JP2700859B2 - Photoconductor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor,
Photoreceptors, especially used in printers, copiers, etc.
Higher than visible light, longer wavelength light and semiconductor laser light
It relates to a photoreceptor exhibiting sensitivity. [0002] 2. Description of the Related Art Conventionally, electrophotography having photosensitivity to visible light
Photoconductors are widely used in copiers, printers, and the like.
Such electrophotographic photoreceptors include selenium and oxygen oxide.
Mainly composed of inorganic photoconductive materials such as lead and cadmium sulfide
Inorganic photoreceptors provided with a photosensitive layer are widely used. Only
On the other hand, such inorganic photoconductors are
Photosensitivity, heat stability, moisture resistance,
Characteristics are not always satisfactory.
No. For example, selenium can stain fingerprints when touched by heat or hands.
Crystallized, etc.
The characteristics are easily degraded. Electron imaging using cadmium sulfide
True photoreceptors have poor humidity resistance and durability, and use zinc oxide.
The electrophotographic photosensitive member has a problem in durability. In addition,
And cadmium sulfide electrophotographic photoreceptors are
There is also a drawback that the restrictions are large. [0003] The problems of such inorganic photoconductive materials have been revised.
Various organic photoconductive materials in order to improve
Attempts have been made to use it for the photosensitive layer of photoreceptors.
Research and development. For example, Japanese Patent Publication No. 50-10496
The report contains poly-N-Vinyl carbazole and 2,4,7-trinit
B) Organic photosensitive having a photosensitive layer containing 9-fluorenone
The body has been described. However, this photoconductor also has sensitivity and
Not long enough. Therefore, the photosensitive layer is divided into two layers.
The carrier generation layer and the carrier transport layer separately,
Each contains a carrier generating substance and a carrier transporting substance.
A function-separated type electrophotographic photoreceptor was developed. This
This means that the carrier generation function and the carrier transport function differ.
Demonstrates each function because quality can be shared individually
You can choose from a wide range of substances
The electrophotographic photoreceptor having arbitrary characteristics can be relatively easily
can get. Therefore, high sensitivity and high durability organic
It is expected that a photoconductor will be obtained. [0004] Such a function-separated type electrophotographic photoreceptor has
Carrier-generating materials effective for the carrier-generating layer include
Many substances have been proposed since then. Examples of using inorganic substances
As described in, for example, Japanese Patent Publication No. 43-16198
And amorphous selenium. This amorphous selenium
The carrier generation layer containing an organic carrier transport material
It is used in combination with a carrier transport layer. I
However, the carrier generation layer made of amorphous selenium
Crystallized due to heat etc. as described, and its characteristics deteriorate
There is a problem. In addition, the organic substance is
Organic dyes and organic pigments
Is mentioned. For example, a photosensitive composition containing a bisazo compound
As those having a layer, JP-A-47-37543,
JP-A-55-22834, JP-A-54-79632, JP-A-56-1
It is already known from 16040 and the like. However, these known bisazotizations
The compound has relatively good sensitivity in the short or middle wavelength range.
As shown, the sensitivity in the long wavelength range is low, and high reliability is expected.
For laser printers using semiconductor laser light sources
It was difficult to be. At present, it is widely used as a semiconductor laser.
Gallium-aluminum-arsenic (Ga / Al / As) system
The light emitting element has an oscillation wavelength of about 750 nm or more. This
In order to obtain an electrophotographic photoreceptor with high sensitivity to long wavelength light,
Conventionally, many studies have been made. For example, in the visible light region
New long wavelength for photosensitive materials such as Se and CdS which have high sensitivity
A method of adding a sensitizer for converting
e, CdS are environmental resistance to temperature, humidity, etc. as described above
Is not enough and there is still a problem. Also, many are known
Organic photoconductive materials also usually have sensitivity as described above.
