JPH1048860A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoreceptor having satisfactory sensitivity to light of long wavelength from semiconductor laser as a light source by forming a photosensitive layer contg. a phthalocyanine pigment and a specified compd. SOLUTION: This photoreceptor has a photosensitive layer contg. a phthalocyanine pigment and a compd. represented by the formula, wherein R1 is lower alkyl, each of R2 and R3 is optionally substd. methylene or ethylene, each of Ar1 and Ar2 is optionally substd. aryl, (l) is an integer of 0-4, each of (m) and (n) is an integer of 0-2, m+n>=2 and l+m+n<=6. The compd. represented by the formula is obtd. by dissolving a deriv. having chloroalkyl groups and hydrocarbon in nitromethane, adding a catalyst such as zinc chloride or aluminum chloride under stirring in a flow of gaseous nitrogen and bringing them into reaction at a low temp. The phthalocyanine pigment is preferably an X or τ type metal-free phthalocyanine pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor, and more particularly to a high-sensitivity electrophotographic photoreceptor containing a phthalocyanine pigment and a specific compound, which is suitably used for a laser printer, a digital copying machine, and a laser facsimile.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as Se, CdS, and ZnO have been used as a photoconductive material for an electrophotographic photoreceptor, but they have problems such as photosensitivity, thermal stability, and toxicity. In recent years, electrophotographic photoreceptors using organic photoconductive materials have been actively developed. The reasons are that an electrophotographic photosensitive member using an organic photoconductive material is inexpensive, suitable for mass production, has no pollution, and has a high degree of freedom in material selection. Further, a function-separated type photoreceptor having a charge generation amount and a charge transport layer has also been proposed, and higher sensitivity and higher durability are expected.

On the other hand, in the copying industry, high image quality, an editing function, and a complex processing function have recently been required. Along with this, non-impact printer technology has been developed, and digital recording apparatuses such as laser printers, laser facsimile machines, digital copiers and the like have been widely used.

As a light source used in the digital recording apparatus, a semiconductor laser is used in many cases because of its small size, low cost, and simplicity. However, the oscillation wavelength of the semiconductor laser currently used is as follows. It is limited to the near infrared region of 750 nm or more. Therefore, at least 750-8 electrophotographic photosensitive members used in these apparatuses are required.
It is required to have photosensitivity in a wavelength region of 50 nm.

As the organic photoconductive material satisfying this requirement, squarium pigment, phthalocyanine pigment, eutectic complex of pyrylium dye and polycarbonate, pyrrolopyrrole pigment, azo pigment and the like are known. Since it has spectral absorption up to a relatively long wavelength region and has photosensitivity, and various variations can be obtained depending on the type of central metal and crystal form, it has been actively studied as an electrophotographic photoreceptor for semiconductor lasers. ing.

[0006] The phthalocyanine pigments having good sensitivity known so far include ε-type copper phthalocyanine, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine, vanadyl phthalocyanine, titanyl phthalocyanine and the like. Depends on the type and crystal type of the pigment.In order to increase the sensitivity, a new charge transport material with high mobility is newly developed, or a new photoreceptor prescription using a different charge generator with high sensitivity is used. It was a disadvantage that it took a lot of cost and time to reassemble.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned conventional problems and to provide a copying machine having good sensitivity to long-wavelength light, especially using a semiconductor laser light as a light source. An object of the present invention is to provide an electrophotographic photosensitive member that is optimal for a recording device such as a printer. Another object of the present invention is to provide an electrophotographic photoreceptor that is easily and highly sensitive without spending time and money.

[0008]

The electrophotographic photoreceptor of the present invention achieves the above objects. According to the present invention,
An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains a phthalocyanine pigment and a compound represented by the following general formula (I) is provided. You.

[0009]

Embedded image (Wherein, R ₁ represents a lower alkyl group, R ₂ and R ₃ represent a substituted or unsubstituted methylene group or an ethylene group;
r ₁ and Ar ₂ represent a substituted or unsubstituted aryl group. l
Is an integer of 0 to 4; m and n are integers of 0 to 2;
+ N is an integer of 2 or more, and l + m + n is an integer of 6 or less. or,
The unsubstituted site on the benzene ring represents a hydrogen atom. )

The compound represented by the general formula (I) is
For example, it can be obtained by dissolving the corresponding chloroalkyl derivative and hydrocarbon in nitromethane, adding a catalyst such as zinc chloride or aluminum chloride under stirring and a nitrogen stream, and reacting at a low temperature. Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited only to these specific examples.

