection range, and has the advantage that an electrophotographic photoreceptor having arbitrary characteristics can be produced relatively easily.

In recent years, the use of electrophotographic photoreceptors has been rapidly increasing not only in copying machines but also in non-impact printers that apply electrophotographic technology. These are laser beam printers that mainly use laser light as a light source, and a semiconductor laser is used as the light source from the viewpoint of cost and device size.

Semiconductor lasers that are currently mainly used have a long oscillation wavelength of 790±20 nm, and efforts have been made to develop electrophotographic photoreceptors that have sufficient sensitivity to light at these long wavelengths.

Sensitivity on the long wavelength side varies depending on the type of charge-generating material, and many charge-generating materials are being considered.

Typical charge generating materials include phthalocyanine pigments, azo pigments, cyanine pigments, azulene pigments, and squarylium dyes.

On the other hand, as charge-generating materials sensitive to long wavelength light, metal phthalocyanines or metal-free phthalocyanines such as aluminum lophthalocyanine, chloroindium phthalocyanine, oxyvanadium phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine, and oxytitanium phthalocyanine have recently been developed. More and more research is being done.

Among these, many phthalocyanine compounds are known to have polymorphisms; for example, metal-free phthalocyanine has an α-type,
There are β-type, γ-type, δ-type, ε-type, τ-type, χ-type, etc. For copper phthalocyanine, α-type, β-type, γ-type, δ-type, χ-type, etc. are known.

It is also known that differences in crystal form have a large effect on electrophotographic properties (sensitivity, potential stability during durability, etc.) and coating properties when made into a paint.

Oxytitanium phthalocyanine, which is particularly sensitive to long-wavelength light, has polymorphisms as well as other phthalocyanines such as the above-mentioned metal-free phthalocyanine and copper phthalocyanine.

For example, Japanese Patent Application Laid-Open No. 59-49544 (USP 4.44
4.861), JP-A-59-166959, JP-A-61-239248 (USP 4,728,59)
2), Japanese Patent Application Laid-Open No. 62-67094 (tJsP4,6
64,997), JP-A-63-366, JP-A-6
Oxytitanium phthalocyanine, which is a crystalline child, has been reported in JP-A No. 3-116158, JP-A-63-198067, and JP-A-64-17066.

However, these oxytitanium phthalocyanines do not have sufficient sensitivity, have poor potential stability during repeated defecation,
There are several problems in actual use, such as poor charging performance and image deterioration due to changes in the usage environment, and so far no product has been fully satisfactory.

By the way, in general, in electrophotographic photoreceptors, a charge transporting material that is effective for a certain charge-generating substance is not necessarily effective for other charge-generating substances; A charge-generating substance that is effective against other charge-transporting substances may not necessarily be effective against other charge-transporting substances. That is, there is always a suitable combination of charge generating substances and charge transporting substances that receive and transfer charges.

Inappropriate combinations may cause a number of problems such as a decrease in sensitivity and an increase in residual potential, deterioration in potential stability during repeated use, and a decrease in charging ability.

Therefore, the combination of a charge-generating substance and a charge-transporting substance is extremely important, but there is no morphic law, and it is not easy to find a charge-transporting substance that is compatible with a specific charge-generating substance.

[Problems to be Solved by the Invention] An object of the present invention is to provide an electrophotographic photoreceptor that has sufficiently high sensitivity in the laser diode oscillation wavelength range, that maintains a stable potential during repeated use, and that can be used easily. It is an object of the present invention to provide an electrophotographic photoreceptor that exhibits stable potential characteristics and image characteristics regardless of the environment (temperature), and to provide an electrophotographic apparatus and a facsimile equipped with the electrophotographic photoreceptor.

[Means for Solving the Problems, Effects] The present invention solves the problem by adjusting the Bragg angle 261 in X-ray diffraction of CuKα.
f0.2" contains crystalline oxytitanium phthalocyanine having strong peaks at 9.0o, 14.2", 23.9" and 27.1°, and has the following general formula (
It is composed of an electrophotographic photoreceptor characterized by containing a dihydrophenanthrene compound represented by the formula (1) or a phenanthrene compound represented by the general formula (2).

General Formula In the general formula, R5, R6, R7, R, , R, , R, , 8 and R8 represent an alkyl group, an aralkyl group, or an aryl group that may have a substituent.

Specifically, examples of the alkyl group include groups such as methyl, ethyl, and propyl; examples of the aralkyl group include groups such as benzyl and phenethyl; and examples of the aryl group include groups such as phenyl and naphthyl.

Examples of substituents that alkyl groups, aralkyl groups, and aryl groups may have include alkyl groups such as methyl, ethyl, and propyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine, chlorine, and bromine; Examples include aryl groups such as phenyl.

The X-ray diffraction pattern of oxytitanium phthalocyanine in the present invention is as shown in FIGS. 1, 2, and 3, with Bragg angles (2θ±0.2°) of 9.0°,
°, 23.9° and 27.1°! shows a strong peak. The above peaks are the top four points with the highest peak intensities, and are the main peaks.