Limited to the visible light region of 700 nm or less, longer wavelength region
Few materials have sufficient sensitivity. Among them, one of the organic photoconductive materials
Phthalocyanine compounds are more sensitive than others
It is known that the range is extended to a long wavelength range. this
Examples of these photoconductive phthalocyanine compounds
For example, α-type titer described in JP-A-61-239248
Nil phthalocyanine. This α-type titanylph
Tarocyanine, as shown in FIG.
The Bragg angles to the lines are 7.5, 12.3, 16.3, 25.3, 2
It has a peak at 8.7. However, this α-type titanyl lid
Russianinine has low sensitivity and low potential for repeated use.
Electrophotographic process using reversal development with poor quality
Then, there is a problem that the ground fog easily occurs. Also,
Due to poor charging ability, it is difficult to obtain a sufficient image density. [0008] As described above, the long wavelength
Phthalo is an organic carrier-generating substance with high sensitivity
Cyanine compounds include α-type titanyl phthalos
Anin is used repeatedly in its manufacturing method and as an electrophotographic photoreceptor.
There is a problem in the potential stability when used. Accordingly, a first object of the present invention is to provide, in particular,
Titanyl lid with high sensitivity to light of wavelengths longer than m
An object of the present invention is to provide a photoreceptor using Russiannin. [0010] A second object of the present invention is to provide a repetitive use.
To provide a photosensitive member having high potential stability. [0011] A third object of the present invention is to provide a sensor having excellent chargeability.
To provide light bodies. A fourth object of the present invention is to provide a reversal development process.
It is to provide an optimal photoreceptor. [0013] That is, the present invention provides a CuKα characteristic.
Of Bragg angle 2θ for neutral X-rays (wavelength 1.541 °)
Peak at least 9.5 degrees ± 0.2 degrees, 9.7 degrees ± 0.2 degrees, 11.7
Degrees ± 0.2 degrees, 15.0 degrees ± 0.2 degrees, 23.5 degrees ± 0.2 degrees, 24.1 degrees ±
Titanyl phthalocyanine at 0.2 ° and 27.3 ° ± 0.2 °
The present invention relates to a photoreceptor containing: The titanyl phthalocyanine according to the present invention comprises
When used as a function-separated type electrophotographic photoreceptor,
Used as a carrier generating substance,
Combined to form a photoreceptor. According to this invention
Titanyl phthalocyanine is the α-type titanyl phthalate described above.
Different from Russian Nin, as shown in Figure 1
Bragg angle for X-ray of CuKα1.541Å (error 2θ ±
0.2 degrees) to 9.5, 9.7, 11.7, 15.0, 23.5, 24.1, 27.3
Major peak(A sharp projection different from noise)Have
X-ray diffraction spectrum. α-type titanyl lid
Bragg angle for X-rays of Russian Nin CuKα1.541Å
Are 7.5, 12.3, 16.3, 25.3, 28.7 as described above
Therefore, it has a crystal form completely different from α-form. The titanyl phthalocyanine of the present invention
Has an unprecedented and unique spectrum as described above.
However, its basic structure is represented by the following general formula. [0016] Embedded image(However, X¹, X^Two, X^Three, X^FourIs Cl or Br
And n, m, l, and k represent an integer of 0 to 4. ) The above X-ray diffraction spectrum was measured under the following conditions.
(The same applies hereinafter). [0018] X-ray tube Cu Voltage 40.0 kV Current 100.0 mA Start angle 6.00 deg. Stop angle 35.00 deg. Step angle 0.020 deg. Measurement time 0.50 sec. Illustrates a method for producing titanyl phthalocyanine according to the present invention
Will be explained. First, for example, titanium tetrachloride and phthalodinit
Is reacted with α-chloronaphthalene in an α-chloronaphthalene solvent.