[0011]

[Table 1-1]

[0012]

[Table 1-2]

[0013]

[Table 1-3]

[0014]

[Table 1-4]

[0015]

[Table 1-5]

[0016]

[Table 1-6]

[0017]

[Table 1-7]

[0018]

[Table 1-8]

[0019]

[Table 1-9]

[0020]

[Table 1-10]

As the phthalocyanine-based pigment, all phthalocyanine-based pigments generally used for electrophotographic photoreceptors can be used, but the X-type metal-free phthalocyanine pigment and the τ-type metal-free Phthalocyanine pigment, Cu-Kα characteristic X-ray (wavelength 1.541
Titanyl phthalocyanine pigment having a main peak of Bragg angle 2θ in at least 9.6 ° ± 0.2 ° and 27.2 ° ± 0.2 ° in X-ray diffraction spectrum using Å), Cu-Kα characteristic X-ray In the X-ray diffraction spectrum using (wavelength 1.541 °), the main peak of the Bragg angle 2θ was at least 9.0 ° ± 0.2 ° and 27.2 ° ±
Titanyl phthalocyanine pigment at 0.2 °, Cu-K
In an X-ray diffraction spectrum using α characteristic X-rays (wavelength: 1.541 °), the main peak at Bragg angle 2θ was 27.
It is preferable to use a titanyl phthalocyanine pigment at only 2 ° ± 0.2 °.

The τ-type metal-free phthalocyanine pigment is Cu-K
In an X-ray diffraction spectrum using an α characteristic X-ray (wavelength: 1.541 °), the main peak at a Bragg angle of 2θ was 7.6.
°, 9.2 °, 16.8 °, 17.4 °, 20.4 °,
20.9 °, 21.7 °, 27.6 ° (± 0.2 each)
2 °), which is a metal-free phthalocyanine pigment present in JP-A-58-182639 and JP-A-60-1915.
It can be obtained by the method described in JP-A No. 4 (Kokai) No. 4 and the like.

The X type metal-free phthalocyanine pigment is Cu-K
In the X-ray diffraction spectrum using the α characteristic X-ray (wavelength 1.541 °), the main peak at the Bragg angle 2θ was 7.5.
°, 9.1 °, 16.7 °, 17.3 °, 22.3 °,
A metal-free phthalocyanine pigment present at 28.8 ° (each ± 0.2 °), described in US Pat. No. 3,579,899, US Pat. No. 3,594,163, JP-B-49-433.
No. 8 and JP-A-60-24389.

The titanyl phthalocyanine pigment used in the present invention is as follows. The basic structure of the titanyl phthalocyanine pigment used in the present invention is represented by the following general formula.

[0025]

Embedded image (Wherein, X1, X2, X3, and X4 each independently represent various halogen atoms, and n, m, l, and k each independently represent 0 to 0.
Represents an integer of 4. )

The titanyl phthalocyanine pigment according to the present invention is obtained by coagulating titanyl phthalocyanine having the above basic structure,
It is crystallized and has Cu-Kα characteristic X-rays (wavelength 1.
541 °), the main peak at Bragg angle 2θ was at least 9.6 ° ± 0.2.
° and 27.2 ° ± 0.2 ° or at least 9.0 ° ± 0.2 ° and 27.2 ° at the main peak at Bragg angle 2θ
The main peak at ± 0.2 ° or Bragg angle 2θ is 27.2
It has a crystal form only at ° ± 0.2 °. Among them, the main peak of the Bragg angle 2θ is 27.2 ° ± 0.2.
The crystal form only at 2 ° refers to a crystal form having a peak intensity of 27.2 ° ± 0.2 ° and any other peak having an intensity (peak height) of 35% or less. These crystalline titanyl phthalocyanine pigments have an absorption peak in the visible / near infrared absorption spectrum of 780 nm to 860 nm.
m, and has extremely high sensitivity to semiconductor laser light as compared with other crystal forms.

