JP2617004B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor containing oxotitanium phthalocyanine and manganese phthalocyanine as a charge generating material in a photosensitive layer.

[Related Art] In recent years, as a terminal printer, a non-impact printer to which electrophotographic technology is applied has been widely used instead of a conventional impact printer. These are mainly laser beam printers using laser light as a light source, and a semiconductor laser is used as the light source in terms of cost, size of the apparatus, and the like.

Currently, mainly used semiconductor lasers have an oscillation wavelength of 790 ± 20 nm, which is a long wavelength, and therefore, development of an electrophotographic photoreceptor having sufficient sensitivity to such long-wavelength light has been advanced.

The sensitivity on the long wavelength side varies depending on the type of charge generation material, and many charge generation materials have been studied.

Representative charge generation materials include phthalocyanine pigments,
Examples include azo pigments, cyanine dyes, azulene dyes, and squarylium dyes.

On the other hand, as charge generation materials sensitive to long-wavelength light, recently, metal phthalocyanines such as aluminum chlorophthalocyanine, chloroindium phthalocyanine, manganese phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine, oxotitanium phthalocyanine (titanyl phthalocyanine) or metal-free materials Many studies have been made on phthalocyanines (metal-free phthalocyanines).

Among them, many phthalocyanine compounds are known to have polymorphs.
Type, β type, γ type, δ type, ε type, χ type, τ type and the like. For copper phthalocyanine, α type, β type, γ type, δ type, ε type, χ type
Types and the like are generally known.

It is also generally known that the crystal type greatly affects the electrophotographic characteristics (sensitivity, potential stability during durable use, etc.) and the characteristics of the paint when formed into a paint.

Furthermore, oxotitanium phthalocyanine, which has high sensitivity particularly to light of a long wavelength, has polymorphs as in the case of many phthalocyanines such as the above-mentioned metal-free phthalocyanine and copper phthalocyanine.

For example, JP-A-59-49544 (corresponding to USP 4,444,
861), JP-A-59-166959, JP-A-61-239248 (corresponding to USP 4,728,592), JP-A-62-67094, (corresponding to USP 4,664,997), and JP-A-63-67094. JP-A-366, JP-A-63-116158, JP-A-63-198067 and JP-A-64-17066 report oxotitanium phthalocyanines having different crystal forms.

[Problems to be Solved by the Invention] The present invention improves the sensitivity of an electrophotographic photoreceptor using oxotitanium phthalocyanine as a charge generating material, and a charged memory (hereinafter referred to as a transfer memory) generated in a transfer step when used in a reversal development system. ) Is mainly intended to improve image defects.

Means for Solving the Problems The present inventors have found a method for improving the sensitivity of an electrophotographic photoreceptor using oxotitanium phthalocyanine as a charge generating material and almost eliminating image defects caused by a transfer memory. Was completed.

That is, the object of the present invention is that the photosensitive layer contains oxotitanium phthalocyanine and 0.1 to 5000 ppm, preferably 0.5 to 3000 ppm, and most preferably 1 to 1000 ppm of manganese phthalocyanine based on the oxotitanium phthalocyanine. Achieved by an electrophotographic photoreceptor.

The structure of oxotitanium phthalocyanine is Is represented by

Here, X ¹ , X ² , X ³ and X ⁴ represent Cl or Br, and n, m,
l and k are integers from 0 to 4.

The method for producing oxotitanium phthalocyanine according to the present invention will be illustratively described.

First, for example, titanium tetrachloride and orthophthalodinitrile are reacted in α-chloronaphthalene to obtain dichlorotitanium phthalocyanine. This is washed with a solvent such as α-chloronaphthalene, trichlorobenzene, dichlorobenzene, N-methylpyrrolidone, N, N-dimethylformamide, and then washed with a solvent such as methanol and ethanol, and then hydrolyzed with hot water. An oxotitanium phthalocyanine crystal is obtained. Since the crystals thus obtained are often a mixture of various polymorphs, they are converted into amorphous oxotitanium phthalocyanine by an acid pasting method.

Next, this amorphous oxotitanium phthalocyanine
Milling at 40-200 ° C, preferably 60-120 ° C,
5 minutes to 24 hours by adding a solvent such as cyclohexanone,
The oxotitanium phthalocyanine crystal of the present invention can be obtained by preferably treating for 15 minutes to 10 hours.

The X-ray diffraction pattern of the oxotitanium phthalocyanine crystal in the present invention shows strong peaks at Bragg angles 2θ ± 0.2 ° of 7.4 °, 9.2 °, 10.4 °, 11.6 °, 13.0 °, 14.3.
゜, 15.0 ゜, 15.5 ゜, 23.4 ゜, 24.1 ゜, 26.2 ゜ and 27.2
The peak is observed at the position of ゜, and the above-mentioned peak is the 16 points with the highest peak intensity. The specific diffraction pattern is, for example, that shown in FIG.

Hereinafter, typical layer constitutions of the electrophotographic photosensitive member of the present invention are shown in FIGS. 2 and 3.