Dichlorotitanium phthalocyanine obtained by
(TiCl_TwoHydrolysis of Pc) with aqueous ammonia
To obtain α-type titanyl phthalocyanine. This is a pull
Then, 2-ethoxyethanol, diglyme, dioxa
, Tetrahydrofuran, N, N-dimethylformamide,
Electric children such as N-methylpyrrolidone, pyridine and morpholine
It is preferred to treat with a donating solvent. Next, this α-type titanyl phthalocyanine is
Crystalline transformation at a temperature of 50-180 ° C, preferably 60-130 ° C
Agitation or mechanical strain for a time sufficient to replace
Milled to produce the titanyl phthalocyanine of the present invention.
It is. The above α-type titanyl phthalocyanine
Another fabrication method for TiCl_TwoPc is preferably 5 ° C or less
Once dissolved or sulfated in sulfuric acid under water or
Is poured into ice water and refolded or hydrolyzed to give α-type
Nylphthalocyanine is obtained. The titanyl phthalocyanate obtained as described above
Nin is preferably used in a dry state,
Can also be used. With the dispersion medium of stirring and kneading
Is usually used for pigment dispersion and emulsification
Well, for example glass beads, steel beads, alumina
Beads and flint stones. However, a dispersion medium is necessary.
I don't need it. Grinding aid is usually used to grind pigments
What is used as an auxiliary may be used, for example, salt,
Examples include sodium bicarbonate and boric acid. But this polish
A grinding aid is not necessarily required. When a solvent is required for stirring, kneading and grinding.
In the case, it may be liquid at the temperature during stirring and kneading,
For example, alcohol solvents such as glycerin and ethylene
Glycol, diethylene glycol or polyethylene
Glycol-based solvent, ethylene glycol monomethyl ester
Or ethylene glycol monoethyl ether.
Rosolve solvent, ketone solvent, ester ketone solvent
It is preferable to select one or more types from the group such as above. The apparatus used in the crystal transition step
A typical example is a general stirrer, such as
For example, homomixer, tisparser, agitator, star
Or kneader, Banbury mixer, ball mill
And sand mills and attritors. The temperature range in the crystal transition step is 50 to 180.
C., preferably in the temperature range from 60 to 130.degree. Also,
Use crystal nuclei as in normal crystal transition process
It is also effective. In the present invention, the titanyl phthalocyanine described above is used.
Other carrier-generating substances in addition to
No. Examples of the carrier generating substance that can be used in combination are, for example, α
Type, β type, γ type, X type, τ type, τ 'type, η type, η' type
Metal-free phthalocyanine,Or various crystal types (α type, β type
Etc.) titanyl phthalocyanineIs mentioned. Also,
Other than the above, phthalocyanine pigments, azo pigments,
Non-pigment, perylene pigment, polycyclic quinone pigment, squarite
And methine citrate pigments. Examples of the azo pigments include the following.
I can do it. [0028] Embedded image [0029] Embedded image [0030] Embedded image[However, in this general formula, Ar₁, Ar_TwoAnd Ar_Three: Replaced or unplaced, respectively
A substituted carbocyclic aromatic ring group, R¹, R^Two, R^ThreeAnd R^Four: Respectively, electron-withdrawing group or water
An elementary atom, R¹~ R^FourAt least one is a cyano group
Electron-withdrawing groups such as [0032] Embedded image [0033] Embedded image (X is a hydroxy group, -N (R⁶) (R⁷) Or
−NHSO_Two−R⁸<However, R⁶And R⁷Is a hydrogen atom
Or a substituted or unsubstituted alkyl group, R⁸Is replacement
Or unsubstituted alkyl group or substituted or unsubstituted ant
Group), Y is a hydrogen atom, a halogen atom,
Represents an unsubstituted alkyl group, alkoxy group, carboxyl
Group, sulfo group, substituted or unsubstituted carbamoyl group or
Is a substituted or unsubstituted sulfamoyl group (where m is
In the case of two or more, the groups may be different from each other. ),
Z is a substituted or unsubstituted carbocyclic aromatic ring or substituted
Or necessary to form an unsubstituted heterocyclic aromatic ring
Atom group, R^FiveIs a hydrogen atom, a substituted or unsubstituted
Groups, substituted or unsubstituted carbamoyl groups, carboxyl groups
A sil group or its ester group, A ′ is substituted or unsubstituted.