The synthesis example of the titanyl phthalocyanine pigment according to the present invention is described in the above-mentioned JP-A 64-17066.
JP, JP-A-2-28265, JP-A-3-35
No. 064, JP-A-3-200790, JP-A-3-269064, JP-A-3-128973, JP-A-3-250059, JP-A-5-981
No. 82, etc.

These phthalocyanine pigments are represented by the general formula (I)
The reason why the compound of the present invention exhibits a good combination and the sensitivity is sensitized is not clear, but the ionization potential matching is appropriate and has an effect of lowering the carrier injection barrier. Further, it is conceivable that the contact state at the interface between the compound of the general formula (I) and the phthalocyanine pigment is good and that the compound has the effect of improving the charge generation efficiency.

Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing a configuration example of the electrophotographic photoreceptor of the present invention. I am taking. FIG. 2 is a sectional view showing another configuration example of the present invention, in which an intermediate layer (13) is provided between a conductive support (11) and a photosensitive layer (15). FIGS. 3 and 4 are cross-sectional views showing another configuration example of the present invention, in which the photosensitive layer (15) is composed of a laminate of a charge generation layer (17) and a charge transport layer (19). FIG. 5 is a sectional view showing still another configuration example of the present invention, in which a protective layer (21) is provided on a photosensitive layer (15).

As the conductive support (11), those having a conductivity of 10 ¹⁰ Ω · cm or less, for example, aluminum, nickel, chromium, nichrome, copper, gold, silver,
Metals such as platinum, tin oxide, metal oxides such as indium oxide, coated on film or cylindrical plastic or paper by evaporation or sputtering,
Alternatively, a plate made of aluminum, an aluminum alloy, nickel, stainless steel, or the like, or a tube formed by extruding, drawing, or the like, and then subjecting to a surface treatment such as cutting, superfinishing, or polishing can be used. Further, an endless nickel belt and an endless stainless belt disclosed in JP-A-52-36016 can also be used as the conductive support (11).

In addition, a support obtained by dispersing a conductive powder on a suitable binder resin on the above support and applying the same can also be used as the conductive support (11) of the present invention. This conductive powder includes carbon black, acetylene black, aluminum, nickel, iron, nichrome, copper,
Metal powder such as zinc and silver, or metal oxide powder such as conductive titanium oxide, conductive tin oxide, and ITO may be used. The binder resin used simultaneously includes polystyrene, styrene-acrylonitrile copolymer, styrene-
Butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, Ethyl cellulose resin,
Thermoplastic, thermosetting or photo-setting resins such as polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin and alkyd resin Is mentioned. Such a conductive layer can be provided by dispersing the conductive powder and the binder resin in an appropriate solvent, for example, tetrahydrofuran, dichloromethane, 2-butanone, toluene, or the like, and applying the dispersion.

Further, the heat-shrinkable tube containing the above-mentioned conductive powder in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon, etc. on a suitable cylindrical substrate is used for the conductive material. Those provided with a layer can also be favorably used as the conductive support (11) of the present invention.

The charge generation layer (17) may be formed of only a charge generation substance, or may be formed by dispersing a charge generation substance in a binder resin. Therefore,
The charge generation layer (17) is obtained by dispersing these components in an appropriate solvent by using a ball mill, an attritor, a sand mill, ultrasonic waves, or the like, and applying this to the conductive support (11) or the intermediate layer (13). , Formed by drying.

As the charge generating substance used in the charge generating layer (17), a phthalocyanine pigment can be used as shown in the present specification. Examples of the binder resin used for the charge generation layer (17) include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral,
Polyvinyl formal, polyvinyl ketone, polystyrene, poly-vinyl carbazole, polyacrylamide,
Examples include polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, and the like.

The amount of the binder resin is 10 to 500 parts by weight, preferably 25 to 30 parts by weight, per 100 parts by weight of the charge generating substance.
0 parts by weight is suitable. The charge generation layer has a thickness of 0.1.
It is from 0.01 to 5 μm, preferably from 0.1 to 2 μm. Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, and ligroin. As a method of applying the coating solution, a method such as a dip coating method, a spray coat, a bead coat, a nozzle coat, a spinner coat, and a ring coat can be used.