FIG. 2 shows that the photosensitive layer 1 comprises a single layer, and the photosensitive layer 1 simultaneously contains a charge generating material 2 and a charge transporting material (not shown).

 Reference numeral 3 denotes a conductive support.

FIG. 3 shows that the photosensitive layer 1 has a laminated structure of a charge generation layer 4 and a charge transport layer 5, and the charge generation layer 4 is formed of a charge generation material 2.
It contains.

Note that the stacking relationship between the charge generation layer 4 and the charge transport layer 5 in FIG. 3 may be reversed.

When the electrophotographic photoreceptor of the present invention is manufactured, the conductive support 3 may have any conductivity as long as it has conductivity, and a metal such as aluminum or corrosion-resistant steel (stainless steel) or a conductive material provided with a conductive layer. Examples thereof include plastic and paper, and examples of the shape include a cylindrical shape and a film shape.

Further, an undercoat layer having a barrier function and an adhesive function can be provided between the conductive support 3 and the photosensitive layer 1.

As a material of the undercoat layer, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, gelatin or the like is used.

These are dissolved in a suitable solvent and coated on a conductive support. The film thickness is usually from 0.2 to 3.0 μm.

When a photosensitive layer consisting of a single layer as shown in FIG. 2 is formed, for example, the oxotitanium phthalocyanine charge generating material of the present invention and a charge transporting material are mixed in a suitable liquid material of a binder resin described later, for example, in a solution, It can be obtained by coating and drying.

A method for forming a charge generation layer of a photosensitive layer having a laminated structure as shown in FIG. 3 is to obtain the oxotitanium phthalocyanine charge generation material of the present invention by dispersing it with an appropriate binder resin solution, coating and drying. Can be. In this case, the binder resin may not be provided.

As the binder resin used here, for example, polyester resin, acrylic resin, polyvinyl carbazole resin, phenoxy resin, polycarbonate resin, polyvinyl butyral resin, polystyrene resin, polyvinyl acetate resin, polysulfone resin, polyarylate resin or vinylidene chloride-acrylonitrile copolymer A coalescing resin or the like is mainly used.

The charge transport layer is mainly formed by applying and drying a paint in which a charge transport material and a binder resin are dissolved or dispersed in a solvent.

Examples of the charge transport material used include various triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, and the like.

Further, as the binder resin, those described above can be used.

As a method for applying these photosensitive layers, dipping, spray coating, spinner coating, bead coating, blade coating, beam coating, and the like can be used.

When the photosensitive layer is a single layer, the thickness is 5 to 40 μm, preferably 10 to 30 μm.

When the photosensitive layer has a laminated structure, the thickness of the charge generation layer is 0.
The thickness is in the range of 01 to 10 μm, preferably 0.05 to 5 μm, and the thickness of the charge transport layer is in the range of 5 to 40 μm, preferably 10 to 30 μm.

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

Next, a synthesis example of the oxotitanium phthalocyanine crystal used in the present invention will be described.

 Hereinafter, "part" indicates "part by weight".

[Synthesis Example 1] In 100 parts of α-chloronaphthalene, 5.0 parts of o-phthalodinitrile and 13.5 parts 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. ,
A paste of dichlorotitanium phthalocyanine was obtained.
Next, this was washed with 100 parts of N, N'-dimethylformamide heated to 100 ° C. with stirring, and then washed twice with 100 parts of methanol at 60 ° C., followed by filtration. Further, the obtained paste was stirred in 100 parts of deionized water at 80 ° C. for 1 hour and then filtered to obtain blue oxotitanium phthalocyanine crystal.

 The elemental analysis values of this compound were as follows.

Elemental analysis _{(C 32 H 16 N 8 TiO} ) C H N Cl Calculated (%) 66.68 2.80 19.44 0.00 Found (%) 66.50 2.99 19.42 0.47 Next, dissolve the crystals in 30 parts of concentrated sulfuric acid, 20 ° C. Was added dropwise to 300 parts of deionized water under stirring to reprecipitate, and then filtered to obtain amorphous oxotitanium phthalocyanine. 10 parts of the thus obtained amorphous oxotitanium phthalocyanine were mixed with 15 parts of sodium chloride and 7 parts of diethylene glycol, and milled in an automatic mortar at 80 ° C. for 60 hours. Next, the treated product was washed sufficiently with water to completely remove sodium chloride and diethylene glycol. After drying under reduced pressure, 200 parts of cyclohexanone and glass beads having a diameter of 1 mm were added, and the mixture was treated by a sand mill for 30 minutes to obtain an oxotitanium phthalocyanine crystal of the present invention. FIG. 1 shows an X-ray diffraction pattern of this oxotitanium phthalocyanine crystal.

The measurement of the X-ray diffraction pattern in the present invention was performed using Cu- _Kα rays under the following conditions.