What is characteristic about the X-ray diffraction diagrams in Figures 1, 2, and 3 is that among the four peaks mentioned above, 27.1' (7
) The peak is −II<, and the 9.0° peak is the second strongest.

There is also a peak weaker than the above four points at a position of 17.9°, and an even weaker peak at a position of 13.3°.

Also 10.5°~13. O @, 14.8° ~ 17.4°
And there is substantially no peak in the range of 18.2° to 23.2°.

In the present invention, the shape of the peak in X-ray diffraction differs slightly depending on the manufacturing conditions and the measurement conditions. For example, the tip of each peak may be split.

In the case of Fig. 1, the peak at 8.9° is seen near 9°4°, and the peak at 14.2° is seen at 14, another split peak near I°.

The structure of oxytitanium phthalocyanine is represented by the following formula.

In the formula, X, , Xi, X-, and x4 are CI2 or B
r, and n, m, I2 and k are integers of O to 4.

Further, the present invention comprises an electrophotographic apparatus equipped with the electrophotographic photoreceptor of the present invention.

Further, the present invention comprises an electrophotographic apparatus equipped with the electrophotographic photoreceptor of the present invention, and a facsimile machine having a receiving means for receiving image information from a remote terminal.

Typical specific examples of the dihydrophenanthrene compound represented by the general formula (1) and the phenanthrene compound represented by the general formula (2) are listed below.

However, it is not limited to these compounds.

The description of compound examples includes the parts that vary in the basic form: R, , R5, R6, R7, R,, R,, R1 and R8.
By showing only.

Basic type 1 Compound example (1) R,: -CH,R2: -Cu3Ps: -CHx R4:
-GHz compound example (2) R1: -CtHs Rz: -CaHmR
-: -CJs R4: -CJ- Compound example (
3) RI: -CJs Rz: -CJsR-nie(:H(CHs12R4: -(:[(:Hslz Compound Example (4) R1: -CtHs Rx: -CzH-R
, Knee CH 2 R4 Knee CH, -@Compound example (5
) R,: -C,HI R,: -C,H.

R...-＠　　　R...tsu Compound example (6) R + Ninny Mountain R2: Se R, Knee (: Mountain R4: Tsu Compound example (7) RI: -CHt4 R;: -.

Rs: -CH, <R4: is ■ Compound example (8
) R, Knee (: H bottle R,: -CHt-.

R, knee C kidney @ R4: -cH, and compound examples (
9) R...@0P or Rs: -C,H,-@R4: -C2H, or compound example (10) Rz-o R2Rz: -cut@R4: -CH.

Compound Example (11) R,: -C2H,R, Rumored R3ney CH2-oR4: -CtHs Compound Example (12
) R1: sha CH, R, ・(arrow CH3 R, knee CH 2 R4 knee mountain @ Compound example (13) R, knee @ R2: 1 Compound example (14) R, knee o-cH, R, knee @ 1 R, knee @ -CH, R4 knee @ Compound example (15) 8, knee OR=: <■ R, knee @ -cH, R4: Mother compound example (16) Compound example (17) Compound example (18) R1: CH3R2 knee @-C: H3R3: (ToC
H-R-+4(:H3 Compound Example (19) R,: +CtHs R2: +ctH5R,: Tatami C2H, R4: +C Mountain Compound Example (20) CH.

RI: Se R2: Meeting CH.

Compound example (21) R1: Tatami 0 pile R2: → R3: ÷0 pile R1: Ya Compound example (22) R+Ninny-0CHx R2knee@-CHzRl:
Pot 0CH3R4: Tapping H3 Compound Example (23) Compound Example (24) R,: -@-cH, R2: ()cH.

R3: *La R4/Mother Compound example (25) CH3 CH.

Compound Example (26) Compound Example (27) R,: -@R, nee o-CH(CH,1
2R3 knee @ R4: ShaC old CH, 12 compound example (28) R, knee @ -C4H, R2 knee @ R, knee @ -C4H, R, knee @ compound example (29) R1: (anti-CiH, R2: ()C,H.

R3: Yutaka C3H7R4: +C5Ht Compound example (30) Compound example (31) Compound example (32) Compound example (33) R,: ocHz R2: No. 0C2H8R3: -@
-0(:H,R,:shaOC2H5 Compound Example (34) 哩R...4 R2・Mother Compound Example (35) R,: -@-CH,Rz:Br 11r Compound Example (36) Compound Example ( 37) R...No. R2-@R...tsu R4-□ Compound example (38) R1: (Ren CH3Rt: No. CH3 R3=(H fin C2H6R4: (o effect) C2H5 Compound example (39) R1: No. CH3Rt・(G■ R3: No. CH, R, +Nawate+ Compound Example (40) R・・-@-o R2・(To@ R・:+@R4・(To@ Compound Example (41) R3'-o R...Mother R3: Sha CH2 rumor R4: -@-cl (2 compound examples (42) R3, publication -@-CHfcH3+ 2 R4: -@-@-C former CH312 compound examples (43) compound examples ( 44) Compound example (45) Compound example (46)
47) R.: kutsu OCH, R, pseudo 8 R3: - to (I;;:]:) -ocu,
R42 -a MiD Compound Example (48) Basic Type 2 Compound Example (49) R,: -CH, R6: -CH3 R7: -CH5R,: -CH.