A substituted aryl group, n is an integer of 1 or 2, m is 0-4
Is an integer. )] [0035] Embedded image [0036] Embedded image[0037] Embedded image [0038] Embedded image[0039] Embedded image [0040] Embedded image[0041] Embedded image [0042] Embedded image[0043] Embedded image [0044] Embedded image[0045] Embedded image The polycyclic quinone pigment is represented by the following general formula:
[II]. [0047] Embedded image (In this general formula, X 'is a halogen atom,
Toro, sialic, acyl or carboxyl groups
And n represents an integer of 0 to 4. ) A specific example is as follows. [0049] Embedded image[0050] Embedded image [0051] Embedded image In the photosensitive member of the present invention, a function-separated type is used.
The carrier transport material used in
Zole derivatives, oxadiazole derivatives, thiazole derivatives
Conductor, thiadiazole derivative, triazole derivative, a
Midazole derivatives, triazole derivatives, imidazole
Derivatives, imidazolone derivatives, imidazolidine derivatives,
Bis imidazolidine derivatives, styryl compounds, hydrazos
Compounds, pyrazoline derivatives, oxazolone derivatives,
Benzothiazole derivatives, benzimidazole derivatives,
Nazoline derivative, benzofuran derivative, acridine derivative
Body, phenazine derivative, aminostilbene derivative, poly
-N-vinylcarbazole, poly-1-vinylpyrene, poly-9
-Vinyl anthracene and the like. For constituting the photosensitive layer of the photosensitive member of the present invention
Is to disperse the above carrier generating material in the binder
The layer may be provided on a conductive support. Or this cap
Combine rear generating material and carrier transport material and stack
Type or dispersion type so-called function separation type photosensitive layer
Is also good. In the case of a function-separated type photosensitive layer, usually, FIGS.
Like 11 That is, the layer configuration shown in FIG.
Includes titanyl phthalocyanine according to the present invention on carrier 1
A carrier generation layer 2 is formed, and the carrier transportation
The photosensitive layer 4 is formed by laminating the carrier transport layer 3 containing
FIG. 7 shows these carrier generation layers 2 and
Photosensitive layer 4 'formed by inverting carrier transport layer 3
The layer configuration of FIG. 8 is electrically conductive with the photosensitive layer 4 having the layer configuration of FIG.
FIG. 9 shows the layer structure of FIG.
An intermediate layer 5 is provided between the photosensitive layer 4 ′ and the conductive support 1.
Injecting free electons into the conductive support 1
The layer configuration shown in FIG.
Launched a carrier mainly composed of titanyl phthalocyanine
The raw material 6 and the carrier transporting material 7 combined therewith
A photosensitive layer 4 ″ was formed.
The conductive layer is formed between the photosensitive layer 4 ″ and the conductive support 1.
An intermediate layer 5 is provided. In forming a photosensitive layer having a two-layer structure,
The carrier generation layer 2 is provided by the following method.
Can be. (A) Dissolve the carrier generating substance in a suitable solvent
Add the binder to the solution or the mixed solution
A method of applying a solution. (B) Using a ball mill, e
Make fine particles in the dispersion medium with
Dispersion obtained by mixing and dispersing by adding a binder according to
How to apply. In these methods, the particles are subjected to the action of ultrasonic waves.