The charge transporting layer (19) can be formed by dissolving or dispersing the charge transporting substance and the binder resin in a suitable solvent, applying the solution on the charge generating layer, and drying. If necessary, a plasticizer, a leveling agent, an antioxidant and the like can be added.

The charge transport material includes a hole transport material and an electron transport material. Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, and benzoquinone derivatives.

Examples of the hole transport material include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, polysilane, Oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives,
α-phenylstilbene derivative, benzidine derivative, diarylmethane derivative, triarylmethane derivative, 9
-Styryl anthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and other known materials. These charge transport materials are used alone or in combination of two or more.

Examples of the binder resin include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polystyrene. Vinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, Urethane resin,
Phenol resin, alkyd resin, JP-A-5-1582
And thermoplastic or thermosetting resins such as various polycarbonate copolymers described in JP-A No. 50 and JP-A-6-51544.

The amount of the charge transporting material is 20 to 300 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the binder resin.
Parts by weight are appropriate. The thickness of the charge transport layer is 5 to 5
Preferably, the thickness is about 0 μm. As the solvent used here, tetrahydrofuran, dioxane, toluene, monochlorobenzene, dichloroethane, dichloromethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used.

In the present invention, a plasticizer, a leveling agent and an antioxidant may be added to the charge transport layer (19).
As the plasticizer, those used as general plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are.
About 0 to 30 parts by weight relative to 0 parts by weight is appropriate. As the leveling agent, silicone oils such as dimethyl silicone oil and methyl phenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain can be used.
0 to 1 part by weight per 100 parts by weight is appropriate. As the antioxidant, an antioxidant such as a hindered phenol compound, a sulfur compound, a phosphorus compound, a hindered amine compound, a pyridine derivative, a piperidine derivative, a morpholine derivative, and a hydroquinone compound can be used. A suitable amount is about 0 to 5 parts by weight based on 100 parts by weight of the resin.

Next, the case where the photosensitive layer (15) has a single-layer structure will be described. Also in this case, in many cases, a function-separated type containing a charge generating substance and a charge transporting substance is exemplified. That is, the compounds exemplified above can be used as the charge generating substance and the charge transporting substance.

The photosensitive layer having a single-layer structure can be formed by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin in a suitable solvent, coating and drying. If necessary, a plasticizer, a leveling agent, an antioxidant and the like can be added.

As the binder resin, the charge transport layer (1
Although the binder resin exemplified in 9) can be used, the binder resin exemplified in the charge generation layer (17) may be mixed and used.

A photosensitive layer in which a hole transporting substance is added to a eutectic complex formed from a pyrylium-based dye or bisphenol-based polycarbonate can also be used as a single photosensitive layer.

The photosensitive layer having a single layer structure is immersed in a coating liquid obtained by dispersing a charge generating substance, a charge transporting substance, a binder resin and the like with a dispersing machine or the like using a solvent such as tetrahydrofuran, dioxane, dichloroethane, cyclohexanone or dichloromethane. It can be formed by coating by a coating method, spray coating, bead coating, or the like. The thickness of the photosensitive layer having a single-layer structure is 5 to 50.
About μm is appropriate.

In the present invention, as shown in FIG. 2, an intermediate layer (13) can be provided between the conductive support (11) and the photosensitive layer (15). The intermediate layer (13) can be made of a material containing a resin as a main component, or a material obtained by adding a fine powder pigment such as a metal oxide to a resin. Considering that the photosensitive layer (15) is coated on the intermediate layer (13) with a solvent, these resins are preferably resins having high solvent resistance to general organic solvents. As such a resin,
Water-soluble resins such as polyvinyl alcohol, casein and sodium polyacrylate, alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-maleic anhydride copolymer, ethylene -Ethylene resins such as vinyl acetate-methacrylic acid copolymers, vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, cellulose derivative resins, polyurethanes, melamen. Resin, phenolic resin, alkyd-melamine resin, acrylic-melamine resin, silicone resin, silicone-alkyd resin, epoxy resin,
Curable resins that form a three-dimensional network structure, such as polyisocyanate compounds, may be mentioned.