Compound example (50) R,: -C2H,R,: -C2H2R,: -C,
H,R,: -C,H5 Compound Example (51) R5neeC,H6R, -C2H.

R, knee CH (CH,], R, knee C knee CH3
12 Compound Examples (52) Rs NiCtHs R-.-C,H.

R, Ni CH*Se Ra Ni Ni H Ba ◇ Compound example (5
3) Rs: -C2H8Ra: -CJsR...be◇
R... Compound Example (54) Rs K2H5Re :Be◇ R,: -C2H,R,:→ Compound Example (55) RS :~CH2-@R6: -@R, KneeC
HI or R8: @ Compound example (56) R8: -CH2@ R,: -c kidney @R? :
-CH2-@R,: -CH2-@Compound example (
57) R6・@R6・SoR? : -C,H4@R・: -C=H layer basic type 3 Compound example (58) R...tsu R...tsu R7 knee CHz R8 knee CH.

Basic type 2 compound example (59) R,: -C,H,R,:yaR,nee cH2+cI2R,: -C crystal compound example (60
) R6・+CH3R,:+cH.

R? Nini H2-@R, Ni CH two compound examples (
61) R5・@R・′@R7・−oR・・Compound example (62) R5 knee@−(:H, R6:−@R, knee knee CH, R, knee.

Compound example (63) R5・be◇　　R6・ya R7: +CH, RIl: Ya Compound example (64) Compound example (65) Compound example (66) R,: -@-cH3R,:sha CH.

R,: -@-(:H,R,: -@-CH3 Compound example (67) R, knee@-C2H5R,: -@-C, H5R7: No. C mountain Rs: +CJs Compound example (68) Basic type 3 ■ Compound example (69) Basic type 2 Compound example (70) R,: -@-ocu, R,・ichiR,nee@-
ocH3Re Ni@ Compound Example (71) Compound Example (72) R,: -@-cH, R,: -@-CH.

Compound example (73) Basic type 4 Compound example (74) Basic type 2 Compound example (75) R5: Say R6: Bay HfCH312R7
Ni (U R8: Published) cH (co,).

Compound example (76) R6: -@-C, HI Re knee@R1:be)
C mountain R゛8: and compound example (77) R5: 4c, o,, R6: b)c, H.

R7: -@-G, H, R: %C, H.

Compound Example (78) Compound Example (79) Compound Example (8o) Compound Example (81) Rs: +O(:Hl' Re Ni@-0C2
H8R, knee o-0(:H,R,:shaOCyama compound example(
82) R8 knee @ R, knee @ (ml Compound example (83) R6: + mountain R6: ☆ r R7: ÷ CH, R6: arrogance r Compound example (84) Compound example (85) R6・package R...tsu Compound Example (86) R: +cH, R6:÷CH.

R7: Hit) c, v, R,! : (o Banknote C mountain compound example (87) R6: Tatami CH, R6: + U R fu: -@-CH3R, Knee 4 Mi + compound example (
88) R,: -@-@ R,: Beto@R7: (To@
R6:4to@Compound example (89) R, knee@R, knee@R,: +c kidney@Ra:'bcH2 rumored compound example (
90) R? : −@−@−cn (CH, + 2Ra
:kCHf(:H31t Compound example (91) Compound example (92) Compound example (93) Compound example (94) R? nee o-CH3R, : -@-cH3 Compound example (
95) Compound Example (96) Basic Type 5 Compound Example (97) R1nee CH3R2•-CH3 R3•-CH3R4•-CH.

Basic type 6 Compound example (98) Rs: -CxHs Rs: -CtHs
Basic type 5 Compound example (99) Compound example (100) R, knee CH3R1: -CHI Basic type 6 Compound example (101) R,: -C,I(,R,: -C2H!R,: -C
2H,R,: -C2H6 Compound example (102) Rs: -CH3Ra: -CHx Basic type 7 Compound example (103) Rs: +CHz Re: -CH3 Basic type 6 Compound example (104) R5: (Kin CH3R6: YuR7・ No. CH3R8 knee @ Compound example (105) R5: -@ R,: -cu2 (C to CH1
Basic type 8 R6 Compound example (106) R...(R...(UR7・ya R・ ■ Basic type 4 Compound example (107) R8neeCH3R,: -CH.

R, knee CH3R,: -CH.

Compound Examples (iog) The combination of a specific crystalline form of oxytitanium phthalocyanine and a specific dihydrophenanthrene compound or phenanthrene compound in the present invention is likely due to matching of ionization potentials or steric interaction at the interface of the charge generating material and the charge transporting material. Due to good target overlap, charge injection from the charge generating material to the charge transporting material is performed well, resulting in good sensitivity, low residual potential, and excellent potential stability during repeated use. It seems that there are.