Dispersing the particles allows for uniform dispersion. Solvents used for forming the carrier generating layer or
N-butylamine, diethylamido
, Ethylenediamine, isopropanolamine, tri
Ethanolamine, triethylenediamine, N, N-dimethyl
Ruformamide, acetone, methyl ethyl ketone, cycle
Rohexanone, benzene, toluene, xylene, chloro
Form, 1,2-dichloroethane, dichloromethane, tetra
Hydrofuran, dioxane, methanol, ethanol,
Isopropanol, ethyl acetate, butyl acetate, dimethyl
Sulfoxide and the like can be mentioned. The carrier generation layer or the carrier transport layer
When a binder is used for the formation,
Can be used, but it is particularly hydrophobic and
High electrical permittivity and electrical insulation film forming ability
High molecular polymers are preferred. Examples of such polymers include
For example, the following can be mentioned, but of course, these are limited to these.
It is not specified. A) Polycarbonate b) polyester c) Methacrylic resin d) Acrylic resin e) Polyvinyl chloride f) Polyvinylidene chloride g) Polystyrene h) Polyvinyl acetate i) Styrene-butadiene copolymer j) Vinylidene chloride-acrylonitrile copolymer k) Vinyl chloride-vinyl acetate copolymer l) Vinyl chloride-vinyl acetate-maleic anhydride copolymer m) Silicon resin n) Silicon-alkyd resin o) Phenol-formaldehyde resin p) Styrene-alkyd resin q) Poly-N-vinyl carbazole r) Polyvinyl butyral s) Polycarbonate Z resin These binders may be used alone or as a mixture of two or more.
Can be used. Also, the cap on the binder
The ratio of the rear generating substance is 10 to 600% by weight, preferably 50 to 4%.
00% by weight, 10 to 500 parts by weight of carrier transport material
Is good. The carrier generation layer thus formed
2 is preferably 0.01 to 20 μm,
It is preferably 0.05 to 5 μm. Carrier transport layer thickness
The thickness is 2 to 100 μm, preferably 5 to 30 μm. The above carrier-generating substance is dispersed and exposed to light.
When forming a layer, the carrier generating substance is
2 μm or less, preferably 1 μm or less
Preferably. In other words, if the particle size is too large,
And the particles partially protrude from the surface
Poor surface smoothness and, in some cases, protrusions of particles
Discharge in a minute or toner particles adhere to it
Toner filming phenomenon easily occurs. Further, the sensitivity of the photosensitive layer is improved and
For the purpose of reducing potential or fatigue during repeated use, etc.
Can contain more than one electron acceptor
You. As an electron accepting substance that can be used here
Are, for example, succinic anhydride, maleic anhydride,
Water succinic acid, phthalic anhydride, tetrachloro phthalic anhydride
Acid, tetrabromophthalic anhydride, 3-nitrophthalic anhydride
Acid, 4-nitrophthalic anhydride, pyromellitic anhydride, anhydride
Melitic acid, tetracyanoethylene, tetracyanoquino
Dimethane, o-dinitrobenzene, m-dinitrobenzene,
1,3,5-trinitrobenzene, paranitrobenzonitrile
, Picryl chloride, quinone chlorimide, chlora
Nil, bulmanil, dichlorodicyanoparabenzoquino
, Anthraquinone, dinitroanthraquinone, 9-full
Olenylidene (dicyanomethylene malonodinitrile),
Linitro-9-fluorenylidene- (dicyanomethylenemalo
Nodinitrile), picric acid, o-nitrobenzoic acid, p-nitric acid
Torobenzoic acid, 3,5-dinitrobenzoic acid, pentafluoro
Benzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicyl
Acid, phthalic acid, melitic acid, and other high electron affinity
Compounds. Also, electron-accepting substances
The addition ratio of the carrier generating substance to the electron acceptor is expressed by weight.
Quality is 100: 0.01 ~ 200, preferably 100: 0.1 ~ 100
You. The support 1 on which the above-mentioned photosensitive layer is to be provided
Is a metal plate, metal drum or conductive polymer, oxide oxide
Conductive compounds such as aluminum, aluminum, palladium, etc.
Coating, vapor deposition, lamination of conductive thin layer made of metal such as
Paper, plastic film, etc.