To the intermediate layer (13), a fine powder pigment of a metal oxide such as titanium oxide, aluminum oxide, silica, zirconium oxide, tin oxide, indium oxide or the like is added in order to prevent moire and reduce residual potential. May be.

Further, as the intermediate layer (13) of the present invention, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, a titanyl chelate compound, a zirconium chelate compound, a titanyl alkoxide compound, and an organic titanyl compound can also be used. These intermediate layers (13) can be formed using an appropriate solvent, dispersion and coating method as in the above-mentioned photosensitive layer.

In addition, the intermediate layer (13) of the present invention includes:
Al ₂ O ₃ provided by anodic oxidation, organic substances such as polyparaxylylene, SiO ₂ , SnO ₂ , TiO ₂ , IT
Those provided with an inorganic substance such as O or CeO ₂ by a vacuum thin film forming method can also be used favorably. The thickness of the intermediate layer (13) is 0 to 1
0 μm is appropriate.

The protective layer (21) is provided for the purpose of improving the durability of the photoreceptor. Materials used for the protective layer are ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, and allyl resin. , Phenolic resin, polyacetal, polyamide, polyamideimide,
Polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate,
Polyether sulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide,
Polysulfone, polystyrene, AS resin, butadiene
Resins include styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, epoxy resin and the like.

For the purpose of improving abrasion resistance, a fluorine resin such as polytetrafluoroethylene, a silicone resin, or an inorganic material such as titanium oxide, tin oxide or potassium titanate is added to the protective layer (21). can do. As a method for forming the protective layer (21), a normal coating method can be used. The thickness of the protective layer (21) is suitably from 0.1 to 10 μm.

In addition to the above, known materials such as aC and a-SiC formed by a vacuum thin film forming method may be used as the protective layer (2).
It can be used as 1). In the present invention, another intermediate layer (not shown) can be provided between the photosensitive layer (15) and the protective layer (21).

The other intermediate layer generally uses a resin as a main component. Examples of these resins include polyamide, alcohol-soluble nylon resin, water-soluble butyral resin, polyvinyl butyral, and polyvinyl alcohol.
As a method for forming the another intermediate layer, a normal coating method can be used as described above. The thickness is 0.05 to
2 μm is appropriate.

The compound represented by formula (I) can be contained in a photosensitive layer, a charge generation layer, and a charge transport layer. When added to the photosensitive layer, it is preferable to add 2 to 30 parts by weight based on 100 parts by weight of the binder resin. When added to the charge generation layer, it is preferable to add 5 to 30 parts with respect to 100 parts by weight of the total of the charge generation substance and the binder resin. When added to the charge transport layer, the binder resin 1
It is preferable to add 2 to 30 parts by weight to 00 parts by weight. When the addition amount is less than the lower limit, the effects described above such as sensitization cannot be obtained, and when the addition amount is larger than the upper limit,
The electrostatic characteristics such as sensitivity are deteriorated, and the strength of the added layer is reduced.

[0056]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. First, among the phthalocyanine pigments used in the examples, specific examples of the titanyl phthalocyanine pigment will be described.

(Synthesis Example 1) 52.5 g of phthalodinitrile
(0.41 mol) and 300 ml of 1-chloronaphthalene
Are stirred and mixed, and 19.0 g of titanium tetrachloride is added under a nitrogen stream.
(0.10 mol) is added dropwise. After dropping, gradually add 2
The temperature was raised to 00 ° C, and the reaction was carried out with stirring for 5 hours while maintaining the reaction temperature between 190 ° C and 210 ° C. After the completion of the reaction, the mixture was allowed to cool to 130 ° C., filtered while hot, and then washed with 1-chloronaphthalene until the powder turned blue.
Next, it is washed several times with methanol, further washed several times with hot water of 80 ° C., and then dried and 42.2 g (yield 73.3%).
Was obtained as a crude titanyl phthalocyanine pigment. 6 of the obtained crude titanyl phthalocyanine pigments subjected to the hot water washing treatment
g was dissolved in 100 g of 96% sulfuric acid at 3 to 5 ° C., dissolved and filtered. The obtained sulfuric acid solution was added dropwise to 3.5 liters of ice water while stirring, and the precipitated crystals were filtered, and then repeatedly washed with water until the washing liquid became neutral to obtain a wet cake of titanyl phthalocyanine pigment. 100 ml of 1,2-dichloroethane was added to the wet cake, and the mixture was added at room temperature for 2 hours.
After stirring for an hour, 300 ml of methanol was further added, followed by stirring and filtration. This was washed with methanol and further dried to obtain 4.9 g of the titanyl phthalocyanine pigment of the present invention.