To exemplify the method for producing crystalline oxytitanium phthalocyanine used in the present invention, for example, titanium tetrachloride and orthophthalodinitrile are reacted in σ-chloronaphthalene to obtain dichlorotitanium phthalocyanine. α-chloronaphthalene, trichlorobenzene, dichlorobenzene, N-methylpyrrolidone,
Wash with a solvent such as N,N-dimethylformamide,
Next, after washing with a solvent such as methanol or ethanol, it is hydrolyzed with hot water to obtain oxytitanium phthalocyanine crystals. The crystals obtained in this way are often a mixture of various polymorphs, and even if this mixture is processed,
It is usually difficult to obtain the crystalline form of oxytitanium phthalocyanine used in the present invention.

Therefore, in order to make it suitable for use in the present invention, it is converted into amorphous oxytitanium phthalocyanine by treatment using an acid basting method.

The obtained amorphous oxytitanium phthalocyanine is treated with methanol at room temperature or under boiling, preferably for 1 hour or more, then dried under reduced pressure, and further treated with n-propyl ether, n-butyl ether, 1so-butyl ether, 5ec-butyl ether, n-amyl ether,
For 5 hours or more using an ether solvent such as n-butyl methyl ether, n-butyl ethyl ether, or ethylene glycol-n-butyl ether, or a monoterpene hydrocarbon solvent such as terpinolene or pinene, or a solvent such as liquid paraffin as a dispersion medium. The crystalline oxytitanium phthalocyanine used in the present invention can be obtained by milling, preferably for 10 hours or more.

Here, the methanol treatment refers to, for example, a suspension stirring treatment of oxytitanium phthalocyanine in methanol.

The milling process is a process performed using a milling device such as a sand mill or a ball mill with a dispersion medium such as glass beads, steel beads, or alumina balls.

An electrophotographic photoreceptor using a crystalline oxytitanium phthalocyanine of the present invention and a dihydrophenanthrene compound or a phenanthrene compound represented by general formula (1) will be described.

A typical layer structure of an electrophotographic photoreceptor is that the photosensitive layer consists of a single layer, and the photosensitive layer simultaneously contains a charge generating material and a charge transporting material, and is formed on a conductive support. be.

In addition, there is a laminated type photosensitive layer in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are sequentially laminated on an N-conducting support; in this case, the charge generation layer The stacking relationship between the charge transport layer and the charge transport layer may be reversed.

The conductive support may be any material as long as it has conductivity, and metals and alloys such as aluminum and stainless steel, metals with conductive layers, plastics, paper, etc. are used, and the shape is cylindrical or film. There are various conditions.

An undercoat layer having barrier and adhesive functions may also be formed between the conductive support and the photosensitive layer.

As the material for the undercoat layer, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, gelatin, etc. are used.

The material is dissolved in a suitable solvent and applied onto a conductive support.

The film thickness is 0.2 to 3.0 LLm.

The photosensitive layer consisting of a sheep layer is prepared by mixing a charge generating material of oxytitanium phthalocyanine crystal used in the present invention and a charge transporting material of a dihydrophenanthrene compound or a phenanthrene compound in a suitable binder resin solution, and then coating and drying the mixture. It is formed.

In the photosensitive layer having a laminated structure, the charge generation layer is formed by dispersing the charge generation material of oxytitanium phthalocyanine crystals used in the present invention together with a suitable binder resin solution, and coating and drying. In this case, there is no binder resin. Good too.

As the binder resin, for example, polyester, acrylic resin, polyvinylcarbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinylidene chloride/acrylonitrile copolymer, etc. are mainly used.

The charge transport layer is formed by coating and drying a paint in which a charge transport material of a dihydrophenanthrene compound or a phenanthrene compound used in the present invention and a binder resin are dissolved in a solvent.

As the binder resin, the same binder resins as those described above can be used.

Examples of the method for coating the photosensitive layer include dip coating, spray coating, spinner coating, bead coating, blade coating, and beam coating.

When the photosensitive layer is a single layer, the film thickness is 5 to 4 oLLm, preferably 10 to 30 um. Further, when the photosensitive layer has a laminated structure, the thickness of the charge generation layer is 0.01 to 10 tLm, preferably 0.05 to 5 um, and the thickness of the charge transport layer is 5 tLm.
-40um, preferably 10-30um.

Furthermore, a thin protective layer may be provided on the surface of the photosensitive layer in order to protect the photosensitive layer from external impact.

When the oxytitanium phthalocyanine crystal of the present invention is used as a charge-generating material, it can be mixed with other charge-generating materials depending on the purpose.

The electrophotographic photoreceptor of the present invention can be used in a laser beam printer,
It can be widely applied not only to printers such as LED printers and CRT printers, but also to ordinary electrophotographic copying machines, facsimile machines, and other electrophotographic application fields.

Next, an electrophotographic apparatus and a facsimile equipped with the electrophotographic photoreceptor of the present invention will be described.

FIG. 10 shows a schematic configuration of a general transfer type electrophotographic apparatus using the drum type photoreceptor of the present invention.

In the figure, reference numeral 1 denotes a drum-type photoreceptor as an image carrier, which is rotated at a predetermined circumferential speed in the direction of the arrow around an axis 1a. The photoreceptor 1 is uniformly charged to a predetermined positive or negative potential on its peripheral surface by the charging means 2 during its rotation process, and then exposed to light image L (
slit exposure, laser beam scanning exposure, etc.).