What is provided on a substrate is used. Adhesive layer
The intermediate layer functioning as a rear layer, etc.
Polymer, polyvinyl chloride, etc.
Nyl alcohol, ethyl cellulose, carboxymethyl
Organic polymer substances such as cellulose or aluminum oxide
What consists of etc. is used. As described above, the photosensitive member of the present invention was obtained.
However, the feature is the titanyl phthalo used in the present invention.
The maximum value of the photosensitive wavelength range of cyanine exists at 817nm ± 5nm
Therefore, it is ideal for a photoreceptor for a semiconductor laser.
The crystal form of this titanyl phthalocyanine is extremely stable
And the transition to another crystal form is unlikely to occur. This
That is, the production of the titanyl phthalocyanine of the present invention described above.
When manufacturing electrophotographic photoreceptors as well as structure and properties
And it is a great advantage in its use. As described above, the present invention relates to the present invention.
Because of using the unique titanyl phthalocyanine,
Suitable for long-range light, especially for semiconductor lasers and LEDs
A photoreceptor having a wavelength range can be obtained. In addition,
The titanyl phthalocyanine according to Ming is solvent, heat, mechanical
Excellent crystal stability against strain force, sensitivity as photoreceptor,
It has the features of being excellent in charging ability and potential stability. [0067] DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
Synthesis Example 1 of titanyl phthalocyanine according to the invention, and ratio
Synthesis Examples 2 and 3 of α-type titanyl phthalocyanine of Comparative Example
Show. (Synthesis Example 1) 10 parts of α-type titanyl phthalocyanine and food as grinding aid
5 to 20 parts of salt, as dispersion mediumAcetophenoneSun 10
Put in a dog grinder and keep at 60 ° C to 120 ° C for 7 to 15 hours
Ground. In this case, when grinding at high temperature,
It is easy to show a crystal form and to be easily decomposed. From the container
Take out the grinding aid and dispersion medium with water and methanol.
After removal, purification with 2% dilute sulfuric acid aqueous solution, filtration, washing with water,
Drying gave clear greenish blue crystals. This crystal is X-ray
By diffraction and infrared spectroscopy, the titanyl lid of the present invention shown in FIG.
It turned out to be Russian Nin. The infrared absorption spectrum is shown in FIG.
It was right. The maximum wavelength of the absorption spectrum (λma
x) is at 817 nm ± 5 nm, which is the α-form titanyl phthalo
This is different from λmax = 830 nm of cyanine. Synthesis Example 2 40 g of phthalodinitrile and 4 salts
A mixture of 18 g of titanium oxide and 500 ml of α-chloronaphthalene
Complete the reaction by heating and stirring at 240-250 ° C for 3 hours under a nitrogen stream.
I let it. Then leaks and the product diclotitaniu
Muphthalocyanine was obtained. Dichlorotitani obtained
Umphthalocyanine and 300 ml of concentrated aqueous ammonia
The mixture was heated to reflux for 1 hour, and the target substance, titanyl phthalocyanine
18 g was obtained. The product is soxhlet with acetone.
The extractor was sufficiently washed. This product is shown in FIG.
α-type titanyl phthalocyanine. (Synthesis Example 3) Titanylphthalocy of Synthesis Example 2
Anin was acid-pasted and the spectrum of FIG.
α-type titanyl phthalocyanine was obtained. [0072]Example 1 1 part of titanyl phthalocyanine of the present invention of Synthesis Example 1, dispersion
Binder resin, polyvinyl butyral resin ("XY
HL ", manufactured by Union Carbide Co., 1 part, Tetrahydrid
Disperse 100 parts of lofran using an ultrasonic disperser for 15 minutes.
Was. The obtained dispersion is treated with a wire bar to remove aluminum.
On conductive support consisting of evaporated polyester film
To form a charge generation layer having a thickness of 0.2 μm. On the other hand, 3 parts of a compound having the following structure and
Carbonate resin (“Panlite L-1250”, Teijin Chemicals
4 parts dissolved in 30 parts of 1,2-dichloroethane.