(Synthesis Example 2) 52.5 g of phthalodinitrile
(0.41 mol) and 300 ml of 1-chloronaphthalene
Are stirred and mixed, and 19.0 g of titanium tetrachloride is added under a nitrogen stream.
(0.10 mol) is added dropwise. After dropping, gradually add 2
The temperature was raised to 00 ° C, and the reaction was carried out with stirring for 5 hours while maintaining the reaction temperature between 190 ° C and 210 ° C. After the completion of the reaction, the mixture was allowed to cool to 130 ° C., filtered while hot, and then washed with 1-chloronaphthalene until the powder turned blue.
Next, it is washed several times with methanol, further washed several times with hot water of 80 ° C., and then dried and 42.2 g (yield 73.3%).
Was obtained as a crude titanyl phthalocyanine pigment. 6 g of the obtained crude titanyl phthalocyanine was converted to 100 g of 96% sulfuric acid.
The mixture was stirred at 3 to 5 ° C, dissolved and filtered. The obtained sulfuric acid solution was dropped into 3.5 liters of ice water while stirring, and the precipitated crystals were filtered, and then washed repeatedly with water until the washing liquid became neutral, and dried to obtain 5.8 g of titanyl phthalocyanine pigment.
I got Next, 100 ml of methanol was added to 4.0 g of the titanyl phthalocyanine pigment subjected to the acid paste treatment, and a suspension and stirring treatment was performed at 30 ° C. for 5 hours. After the treatment, the mixture is filtered and dried to obtain 3.6 g of titanyl phthalocyanine pigment.
I got Further, 70 ml of n-butyl ether was added to 3.6 g of the obtained pigment, and milling was performed at room temperature for 24 hours together with 1 mmφ glass beads. Glass beads were removed from the dispersion, filtered, washed with methanol, and dried to obtain 3.4 g of the titanyl phthalocyanine pigment of the present invention.

Synthesis Example 3 35.0 g of 1,3-diiminoisoindoline and 240 ml of α-chloronaphthalene were mixed, and 24.5 g of titanium butoxide was added under a nitrogen atmosphere. The mixture was heated at 140 to 150 ° C. for 2 hours in a nitrogen atmosphere and further reacted at 180 ° C. for 3 hours. After cooling, the precipitate was filtered, washed with α-chloronaphthalene, thoroughly washed with DMF at 90 ° C., finally washed with methanol, and dried to obtain 29.8 g of titanyl phthalocyanine. 4.1 g of the titanyl phthalocyanine pigment obtained as described above was trifluoroacetic acid / dichloromethane = 8 m
Dissolved in 1/32 ml of a mixed solvent, this was added dropwise to an ice-cooled mixed solvent of methanol / water = 100 ml / 100 ml with stirring to precipitate crystals, and then allowed to stand. After the crystals precipitated, the supernatant was removed, 100 ml of methanol was added, and the mixture was stirred for 30 minutes and filtered. The obtained solid is 200
The resultant was dispersed in ml of hot water and repeatedly washed to obtain a wet cake of titanyl phthalocyanine pigment. Next, the wet cake is dispersed in 100 ml of monochlorobenzene,
The mixture was stirred for 0 minute, filtered and dried to obtain 3.6 g of a titanyl phthalocyanine pigment according to the present invention.

The X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained above was measured under the following conditions. X-ray tube Cu voltage 40 kV Current 20 mA Scanning speed 1 ° / min Scanning range 3 ° to 35 ° Time constant 2 seconds The X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained in Synthesis Example 1 is shown in FIG. FIG. 7 shows an X-ray diffraction spectrum of the obtained titanyl phthalocyanine pigment, and FIG. 8 shows an X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained in Synthesis Example 3. As shown in FIG. 6, it can be seen that the titanyl phthalocyanine pigment obtained in Synthesis Example 1 has main peaks at Bragg angles 2θ of 9.5 ° and 27.2 °. It can be seen that the pigment obtained in Synthesis Example 2 has main peaks at Bragg angles 2θ of 9.0 ° and 27.2 ° as shown in FIG. This pigment obtained according to Synthesis Example 3 has a maximum peak at a Bragg angle 2θ of 27.2 ° as shown in FIG.
It can be seen that the intensity (comparison of peak heights) of all other peaks is 35% or less with respect to the peak intensity of 2 ° ± 0.2 °.