As a result, electrostatic latent images corresponding to the exposed images are sequentially formed on the circumferential surface of the photoreceptor.

The electrostatic latent image is then developed with toner by the developing means 4,
The toner developed (the image is sequentially transferred by the transfer means 5 to the surface of the transfer material P that is fed from a paper feeding section (not shown) between the photoreceptor 1 and the transfer means 5 in synchronization with the rotation of the photoreceptor 1. It will be done.

The transfer material P that has undergone the image transfer is separated from the photoreceptor surface and introduced into the image fixing means 8, where the image is fixed and a copy is produced.
will be printed out on the outside of the aircraft.

After the image has been transferred, the surface of the photoreceptor 1 is cleaned by a cleaning means 6 to remove residual toner, and subjected to a charge removal process by a pre-exposure means 7, and is repeatedly used for image formation.

As the uniform charging means 2 for the photoreceptor 1, a corona charging device is generally widely used.

Further, as for the transfer device 5, a corona transfer means is generally widely used.

An electrophotographic apparatus is constructed by combining a plurality of components such as the above-mentioned photoreceptor, developing means, and cleaning means into an apparatus unit, and this unit is configured to be detachable from the apparatus main body. It's okay. For example, the photoreceptor 1 and the cleaning means 6 may be integrated into one device unit, and configured to be detachable using a guide means such as a rail of the device body. At this time, the above-mentioned device unit may include a charging means and/or a developing means.

In addition, when an electrophotographic device is used as a copying machine or a printer, light image exposure involves scanning the reflected light or transmitted light from the document, or by reading the document and converting it into a signal. driving the array,
Alternatively, it is performed by driving a liquid crystal shutter array.

Furthermore, when used as a facsimile printer, the optical image exposure is exposure for printing received data.

FIG. 11 is a block diagram showing an example of this case.

A controller 10 controls an image reading section 9 and a printer 18.

The entire controller 10 is controlled by the CPU 16.

The read data from the image reading section is transmitted to the partner station through the transmitting circuit 12. Data received from the partner station is sent to the printer 18 through the receiving circuit 11. Predetermined image data is stored in the image memory. A printer controller 17 controls a printer 18. 13 is a telephone.

The image received from the line 14 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 11, and then the CPo 16 performs signal processing on the image information and sequentially stores it in the image memory 15. Ru. and at least 1
When the image of the page is stored in the memory 16, the image of the page is stored.

The CPTJ 16 reads one page of image information from the memory 15 and sends a signal to the printer controller 17.
Sends page image information.

When the printer controller 17 receives one page of image information from the CPU 16, it controls the printer 18 to record the image information of that page.

Note that during recording by the printer 18, the CPU 16
The next page is being received.

As described above, images are received and recorded.

Next, an example of producing oxytitanium phthalocyanine crystals used in the present invention will be shown.

Production Example 1 In 100 g of a-chloronaphthalene, 50 g of O-phthalodinitrile and 2.0 g of titanium tetrachloride were heated and stirred at 200°C for 3 hours, then cooled to 50°C and the precipitated crystals were separated by filtration to obtain dichlorotitanium. A phthalocyanine paste was obtained.

Next, this was washed with N,N-dimethylformamide Roomε at 100° C. under stirring, and then washed twice with 100 m of methanol at 60° C., and then filtered. Furthermore, the obtained paste was soaked in 100 mj2 of deionized water.
The mixture was stirred at 80° C. for 1 hour and filtered to obtain blue oxytitanium phthalocyanine crystals. Yield 4.3g Elemental analysis value (C3□H+sN s T 10 ) Calculated value (%) Actual value (%) C66,6866,50 H2,802,99 N 19.44 19.42 CJ2 0.00 0.47 Next Next, the crystals were dissolved in 30 mg of concentrated sulfuric acid and added dropwise to 300 m of deionized water at 20° C. under stirring to cause reprecipitation, filtration, and thorough washing with water to obtain amorphous oxytitanium phthalocyanine.

4.0 g of the amorphous oxytitanium phthalocyanine thus obtained was dissolved in 100 methanol at room temperature (22°C).
The mixture was suspended and stirred for 8 hours, filtered, and dried under reduced pressure to obtain low-crystalline oxytitanium phthalocyanine.

40 mff of n-butyl ether was added to 2.0 g of this oxytitanium phthalocyanine, and a milling process was performed at room temperature (22°C) for 20 hours with glass beads of 1 mm diameter.

The solid content was taken out from this dispersion, thoroughly washed with methanol and then with water, and dried to obtain crystalline oxytitanium phthalocyanine used in the present invention. Yield: 1.8g Crystalline form of oxytitanium phthalocyanine
A line diffraction diagram is shown in FIG.

In addition, KBr pellets were prepared and the infrared absorption spectrum of this crystal was measured, and the results are shown in FIG.

FIG. 8 shows the results of an ultraviolet absorption spectrum measured using a dispersion of this crystal in n-butyl ether.