The solution was applied on the charge generation layer and dried to a thickness of 18 μm.
m of a charge transport layer, thereby forming an electrophotographic photosensitive member of the present invention.
Created body. [0074] Embedded image [0075]Example 2 Instead of the charge transport material of Example 1, the charge transport material having the following structure was used.
An electrophotographic photoreceptor similar to that of Example 1 except that a carrier material was used.
It was created. The molecular sensitivity distribution of this photoreceptor is as shown in FIG.
The long wavelength sensitivity was good. [0076] Embedded image [0077]Comparative Example 1 In Example 1, X shown in FIG.
Charge generation material having an X-ray diffraction spectrum (Synthesis Example 2
Comparative Example 2 except that
Body 1 was made. [0078]Comparative Example 2 In Example 1, X shown in FIG.
Charge generation material having an X-ray diffraction spectrum (Synthesis Example 3
Comparative Example 2 except that
Body 2 was created. [0079]Example 3 Salt on polyester with aluminum foil laminated
Vinyl chloride-vinyl acetate-maleic anhydride copolymer ("S
LEC MF-10 ", manufactured by Sekisui Chemical Co., Ltd.)
An intermediate layer of 1 μm was formed. Next, titanylph of the present invention is used as CGM.
Tarocyanine is ground in a ball mill for 24 hours,
Nate resin ("Panlite L-1250", manufactured by Teijin Chemicals Ltd.)
1,2-dichloroethane solution containing 6% by weight of
Phthalocyanine / polycarbonate resin = 30/100 (weight
Volume ratio), and further ball mill for 24 hours
Scattered. CTM (Compound Example 1) was added to the dispersion
75% by weight based on Bonate resin
Lebenzene / 1,2-dichloroethane = 3/7 (volume ratio)
Spray coated on the intermediate layer
Coating method to form a 20 μm thick photosensitive layer.
A light photoreceptor sample was obtained. [0081]Example 4 Polyester film laminated with aluminum foil
An intermediate layer exactly as in Example 1 was formed thereon. Next, CTM (Compound Example 2) / polycarbonate
Nate resin ("Panlite L-1250", manufactured by Teijin Chemicals Ltd.)
= 1,2-dichloromethane containing 16.5% by weight of 60/100 (weight ratio)
Dip the loethane solution onto the intermediate layer and dry.
Thus, a CTL having a thickness of 15 μm was obtained. Next, the titanyl phthalate of the present invention is used as CGM.
Pulverize Russian Nin with a ball mill for 24 hours and use polycarbonate
Resin (“Panlite L-1250”, Teijin Chemicals Ltd.)
A 1,2-dichloroethane solution containing 6% by weight was titanyl
Tarocyanine / polycarbonate resin = 30/100 (weight
Ratio) and further dispersed for 24 hours in a ball mill
did. CTM (Compound Example 2) was added to this dispersion liquid in polycarbonate.
75% by weight with respect to the acid resin
Add benzene to monochlorobenzene / 1,2-dichloroe
The one prepared so that tan = 3/7 (volume ratio)
Sprayed on the intermediate layer by spray coating method, thickness 5μ
m of the photosensitive layer was formed to obtain a photosensitive member sample of the present invention. Each of the photoconductors thus obtained was subjected to an electrostatic tester.
("EPA-8100", manufactured by Kawaguchi Electric Works).
The following property test was performed.[0085] "Electrometer SP-428" (Kawaguchi
ElectricMachine(Manufactured by Seisakusho Co., Ltd.).