Example 1 3 parts by weight of an alcohol-soluble polyamide (CM-8000, manufactured by Toray Industries, Inc.) was mixed with methanol / n-butanol = 8/2.
The mixture was dissolved by heating in 100 parts by weight of a mixed solvent (vol ratio) to prepare a coating liquid for an intermediate layer. This was applied on an aluminum plate having a thickness of 0.2 mm (A1080: manufactured by Sumitomo Light Metal Co., Ltd.), and 13
After drying at 0 ° C. for 10 minutes, an intermediate layer having a thickness of 0.1 μm was formed. Next, 2 parts by weight of an X-ray type metal-free phthalocyanine pigment and 2 parts by weight of a polyvinyl butyral resin (BM-2: manufactured by Sekisui Chemical Co., Ltd.) were added to 100 parts by weight of cyclohexanone, and the mixture was subjected to sand milling using 1 mmφ glass beads.
Time dispersion was performed. After the dispersion was completed, 100 parts by weight of methyl ethyl ketone was added and diluted to prepare a coating liquid for a charge generation layer. This was applied on the intermediate layer and dried at 80 ° C. for 10 minutes to form a 0.2 μm-thick charge generation layer. next,
7 parts by weight of a compound represented by the following structural formula (A), polycarbonate resin (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company) 1
0 parts by weight, 0.002 parts by weight of silicone oil (KF-50: manufactured by Shin-Etsu Chemical Co., Ltd.),
(I) -12, 1 part by weight was dissolved in 100 parts by weight of dichloromethane to prepare a coating solution for a charge transport layer. This was applied on the charge generation layer and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 20 μm. Obtained.

[0062]

Embedded image Further, after providing an intermediate layer and a charge generation layer on an aluminum plate in the same manner as described above, a charge transport layer was formed in the same manner as described above except that the exemplary compound of the present invention was not added. An electrophotographic photoreceptor to which the compound of (I) was not added was obtained.

The electrophotographic photoreceptor obtained as described above (with or without the compound of the formula (I)) was added at 25 ° C. /
The electrostatic characteristics were evaluated in a dynamic mode using EPA-8100 (manufactured by Kawaguchi Electric Works) in an environment of 50% RH. First, the photosensitive member is negatively charged by performing a corona discharge of -5.5 kV for 5 seconds, and when the surface potential becomes -800 V, a tungsten lamp white light (3 l) having a color temperature of 2856 K is used.
ux), and an exposure amount E1 / 5 (lux · sec) required for light attenuation of the surface potential to -160 V is measured.
Sensitivity difference ΔE1 / depending on the presence or absence of the compound of general formula (I)
5 (lux · sec) was measured. As a result, when the compound of the general formula (I) of the present invention was not added, E1 / 5 was 2.
06lux · sec was added,
1.83 lux · sec, 0.23 lux · sec
It was confirmed that c was sensitized. That is, ΔE1 / 5 was −0.23 lux · sec.

Examples 2 to 20 Example 1 was repeated except that the X-type metal-free phthalocyanine pigment as the charge-generating substance, the compound of the general formula (I) of the present invention and the amount of addition were as shown in Table 2. In the same manner as in Example 1, an electrophotographic photosensitive member to which the general formula (I) of Examples 2 to 20 was added was obtained.

[0065]

[Table 2] The above photoreceptor is represented by the general formula (I) in the same manner as in Example 1.
ΔE1 / 5 (lux · sec) depending on the presence or absence of compound
Was measured. Table 3 shows the results.

[0066]

[Table 3] As described above, ΔE1 / 5 is negative in all cases, indicating that the sensitization is increased.