Production Example 2 2.0 g of methanol-treated oxytitanium phthalocyanine obtained in the same manner as Production Example 1 was added with 50 m of pinene.
! was added, and milling was performed at room temperature (22° C.) for 20 hours with glass beads of 1 mm diameter. The solid content was taken out from this dispersion, thoroughly washed with methanol and then with water, and dried to obtain crystalline oxytitanium phthalocyanine used in the present invention. Yield: 1.8g Crystalline form of oxytitanium phthalocyanine
A line diffraction diagram is shown in FIG.

Production Example 3 Amorphous oxytitanium phthalocyanine obtained by the same method as Production Example 14. Methanol at 100 m°C was added to Og, and the mixture was boiled for 30 hours under suspension stirring, followed by filtration and drying under reduced pressure to obtain oxytitanium phthalocyanine crystals. Yield: 3.6g Next, 60mj2 of ethylene glycol-n-butyl ether was added to this oxytitanium phthalocyanine 2.0g, and milling was performed at room temperature (22°C) for 15 hours with glass beads of 1 mmφ. The solid content was taken out from this dispersion, thoroughly washed with methanol and then with water, and dried to obtain crystalline oxytitanium phthalocyanine used in the present invention. Yield: 1.8g Crystalline form of oxytitanium phthalocyanine
A line diffraction diagram is shown in FIG.

Comparative Production Example 1 JP-A No. 61-239248 (USP 4°728.
592), the so-called α
A crystalline form of oxytitanium phthalocyanine called type was obtained.

This X-ray diffraction diagram is shown in FIG.

Comparative Production Example 2 JP-A-62-67094 (USP 4,66499)
According to the production example disclosed in No. 72), a crystalline oxytitanium phthalocyanine, so-called type A, was obtained.

This X-ray diffraction diagram is shown in FIG.

Comparative Production Example 3 According to the production example disclosed in JP-A-64-17066, oxytitanium phthalocyanine having the same crystal form as that disclosed in JP-A-64-17066 was obtained.

This X-ray diffraction diagram is shown in FIG.

Note that the X-ray diffraction measurements were performed using Cu Ka rays under the following conditions.

Convenient measuring device: Rigaku Denki X-ray diffraction device RAD-A system .020deg.

Start angle (2θ): 3deg.

Stop angle (2θ): 40d, eg Divergence slit 0.5deg Scattering slit 0.5deg.

Receiving slit: 0.3mm curved monochromator for convenience [Example 1 Parts in the following examples are parts by weight.

Example 1 A 0.9 LLm undercoat layer made of vinyl chloride-maleic anhydride-vinyl acetate copolymer was formed on an aluminum plate.

Next, 4 parts of crystalline oxytitanium phthalocyanine obtained in Production Example 1 and 2 parts of polyvinyl butyral were added to 100 parts of cyclohexanone and dispersed for 12 hours using a schisand mill, and diluted by adding 100 parts of methyl ethyl ketone. , this dispersion was applied onto the undercoat layer so that the film thickness after drying was 0.
A charge generation layer of 15 μm and 15 μm was formed.

Next, 5 g of the dihydrophenanthrene compound of Compound Example (18) and 4 g of bisphenol Z type tricarbonate (viscosity average molecular weight 35,000) were dissolved in 40 g of tetrabenzene, and this was placed on the charge generation layer after drying. A charge transport layer was formed by coating with a Mayer bar to a thickness of 17 um, and an electrophotographic photoreceptor was prepared, which was designated as photoreceptor 1.

Comparative Example 1 An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the σ-type oxytitanium phthalocyanine obtained in Comparative Production Example 1 was used, and this was designated as Comparative Photoreceptor 1.

Comparative Example 2 An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that the A-type oxytitanium phthalocyanine obtained in Comparative Production Example 2 was used, and this was designated as Comparative Photoreceptor 2.

Comparative Example 3 An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the same crystal form of oxytitanium phthalocyanine as disclosed in JP-A-64-17066 obtained in Comparative Production Example 3 was used. This will be referred to as comparative photoreceptor 3.

Each electrophotographic photoreceptor, Photoreceptor 1, Comparative Photoreceptor 1.2, and 3, was printed using a laser beam printer (product name: LBP-SX,
Paste it on the cylinder of a modified Canon machine, set it to charge so that the dark potential is 1700V, and irradiate it with a laser beam with a wavelength of 802 nm to lower the 1700V potential to -toov. The amount of light EΔsoo required for this was measured.

゛Furthermore, the potential when a light intensity of 20 uJ/cm 2 was irradiated was measured as the residual potential vr.

Example 1 1 0.28 10 Comparative Example 1 Comparative 1' 0.86 45//2//2 0
．． 84 40 Tsuno 3 no t30.5935 In addition, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the crystalline oxytitanium phthalocyanine obtained in Production Example 2 and Production Example 3 was used as the charge generating material. These will be referred to as photoreceptor 2 and photoreceptor 3.

When sensitivity was measured in the same manner as in Example 1, high sensitivity characteristics similar to those of Photoreceptor 1 were obtained.