That is, the surface of the photoconductor is charged with a charging voltage of -6 k or +6.kWith bolts
Accepting potential V when charged for 5 seconds_A(Volts) and 5 seconds
Potential V after dark decay_I(Initial potential volt) reduced by half
Exposure E1 / 2 (looks-seconds) and darkening required for attenuation
Decay rate (D.D = (V_A-V _I ) / V _I X100 (%)
Was. Next, chargingvesselMark -6kV or + 6kV voltage on
After charging the photosensitive layer by corona discharge for 5 seconds,
Leave for 5 seconds (this potential is called the initial potential)
Next, the light intensity on the surface of the photosensitive layer is 5 erg / cm.^Two・ Sec and
The light of the xenon lamp is split into
Irradiate light and raise initial potential from +600 or -600 volts to +30
0 or [0087] [Outside 1] The results are summarized in Table 1 below. [0089] [Table 1] From the results, the photoreceptor according to the present invention was
Good long-wavelength sensitivity, stable potential for repeated use, charging
It turns out that it is excellent in performance. Next, an example applied to the reversal development process will be described.
I will tell. Examples 1 to 4 and Comparative Examples 1 and 2 described above.
6 types of photoreceptors are laser printer ("LP-301
0 ", Konishi Roku Photo Industry Co., Ltd.)
Charged two-component developer containing positive or negative toner respectively
Reversal development using, 1000 times repeated image formation,
For each image density, the amount of black spots on the white background◎",
"○”And“ × ”, and the results are shown in Table 2 below.
It was shown to. The light source is a semiconductor laser (780nm) and
And LED (680 nm). [0093] [Table 2] However, the amount of black spots is ◎ 0 / cm^Two ○ 3 / cm^TwoLess than × 3 pieces / cm^Twothat's all Image density measured with Sakura Densitometer PDA-65
did. ◎ Reflection density 1.0 or more ○ Reflection density 0.6 ~ 1.0 × Reflection density 0.6 or less Thus, the photoreceptor according to the present invention is suitable for reversal development.
You can see that there is. [0096] According to the present invention, the photoreceptor of the present invention can emit light having a wavelength of 600 nm or more.
Contains titanyl phthalocyanine with high sensitivity to
High stability by repeated use and good chargeability
Excellent and shows the best effect for the reversal development process.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an X-ray diffraction diagram of titanyl phthalocyanine of the present invention. FIG. 2 is an X-ray diffraction diagram of two examples of α-type titanyl phthalocyanine. FIG. 3 is an X-ray diffraction diagram of two examples of α-type titanyl phthalocyanine. FIG. 4 is an absorption spectrum of a charge generation layer according to the present invention. FIG. 5 is a spectral sensitivity diagram of a photoreceptor according to the present invention. FIG. 6 is a cross-sectional view showing a specific example of a layer configuration of the electrophotographic photosensitive member of the present invention. FIG. 7 is a cross-sectional view showing a specific example of a layer configuration of the electrophotographic photosensitive member of the present invention. FIG. 8 is a cross-sectional view showing a specific example of a layer configuration of the electrophotographic photosensitive member of the present invention. FIG. 9 is a cross-sectional view showing a specific example of a layer configuration of the electrophotographic photoconductor of the present invention. FIG. 10 is a cross-sectional view showing a specific example of a layer configuration of the electrophotographic photosensitive member of the present invention. FIG. 11 is a cross-sectional view showing a specific example of a layer configuration of the electrophotographic photosensitive member of the present invention. [Description of Signs] 1 conductive support 2 carrier generation layer 3 carrier transport layers 4, 4 ', 4 "photosensitive layer 5 intermediate layer

Claims (1)

(57) [Claims] Main peak of Bragg angle 2θ for CuKα characteristic X-ray (wavelength 1.541 °) is at least 9.5 degrees ± 0.2 degrees, 9.7 degrees ± 0.2 degrees, 11.7 degrees ± 0.2 degrees, 15.0 degrees ± 0.2 degrees, 23.5 degrees ± 0.2
Photoreceptor containing titanyl phthalocyanine at 24.1 degrees ± 0.2 degrees and 27.3 degrees ± 0.2 degrees.