Comparative Example 1 The electrophotographic photoreceptor of Comparative Example 1 was prepared in the same manner as in Example 1 except that an azo pigment represented by the following structural formula (II) was used in place of the X-type metal-free phthalocyanine pigment. Was prepared, and ΔE1 / 5 (lux · sec) was evaluated. The result was ΔE1 / 5 = 0.15 lux · sec.

[0068]

Embedded image

Comparative Example 2 The electrophotographic photoreceptor of Comparative Example 1 was prepared in the same manner as in Example 1 except that an azo pigment represented by the following structural formula (III) was used instead of the X-type metal-free phthalocyanine pigment. Was prepared, and ΔE1 / 5 (lux · sec) was evaluated. The result was ΔE1 / 5 = 0.17 lux · sec.

[0070]

Embedded image

Comparative Example 3 The electrophotographic photosensitive member of Comparative Example 1 was prepared in the same manner as in Example 1 except that an azo pigment represented by the following structural formula (IV) was used in place of the X-type metal-free phthalocyanine pigment. Was prepared, and ΔE1 / 5 (lux · sec) was evaluated. The result was ΔE1 / 5 = 0.25lux · sec.

[0072]

Embedded image As can be seen from the results of the comparative examples, when a substance other than the phthalocyanine pigment was used as the charge generating substance, the sensitivity was conversely reduced.

[0073]

As described above in detail and specifically,
The electrophotographic photoreceptor of the present invention can be easily sensitized to a phthalocyanine pigment having a good sensitivity to long-wavelength light, and is extremely excellent in practical value.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a layer configuration of an electrophotographic photoreceptor of the present invention.

FIG. 2 is a cross-sectional view illustrating another layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a cross-sectional view illustrating still another layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a cross-sectional view illustrating still another layer configuration of the electrophotographic photoreceptor of the present invention.

FIG. 5 is a cross-sectional view illustrating still another layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 6 is an X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained in Synthesis Example 1 in the present invention.

FIG. 7 is an X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained in Synthesis Example 2 in the present invention.

FIG. 8 is an X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained in Synthesis Example 3 in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 11 conductive support 13 intermediate layer 15 photosensitive layer 17 charge generation layer 19 charge transport layer 21 protective layer

Claims (6)

[Claims] 1. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains a phthalocyanine pigment and a compound represented by the following general formula (I). Photoconductor. Embedded image (Wherein, R ₁ represents a lower alkyl group, R ₂ and R ₃ represent a substituted or unsubstituted methylene group or an ethylene group;
r ₁ and Ar ₂ represent a substituted or unsubstituted aryl group. l
Is an integer of 0 to 4; m and n are integers of 0 to 2;
+ N is an integer of 2 or more, and l + m + n is an integer of 6 or less. or,
The unsubstituted site on the benzene ring represents a hydrogen atom. ) 2. The electrophotographic photoreceptor according to claim 1, wherein the phthalocyanine pigment is an X-type metal-free phthalocyanine pigment. 3. The electrophotographic photoreceptor according to claim 1, wherein said phthalocyanine pigment is a τ-type metal-free phthalocyanine pigment. 4. The X-ray diffraction spectrum of the phthalocyanine pigment using Cu-kα characteristic X-rays (wavelength: 1.541 °), wherein the main peak of Bragg angle 2θ is at least 9.6 ° ± 0.2 ° and 27. 2. The electrophotographic photoconductor according to claim 1, wherein the electrophotographic photoreceptor is a titanyl phthalocyanine pigment at an angle of 2 ° ± 0.2 °. 5. The X-ray diffraction spectrum of the phthalocyanine pigment using Cu-kα characteristic X-rays (wavelength 1.541 °), wherein the main peak at a Bragg angle 2θ is at least 9.0 ° ± 0.2 ° and 27. 2. The electrophotographic photoconductor according to claim 1, wherein the electrophotographic photoreceptor is a titanyl phthalocyanine pigment at an angle of 2 ° ± 0.2 °. 6. The X-ray diffraction spectrum of the phthalocyanine pigment using Cu-kα characteristic X-rays (wavelength 1.541 °), wherein the main peak at a Bragg angle 2θ is 27.2 °.
2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is a titanyl phthalocyanine pigment having an angle of only ± 0.2 °.