Next, photoreceptor 1. Regarding comparative photoreceptors 1.2 and 3,
3 consecutive times with each photoconductor set to dark potential -700V and light potential -100V in the following environments: humidity 10%, temperature 5℃, humidity 50%, temperature 18℃, humidity 80%, and temperature 35℃. A durability test of 1,000 sheets of paper was conducted to measure the dark area potential and bright area potential and evaluate the image after the durability test.

Photoconductor 1 produced images as good as the initial image in all environments and after durability, but Comparative Photoconductors 1, 2 and 3 had blurring on the white background in all environments, and %, which was even more remarkable at an air temperature of 35° C., especially in comparison photoreceptor 3.

In addition, when comparative photoreceptors 1.2 and 3 were adjusted using the density adjustment lever to remove ground blur, the density of the black background portion was insufficient.

FIG. 9 shows the distribution of spectral sensitivity when the maximum value of spectral sensitivity of photoreceptor 1 is set to 100.

In this way, the electrophotographic photoreceptor of the present invention has a molecular weight of 770 to 810.
It exhibits stable high sensitivity characteristics in the long wavelength region around nm.

Examples 2 to 10 Electrophotographic photoreceptors were prepared in the same manner as in Example 1 except that the oxytitanium phthalocyanine crystal obtained in Production Example 1 was combined with several of the compound examples, and designated as photoreceptors 2 to 1o.

As in Example 1, each photoconductor was attached to the cylinder of a modified laser beam printer (product name LBP-5X, manufactured by Canon ■), charged so that the dark area potential was 1700 V, and the wavelength The amount of light EΔgoo required to lower the potential from -700V to -100V by emitting a laser beam of 802 nm was measured.

Furthermore, the potential when a light intensity of 20 uJ/cm 2 was irradiated was measured as the residual potential (1).

In addition, each photoreceptor was set to a dark area potential of -700V and a bright area potential of -10V.
A continuous paper passing durability test of 3,000 sheets was conducted with the setting reset to 0 V, and the amount of variation ΔV and Δvj in the dark potential and bright potential during the initial stage and after the 3,000-sheet durability test were determined. Show the results.

2 2 (2) 0.413 3
(12) 0.284 4 (1
6) 0.205 5 (20)
0.196 6 (34) 0.26
7 7 (52) 0.
408 8 (66) 0
．． 209 9 (69)
0.2410 10 (87)
0.212 2 +25 20
153 3 -1.5
10 101010'-555 Comparative Examples 4 to 21 Example 2.4 except that the oxytitanium phthalocyanine produced in Comparative Production Examples 1 to 3 and the dihydrophenanthrene compound or phenanthrene compound used in the previous example were used in combination. Electrophotographic photoreceptors were prepared in the same manner as in 5.6.8 and 9, and evaluated in the same manner.

10 10 1 (2]],,5
15 3 (34) 4 1.24+7
5 50 605 1.14+60
50 656 0.91 +65
35 657 0.82-45 45
358 0.73-40 50
459 0.64-35 40 50
10 0.81 -45 50 401
1 0.72-30 55 4512
0.59-30 40 4513
0.79-40 35 5514
0.81 -45 45 4515
0.58-35 50 3516
0.83-50 35 4017
0.89-45 30 3518
0.61 -40 30 35], 9
0.94 -55 45 4520
0, 89 -40 40 4021
0.64-35 35 35 Comparative Example 22
~27 In Example 2, compounds H-1, H-2, H-3, H-4 having the following structural formula were used instead of the dihydrophenanthrene compound.
.

2222H-1 2323H-2 2424H-3 2525H-4 2626H-5 2727H-6 220,50353585 230,52754575 240,70505565 250,41554560 260,58402515 270,586550 25 From the above results, the electrophotographic photoreceptor of the present invention has high sensitivity, It can be seen that the residual potential and repetition characteristics are extremely excellent.

Example 11 Example 1 was deposited on an aluminum sheet substrate having a thickness of 50 LLm.
An undercoat layer similar to that in Example 1 was formed using a bar code, and a charge transport layer similar to that in Example 1 was further formed thereon to a thickness of 20 LLm.

Next, 5 parts of bisphenol Z type car recarbonate were dissolved in 68 parts of cyclohexanone, 3 parts of oxytitanium phthalocyanine showing the X-ray diffraction pattern obtained in Production Example 1 was mixed with this solution, and the solution was mixed with a sand mill for 1 hour. After dispersion, 5 parts of bisphenol Z type polycarbonate and 10 parts of the charge transport material used in Example 1 were dissolved, and 40 parts of tetrahydrofuran and 40 parts of dichloromethane were added to dilute the solution to prepare a dispersed coating. This paint is applied onto the charge transport layer by a spray coating method and dried to form a charge generation layer with a thickness of 6 LLm, thereby producing an electrophotographic photoreceptor, which is referred to as photoreceptor 11.

Comparative Example 28 An electrophotographic photoreceptor was prepared in the same manner as in Example 11 except that the α-type oxytitanium phthalocyanine produced in Comparative Production Example 1 was used as the charge-generating material, and this was used as Comparative Photoreceptor 2.
8.