Measuring machine used: Rigaku Denki X-ray diffractometer X-ray bulb: Cu Voltage: 50kV Current: 40mA Scanning method: 2θ / θ scan Sampling interval: 0.020deg. Start angle (2θ): 3deg. Stop angle (2θ): 40deg Divergence slit: 0.5deg. Scattering slit: 0.5deg. Receiving slit: 0.3mm Using curved monochromator The electrophotographic photoreceptor of the present invention can be used not only for printers such as laser beam printers, LED printers and CRT printers, but also for ordinary printers. It can be widely applied to electrophotographic copying machines and other electrophotographic application fields.

Further, the oxotitanium phthalocyanine used in the present invention is not limited to those having the above-mentioned crystal structure. For example, JP-A-61-239248 (corresponding to:
U.S. Pat. No. 4,728,592) discloses an oxotitanium phthalocyanine crystal referred to as .alpha.
No. 094 (corresponding to US Pat. No. 4,664,997), an oxotitanium phthalocyanine crystal called type A, and an oxotitanium phthalocyanine crystal having a crystal type disclosed in JP-A-64-17066. Can also be used.

Example 1 50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resole type phenol resin,
20 parts of methyl cellosolve, 5 parts of methanol and 0.002 part of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3000) were mixed and dispersed for 2 hours in a sand mill device containing glass beads having a diameter of 1 mm for a conductive layer paint. Was prepared.

Aluminum cylinder (outer diameter 30mm x length 260.5mm)
The above paint is applied by dip coating and dried at 140 ° C for 30 minutes.
A conductive layer having a thickness of 20 μm was formed.

A solution obtained by dissolving 5 parts of a 6-66-610-12 quaternary polyamide copolymer resin in a mixed solvent of 70 parts of methanol and 25 parts of butanol was applied by dipping and dried to reduce the thickness to 1 μm. Layers were provided.

Next, 4 parts of the oxotitanium phthalocyanine crystal obtained in Synthesis Example 1 of the present invention and 0.1 ppm of manganese phthalocyanine and 2 parts of a polyvinyl butyral resin with respect to the oxotitanium phthalocyanine crystal were added to cyclohexanone 100%.
Was mixed and dispersed in a sand mill containing glass beads having a diameter of 1 mm for 2 hours, and 100 parts of methyl ethyl ketone was added thereto. After diluting, the mixture was recovered to obtain a coating solution, which was applied on the undercoat layer. After that, the resultant was dried at 80 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.

Next, the following structural formula A solution was prepared by dissolving 10 parts of the charge transporting material represented by the following formula and 10 parts of a bisphenol Z-type polycarbonate resin in 60 parts of monochlorobenzene, and applied to the charge generating layer by dipping. This is dried at a temperature of 110 ° C. for 1 hour to form a film 2
A charge transport layer of 0 μm was formed.

Example 2 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 0.5 ppm.

Example 3 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 1 ppm.

Example 4 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 10 ppm.

Example 5 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 100 ppm.

Example 6 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 1000 ppm.

Example 7 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 3000 ppm.

Example 8 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 5000 ppm.

Comparative Example 1 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that manganese phthalocyanine was not contained.

Comparative Example 2 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 0.01 ppm.

Comparative Example 3 In Example 1, the content of manganese phthalocyanine was
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the amount was 10,000 ppm.

<Sensitivity and Image Evaluation> Each of the photoreceptors obtained in Examples 1 to 8 and Comparative Examples 1, 2 and 3 was subjected to a laser beam printer [trade name: L
BP-SX (manufactured by Canon)] and the dark area potential is -700.
(V), and when irradiated with a laser beam having a wavelength of 802 nm, the potential of -700 (V) is set to -150.
The sensitivity was measured by measuring the amount of light required to change the value to (V).

Next, in the above-mentioned potential setting, obtained in each of the above experimental examples.
After conducting a durability test of 4000 continuous sheets of B5 size paper using 11 types of photoconductors, focusing on the density of the image caused by the transfer memory of the A4-B5 section in the section on the paper, image evaluation Was performed.

 Table 1 shows the results.

As can be seen from Table 1, addition of manganese phthalocyanine to oxotitanium phthalocyanine in an amount of 0.1 to 5000 ppm made it possible to improve sensitivity and substantially eliminate image defects due to transfer memory.

[Effects of the Invention] The photosensitive layer of the present invention contains 0.1 to 5000 ppm of manganese phthalocyanine together with oxotitanium phthalocyanine, thereby making it possible to improve sensitivity and substantially eliminate image defects due to transfer memory. .

[Brief description of the drawings]

[Types of Drawings] FIG. 1 is an X-ray diffraction diagram of the oxotitanium phthalocyanine crystal of the present invention, and FIGS. 2 and 3 are schematic cross-sectional views of a layer structure of an electrophotographic photosensitive member. [Main Signs in the Drawing] 1 ... Photosensitive layer, 2 ... Charge generating material, 3 ... Conductive support, 4 ... Charge generating layer, 5 ... Charge transport layer.

Claims (1)

(57) [Claims] An oxotitanium phthalocyanine and 0.1 to 5 parts by weight of the oxotitanium phthalocyanine in the photosensitive layer.
An electrophotographic photoreceptor containing 000 ppm of manganese phthalocyanine.