Comparative Example 29 An electrophotographic photoreceptor was prepared in the same manner as in Example 11 except that the A-type oxytitanium phthalocyanine produced in Comparative Production Example 2 was used as the charge-generating material, and this was used as Comparative Photoreceptor 2.
9.

Comparative Example 30 JP-A-64 produced in Comparative Production Example 3 as a charge generating material
An electrophotographic photoreceptor was prepared in the same manner as in Example 11, except that oxytitanium phthalocyanine having the same crystal form as disclosed in Japanese Patent No. 17066 was used, and this was designated as Comparative Photoreceptor 30.

Photoconductor 11, comparison photoconductors 28, 29, and 30 were tested using an electrostatic tester (EPA-8100, manufactured by Kawaguchi Denki ■).
It was evaluated using

The evaluation begins with a surface potential of +700 due to positive corona charging.
V, and then exposed to 802 nm monochromatic light separated by a monochromator to raise the surface potential to +
The amount of light when the amount of light decreased to 200 square meters was measured and defined as the sensitivity. Show the results.

EΔ5oo(u J/cm21 Example 11 0.35 Comparative example 28 1.13 Comparative example 29 1 10 Comparative example 3o o, g.

[Effects of the Invention] The electrophotographic photoreceptor of the present invention has a photosensitive layer containing a specific crystal form of oxytitanium phthalocyanine as a charge-generating material and a specific dihydrophenanthrene compound or phenanthrene compound as a charge-transporting material. 1) It has high sensitivity at the laser diode oscillation wavelength, (2) It shows stable image characteristics in the electrophotographic process, and (3)
It has the remarkable effect of superior positional stability.

Furthermore, similar effects can be achieved in electrophotographic devices and facsimile machines equipped with the electrophotographic photoreceptor.

[Brief explanation of drawings]

Figure 1 is an XwA diffraction diagram of crystalline oxytitanium phthalocyanine obtained in Production Example 1, Figure 2 is an X-ray diffraction diagram of crystalline oxytitanium phthalocyanine obtained in Production Example 2, and Figure 3 is the produced 3 is an X-ray diffraction diagram of crystalline oxytitanium phthalocyanine obtained in Example 3. FIG. Figure 4 is an X-ray diffraction diagram of oxytitanium phthalocyanine obtained in Comparative Production Example 1, Figure 5 is an X-ray diffraction diagram of oxytitanium phthalocyanine obtained in Comparative Production Example 2, and Figure 6 is an X-ray diffraction diagram of oxytitanium phthalocyanine obtained in Comparative Production Example 2. FIG. 2 is an X-ray diffraction diagram of oxytitanium phthalocyanine obtained in FIG. Figure 7 is an infrared absorption spectrum diagram (KBr method) of crystalline oxytitanium phthalocyanine obtained in Production Example 1;
FIG. 8 is an ultraviolet absorption spectrum diagram of crystalline oxytitanium phthalocyanine obtained in Production Example 1. FIG. 9 shows the electrophotographic photoreceptor (photoreceptor 1) prepared in Example 1.
) is a spectral sensitivity distribution diagram. FIG. 10 is a schematic diagram of a general transfer type electrophotographic apparatus using the drum type photoreceptor of the present invention. Reference numeral 1 is a drum-type photoreceptor (electrophotographic photoreceptor of the present invention) as an image carrier, and 2 is a corona charging device! , 3 is the exposure section, 4
is a developing means, 5 is a transfer means, 6 is a cleaning means, 7
8 is a pre-exposure means, 8 is an image fixing means, L is a light image exposure, and P is a transfer material subjected to image transfer. FIG. 11 is a block diagram of a facsimile machine using an electrophotographic device as a printer. Reference numeral 9 is an image reading unit, 10 is a controller, 11 is a receiving circuit, 12 is a transmitting circuit, 13 is a telephone, 14 is a line, 1
5 is an image memory, 16 is a CPU, 17 is a printer controller, and 18 is a printer.

Claims (1)

[Claims] 1. Bragg angle 2θ±0 in X-ray diffraction of CuKα.
2° is 9.0°, 14.2°, 23.9° and 27.
It is characterized by containing crystalline oxytitanium phthalocyanine having a strong peak at 1°, and containing a dihydrophenanthrene compound represented by the following general formula (1) or a phenanthrene compound represented by the general formula (2). Electrophotographic photoreceptor. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) In the formula, R_1, R_2, R_3, R_4, R_5, R_
6, R_7 and R_8 represent an alkyl group, an aralkyl group, or an aryl group that may have a substituent. 2. The electrophotographic photosensitive material according to claim 1, wherein in the dihydrophenanthrene compound represented by the general formula (1), at least two or more of R_1, R_2, R_3 and R_4 are phenyl groups which may have a substituent. body. 3. The electrophotographic photoreceptor according to claim 1, wherein in the phenanthrene compound represented by general formula (2), at least two or more of R_5, R_6, R_7 and R_8 are phenyl groups which may have a substituent. 4. An electrophotographic apparatus comprising the electrophotographic photoreceptor according to claim 1. 5. A facsimile machine comprising an electrophotographic apparatus comprising the electrophotographic photoreceptor according to claim 1 and a receiving means for receiving image information from a remote terminal.